LECTURE 17 Electrochemistry 2025 OK UPDATE OK OK

LECTURE-17 PROF-ASHFAQ-ANSARI-MDCAT-0345-78-38-112 1
PROF-ASHFAQ-ANSARI-0345-78-38-112
MDCAT-NMDCAT
ELECTROCHEMISTRY
Course Contents
(i) Oxidation number or state
(ii) Explanation of electrolysis
(iii) Electrode potential
(iv) Balancing of redox equation by ion-electron method
(v) Balancing redox equations by oxidation number method
IMPORTANT DEFINITIONS
Electrochemistry is concerned with the conversion of electrical energy into chemical
energy in electrolytic cells as well as the conversion of chemical energy into electrical energy in
galvanic or voltaic cells.
2022-UHS
Q.1 An electrochemical cell is based upon which reaction?
A) Acid-base reaction B) Nuclear reaction
B).. Redox reaction D) Neutralization reaction
2009-UHS
Q.2 In all oxidation reactions, atoms of an element in a chemical species loses electrons and
increases their:
A). Oxidation state B) Electrode
C) Reduction states D) Negative charges
2010-UHS
Q.3. The reaction which is responsible for the production of electricity in the voltaic cell is:
A) Hydrolysis C) Oxidation
B) Redox D) Reduction
Basic Terminology
Current "The flow of electric charge is called current (unit of current is ampere).
Condustor The substance through which electricity can pass is called conductor.
All metals are good conductor of electricity due to the presence of free electrons in them.
Conductor are of two types:
(i) Electronic Conductor The flow of charge in an electronic conductor is due to flow of
electrons. So, no transfer of material takes place. Metals are electronic conductor.
(ii) Electrolytic Conductor The flow of charge in an electrolytic conductor is due to
movement of ions. Electrolytic conductors are called electrolytes. For example aqueous solution of
NaCl, molten NaCl, some salts, acids or bases in water.
MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112
LECTURE-17 PROF-ASHFAQ-ANSARI-MDCAT-FUNGAT-0345-78-38-112 2
Ionization the process in which an ionic compound when fused or dissolved in water split into
negative and positive ions. Examples.
H2 O
PbBr2 (s)  Pb2+ (aq) + 2Br– (aq)
H2 O
NaCl (s)  Na+ (aq) + Cl– (aq)
Heat
NaCl (s)  Na+ (l) + Cl– (l)
Electrolysis “A chemical change caused by the passage of electricity through a molten
compound or through a solution that contains ions."
Electrode "The surface of a cell at which electron transfer reaction takes place."
Electrolyte The substance that give ions in aqueous solution and then solution conduct
electricity. For example aqueous NaCl, aqueous CuSO4 solutions.
Spontaneous Reaction "The reaction, that takes place it self without changing the condition of
reaction is called spontaneous reaction."
Zn + CuSO4  ZnSO4 + Cu
Non-spontaneous Reaction "The reaction, which does not take place or completed without
applying external force is called non-spontaneous reaction."
Electrolysis
2NaCl  2Na + Cl2
Electrolysis
2NaCl + 2H2O  2NaOH + H2 + Cl2
Difference between oxidation and reduction
OXIDATION REDUCTION
 Addition of oxygen atom  Removal of oxygen atom
 Addition of electronegative atom  Removal of electronegative atom
 Removal of hydrogen  Addition of hydrogen
 Removal of electropositive atom  Addition of electropositive atom
 Removal of electron  Addition of electron
 Increase in O.S.  Decrease in O.S.
 It is the- addition of oxygen, loss of  It is the loss of oxygen, addition of
hydrogen or loss of electrons from a hydrogen or addition of electrons
species. from a species.
Example: Example:
Zn (S) + Cu (aq)  Zn (aq) + Cu (s)
+2 +2
Zn (s) + Cu+2 (aq)  Zn+2 (aq) + Cu (s)
 In this reaction, Zn is oxidized as Zn  In this reaction, Cu+2 is reduced as
loses two electrons to form Zn2+ ions. Cu2+ gains two electrons to form Cu.
Oxidation number
The apparent charge which an atom would have in a molecule. It may be zero, positive,
negative and in fraction.

Rules to Find Oxidation Number
(i) The oxidation number of all elements in the free state (uncombined) is zero. This is often
shown as a zero written on the symbol. For example, H2. , Na., Mg..
(ii) The oxidation number of an ion, consisting of a single element, is the same as the charge on
the ion. For example, the oxidation number of K+, Ca2+, Al3+, Br–1 , S2– are + 1, +2, +3, –1,
–2, respectively.The elements of IA , IIA and IIIA are non-variable oxidation(fixed O.S.)
state in redox reactions.
(iii) The oxidation number of hydrogen in all its compounds except metal hydrides is +1. In
metal hydrides it is –1. (Na+H–, Mg2+H(–1)2
2 )
(iv) The oxidation number of oxygen in all its compounds except in peroxides, OF2 and in
super oxides is –2. It is –1 in peroxides and +2 in OF2.
(v) In neutral molecules, the algebraic sum of the oxidation numbers of all the elements is
zero.
(vi) In ions, the algebraic sum of oxidation number equals the charge on the ion.
(vi) In any substance the more electronegative atom has the negative oxidation number.
 Normal oxide: is -2 e.g. ZnO , MgO .
 Peroxide: -1 e.g. H2O2 BaO2
 Super oxide : -1/2 e.g. KO2, RbO2
 Suboxide: -2 , +2 , +1 . e.g. C3O2
 KO2 Oxygen show fractional O.S.
 Oxidation number of C in C6H12O6, C12H22O11 = 0
2022-UHS
Q.1 . In which of the following, oxygen shows fractional oxidation number?
A) OF2 B).. KO2
C) Na2O2 D) Cl2O7
2022-UHS
Q.2. Oxidation number of free magnesium is?
A. 0 C. +2
B. +1 D. +3
Q.3. Oxidation number of an element in free state is:
(A) Zero (B) 1 (C) 2 (D) 3
UHS-2011
Q.4. In SO2–
4 the oxidation number of Sulphur is :
(A) –8 (B) +8 (C) –6 (b) +6
Q.5. The oxidation state of carbon in C12H22O11 :
(A) zero (B) –6 (C) +6 (D) 12

UHS-2012
Q.6. In MgCl2, the oxidation state of 'Cl' is:
(A) zero (B) +2 (C) –2 (D) –1
UHS-2012
Q.7. Oxidation state of 'Mn' in KMnO4, K2MnO4 MnO2 and MnSO4 is in the order:
(A) +7, +6, +2, +4 (B) +6, +7, +2, +4
(C) +7, +6, +4, +2 (D) +4, +6, +7, +2
UHS-2013
Q.8 Which one pair has the same oxidation state of 'Fe'?
(A) FeSO4 and FeCl3 (B) FeCl2 and FeCl3
(C) FeSO4 and FeCl2 (D) Fe2(SO4)3 and FeSO4
Q.9. In the conversion of Br2 to BrO3–1, the oxidation state of Bromine changes from:
(a) 2 to 5 (b) 1 to 5 (c) 0 to -3 (d) 0 to 5
Q.10 Oxidization number of C in CH2Cl2 is:
(a) +2 (b) +4 (c) –4 (d) 0
Q.11.The sum of oxidation number of a neutral compound is always:
(a) Positive (b) Negative (c) zero (d) equal
Q.12. All of the following are oxidation number rules EXCEPT:
A) The oxidation number of any uncombined element is zero
B) The elements of IA, IIA and IIIA groups show non-variable oxidation state in redox
reactions
C) H-atom has +1 oxidation state EXCEPT in metal hydride -1
D) O-atom has -2 oxidation state in OF2
ANSWER EXPLANATION: (D)
It is incorrect statement. In fact, correct statement is as follow:
O-atom has +2 oxidation state in OF2
UHS-2012
Q.13. In MgCl2, the oxidation state of Cl is:
A) Zero C) -2
B) +2 D) -1
In MgCl2, the oxidation state of Cl is –1.
Q.14 In potassium dichromate (K2Cr2O7), what is the oxidation number of chromium:
A) +2 ..C) +6
B) +4 D) +8
–
Q.15. In NO3 the oxidation number of N is:
A) +5 C) +3
C) +2 D) –3

ANSWER EXPLANATION: (A)
–
In NO3 the oxidation number of N is +5.
Oxidizing and Reducing Agent

Oxidizing agent / oxidants
The species which oxidizes others but itself get reduced.
Some facts about oxidizing agents
 Oxidizing agent make other species oxidized.
 Itself get reduced.
 Itself gain electron from others electron acceptor.
 Mostly non metal
 High reduction potential
 Lower positron in electrochemical series.
 Oxidizing power  reduction potential
 Electronegativity
+7 +6
 Elements in their higher oxidation state like KMnO4 , H2SO4
 Some oxides like MgO, CaO, CrO3, H2O2
Reducing agent or reductant
The species which reduces other but get oxidized itself.
Some facts about Reducing agent
 Reducing agent make the other species reduced.
 Itself get oxidized
 Itself looses electron
 Mostly metals
 Low reduction potential
 Higher positron in electrochemical series
1
 Reducing power  Reductional Potential
 Metals of group IA and IIA
 Non metals like C, S, P, H
 HX like HBr, HCl, HI
 Metal hydride like LiH, CaH2
+1
 Molecules OR compounds in which the elements in their lower oxidation states like H
–2 +1
gCl2, H2 S , Cu2O, SnCl2, FeCl2
 Some organic acids HCOOH (COOH)2
Balancing equation by oxidation number (Redox method)
 Write the skeleton of equation
 Identification of elements with Change in oxidation number

Record the oxidation number on symbol of those elements whose oxidation number have
changed.
 Indicating electrons gained or lost.
 Equate the electrons gained or lost by multiplying with suitable digit.
 Balance rest of equation by inspection method.
EXAMPLES
 Skeleton
0
Cu + HNO3  Cu(HNO3)2 + NO2 + H2O
 Assigning O.N to each element
–6 +10 –12 +4–4 +2
0 +1 +5 –2 +2 +5 –2 –2 +1
Cu + H N O3  Cu (N O3 )2 + N O3 + H2O
 Identification of element with change O.N (change per atom)
+2 –2
 +5 +2 +5 +4 +1
Cu + HN O3  Cu (N O3)2 + N O2 + H2 O
 O.N of nitrogen is changed and not changed in this case it is written twice.
Oxidation
0 +5 +2 +4
Cu + HN O3 + HNO3  Cu (NO3)2 + N O2 + H2O
Reduction
– –
Loss of e gain of e
– –
2e 1e
– –
1 × 2e 1e × 2 = (Multiple with digit to equate the total gained and lost)
Cu + HNO3 + HNO3  Cu(NO3)2 + NO2 + H2O
 Make the multiplier coefficient on both sides
0
1Cu + 2HNO3 + HNO3  1Cu(NO3)2 + 2NO2 + 2H2O
 Balance the remaining equation by inspection method
1Cu + 2HNO3 + 2HNO3  1Cu(NO3)2 + 2NO2 + 2H2O
Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O
Balancing equation by ion electron method
STEP 1 Separate the equation into the half reaction one for oxidation and other for reduction.
STEP 2 Balance each half separately by
(i) Balance all the atom except hydrogen and oxygen
(ii) Balance oxygen atom by adding H2O
(iii) Balance hydrogen atom by adding H+ ions
(iv) Balance charges by adding electron
STEP 2 Add the above steps so as to cancelled out electrons

STEP 4 Subtract any duplication
+2
EXAMPLE 1 MnO4–1 + C2O4–2  Mn + CO2
REDUCTION OXIDATION
MnO–1
4  Mn+2 C2O4–2  2CO2
MnO–1
4  Mn+2 + 4H2O C2O4–2  2CO2
MnO–1
4 + 8H
+
 Mn+2 + 4H2O C2O4–2  2CO2
MnO–1 +
4 + 8H +5e
–  Mn+2 + 4H2O C2O4–2  2CO2 + 2e–
2(MnO4–1 + 8H+ +5e–  Mn+2 + 4H2O)

5(C2O–2  2CO2 + 2e– )
4
2 MnO–1
4 + 16H
+
+ 5C2O4–2  2Mn+2 + 8H2O + 10CO2
Q.1 In each of the following equation, which stated reactant has been oxidized.
I. PbO + H2  Pb + H2O II. CO + Ag2O  2Ag + CO2
III) 2Mg + CO2  2MgO + C
A) I (H2) only C) I, II
B) II (CO) only D) I, II, III
In each of the following equation, the stated reactant as underlined in the equation has
been oxidized as shown in the reaction.
 PbO + H2  Pb + H2O (H2 is oxidized to H2O)
 CO + Ag2O  2Ag + CO2 (CO is oxidized to CO2)
 2Mg + CO2  2MgO + C (Mg is oxidized to MgO)
UHS-2013
Q.2.Which one of the following is a redox reaction?
(A) NaCl + AgNO3  NaNO3+AgCl (B) Cl2 + 2e–  2Cl–
(C) 2Na + Cl2  2NaCl (D) Na+ + le–  Na
Q.3. Consider the following balanced equation involving redox reaction.
P + 5HNO3 (conc.)  H3PO4 + 5NO2 + H2O
Oxidation number of P changes from _____ to _______. :
A) 0 to +5 C) +2 to +4
B) +1 to +5 D) +3 to +5
Oxidation number of P changes from 0 to +5.
Po +5HNO3 (conc.)  H3P+5O4 + 5NO2 + H2O
Q.4. The unbalanced equation for the reaction of SO2 with Br2 is shown below:
SO2 + Br2 + H2O  SO4–2 + Br + H+

oxidation state of S changes from SO2 to SO4–2 is:
A) +2 to +4 C) +1 to +2
B) +4 to +6 D) +3 to +4
ANSWER EXPLANATION: (B) In this reaction
SO2 + Br2 + H2O  SO4–2 + Br + H+
oxidation state of S changes from SO2 to SO4–2 is +4 to +6 respectively.
Q.5. Solid potassium halides react with concentrated sulphuric acid, according to the
following equations.
Reaction-1: 2KCl + H2SO4 K2SO4 + 2HCl
Reaction-2: 2KBr + 2H2SO4  K2SO4 + SO2 + Br2 + 2H2O
Reaction-3: 8KI + 5H2SO4  4K2SO4 + H2S + 4I2 + 4H2O
What is the largest change in the oxidation number of sulphur in each of these reactions?
Options Reaction-1 Reaction-2 Reaction-3
A) 0 0 4
B) 0 2 4
C) 0 2 8
D) 0 4 8
ANSWER EXPLANATION: (C)

Solid potassium halides react with concentrated sulphuric acid, according to the following
equations
Options Reaction-1 Reaction-2 Reaction-3
C) 0 2 8
TYPES OF ELECTRODES
ANODE CATHODE
 Through which electrons leave the  Through which electrons enter the
solution. solution
 Positively charged  Negatively charged
 Negative ions migrate  Positive ions migrate
 Oxidation takes place  Reduction takes place
 Oxidation number of species increases  Oxidation number of species decrease
 Direction of movement of elec-trons  Direction of movement of electron
out of cell into the cell
 Show by longer line  Show by smaller line
 In Galvanic cell mass of anode is  In Galvanic cell mass of cathode is
decrease (eaten way) increase
o o
 Eoxi developes on it  ERed developes on it
Q.1. Which of the following statements is incorrect about anode and cathode electrode:
Options Anode Cathode
A) It is shown by longer line It is shown by smaller line

B) In galvanic cell mass of In galvanic cell mass of
anode increases cathode decreases
C) Oxidation takes place on it Reduction takes place on it
D) Eored develops on it Eored develops on it
ANSWER EXPLANATION: (B)

It is incorrect statement. The correct statement is as follow:
Opt. Anod Cathod
B) e
In galvanic cell mass of In galvanic celle mass of
anode decreases cathode increases
ELECTROLYSIS:
Break down of an electrolyte by electricity through an aqueous solution or molten state.
Facts about electrolysis
 It takes place at electrode.
 It occurs in electrolytic cell
 At anode oxidation takes place
 At cathode reduction takes place
 Current enter the electrolyte through cathode and leaves through anode.
 Electrolyte as whole remains neutral during the process of electrolysis as equal no of
charges are neutralized at the electrodes.
Products of electrolysis
 Reduction potential of H2O > Reduction potential of cations of group 1, 2 and 13 of
+ +2 +2 +3
periodic table like Na , Ca , Mg , Al , then reduction of H2O occurs at cathode.
2H2O + 2e–  H2 + 2OH–
H2 is produced at cathode in this case.
 Reduction potential of H2O < Reduction potential of other cation other than group 1, 2 and
13 like Cu+2 , Ag+1 , Au+3 , Zn+2 , Cd+2 since the reduction potential of these cation is more
so these undergo reduction and in this case reduction of H2O does not occur at cathode.
Example
Aqueous
CuSO4
Cu+2 SO4–2
H2O
H2O
Cu+2 more reduction potential > H2O

At Anode
 Oxidation of H2O > Oxidation potential of these anions
F- , NO–3 , SO–2 –2 –2
3 , SO4 , S2O3 , so oxidation of H2O occurs at anode

H2O  O2 + 4H+ + 4e–

and O2 is produced at anode in this case.
 Oxidation potential of H2O < Cl–, Br–, I–, so oxidation of these ions occurs at anode Cl2,
Br2, I2.
Conductivity of electrolytic solution depend upon
Strong Completely ionized 
more ions conductivity increases
 Nature of electrolyte
Weak Incompletely ionized less

ions conductivity decrease
 Size of ions
o Size of ions increases
o Rate of migration of ions is slow
o Conductivity decreases
 Solvation (Hydration)
o Interaction of ions with solvent increase
 Nature of Solvent
o If ionic solvent conductivity increases
o Ions are more soluble in polar solvent
o No of ions increases
o Conductivity increases
 Viscosity of solvent
o Viscosity increases
o Migration decreases
 Concentration of solution
o If concentration of electrolyte in solvent increases
o Inter ionic inter action increases
 Temperature
o Temperature increases
o Ionization increases
o No of ions increases
o Conductivity increases
Electrochemical cell Electrolytic cell

 It is combination of the half cell.  It is a single cell containing the same
Containing the same or different electrode present in the same
electrode in same or different electrolyte
electrolyte.  Anode is positive and cathode is
 Anode is negative cathode is positive angular
 Electrons move from anode to cathode  Electrons enter through cathode and
through external circuit leave through anode
 It converts chemical energy into  It converts electrical energy into
electrical energy chemical energy
 Reaction is spontaneous  Reaction is non spontaneous
 Salt bridge is required  Salt bridge is not required
Commercial Preparation of Caustic Soda (NaOH) NaOH is prepared in the Nelson's cell
(Diaphragm cell) by the electrolysis of brine (aqueous NaCl solution). Caustic soda is
produced by electrolysis of an aq. solution of NaCl between Titanium anode and Hg or
Ag cathode. The process is carried out in Nelson's cell or Castner - Kellner cell or Hg -
cell.
Anode is made of graphite.
Cathode is made of steel line with asbestos.
Electrolyte is aqueous NaCl solution (brine).
H2O
NaCl Na+ + Cl–
At anode: 2Cl–  Cl2 + 2e– (Oxidation)
At cathode: 2H2O  H2 + 2OH– (Reduction)
"Na+ ions are called spectator ions".
Reaction between Cl2 and OH ion is stopped by using asbestos diaphragm.
OH– may produce O2 which may contaminate Cl2.
It is stopped by keeping a node level slightly higher.
It produced 11 % NaOH and 16% NaCl.
After evaporation 50% NaOH is obtained with 1% NaCl as impurity.
Industrial importance of Electrolysis:
(1) Electrolytic cell is used for preparation of sodium metal and Cl2. (Down's cell).
Anode is made of graphite.
Cathode is made of Copper or iron .
The sodium metal is produced in Down's cell commercially by the electrolysis of fused NaCl.
NaCl Na+(aq) + Cl–(aq)
At Anode f Oxidation
2Cl– (aq)  Cl2(g) + 2e–
At Cathode ( Reduction )

2Na+ (aq) + 2e–  2Na (s)
Net Reaction
2Na+ + 2Cl–  2Na + Cl2
Advantages of Down’s cell.
(a) The metallic fog is not produced.
(b) Liquid sodium can easily be collected at 600°C.
(c) Material of the cell is not attacked by the products formed during the electrolysis.
(d) Dry chlorine and 99.9% pure sodium is obtained.
(2) Caustic soda is obtained on industrial scale by the electrolysis of concentrated aqueous
solution of sodium chloride using titanium anode and mercury or steel cathode (Nelson's
cell).
(3) Magnesium and calcium metals are extracted by electrolysis of their fused chlorides.
(4) Aluminium is extracted by electrolyzing fused bauxite (A1203.2H20) in the presence of
fused cryolite (Na3AlF6). Both anode and cathode is made of carbon
(5) Anodized Aluminium is prepared by making it an anode in an electrolytic cell containing
sulphuric acid or chromic acids, which coats a thin layer of oxide on it. The aluminum
oxide layer resists attack by corrosive agents. The freshly anodized aluminum is hydrated
and can absorb dyes.
(6) Electrolytic cell can also be used for the purification of copper where impure copper is
made'the anode and a thin sheet of pure copper is made the cathode. Copper sulphate
solution is used as an electrolyte.
(7) Copper, silver, nickel or chromium plating is done by various types of electrolytic cells.
UHS-2010
Q.1. Metallic conduction involves the relatively free movement of their _____throughout the
metallic lattice:
(A) Atoms (B) Molecules (C) Electrons (D) Ions
Q.2. Nelson's cell and Down's cell are examples of :
(A) electrochemical cell (B) galvanic cell
(C) electrolytic cell (D) none of these
Q.3. For the purification of copper, impure copper is used as _________ :
A) Cathode C) Solution
B) Anode D) Both A and B
For the purification of copper, impure copper is made the anode
Q.4. In the electrolysis of aqueous solution of CuSO4 by using (Cu) electrode, which of
the following is deposited/released on the cathode electrode:
A) Cu C) H2
B) O2 D) S

In the electrolysis of aqueous solution of CuSO4 by using (Cu) electrode, Cu is
deposited/released on the cathode electrode.
Q.5. All of the following are application of electrolysis EXCEPT:
A) Mg and Ca are extracted by the electrolysis of their fused chlorides
B) Al is extracted by the electrolysis of purified bauxite in the presence of cryolite
C) All the metals like Fe, Cu are obtained by electrolysis of their fused minerals
D) Electrolytic cell is used to obtain electrolytic copper from blistered copper
It is incorrect statement. All the metals like Fe, Cu are not obtained by electrolysis of their
fused minerals.
is due to the movement of ions.
Q.6. By electrolysis of brine (30% saturated solution of NaCl) using a diaphragm cell
which of the following is deposited/released at anode:
A) H2(g) C) Cl2(g)..
B) O2(g) D) HCl(g)
Q.7. The electrode through which the electron enter the electrolytic solution is:
A) Anode C) Salt bridge
B) Cathode D) Electrolyte
The electrode through which the electron enter the electrolytic solution is cathode.
Q.8 The extraction of aluminum involves the electrolysis of purified bauxite dissolved in
molten cryolite, (Na3AlF6). This is known as Hall-Broult’s electrolytic process what is
the main purpose of the cryolite?
A) To decrease the melting point of the mixture
B) To provide an additional source of aluminium
C) To increase the electrical conductivity of the melting point
D) To prevent the reoxidation of the aluminium formed at the cathode
The extraction of aluminum involves the electrolysis of purified bauxite dissolved in
molten cryolite, (Na3AlF6). This is known as Hall-Broult’s electrolytic process. The main
purpose of the cryolite is to decrease the melting point of the mixture.
Q.9 Which of the following is correct order of deposition of negative ions on the anode
electrode during electrolysis of aqueous solution of an electrolyte?
A).. I– , Br– , OH– , Cl– , NO3–1 C) OH– , Br– , I– , NO3– , Cl–
B) Br– ,Cl– , OH– , NO3–1 D) NO3–1 , Cl– , Br– , OH– , I–
The Daniell Cell or Galvanic cell or Voltaic cell
A typical galvanic cell is designed to make use of spontaneous redox reaction between zinc and
cupric ion to produce an electric current.
Facts
 The Daniel cell can be conventionally represented Zn / ZnSO4 // CuSO4 / Cu

 In Daniel cell electrons flow from Zinc electrode to copper electrode through external
circuit.
 Metal ions flow from one half cell to another half cell through salt bridge.
 Current flow from copper electrode to zinc electrode that is cathode to anode via external
circuit.
 Daniel is reversible while voltaic cell may be reversible or irreversible.
 A voltaic cell is reversible when it follows the following conditions.
 The emf of external source is more than that of voltaic cell. So that current may flow from
external source into voltaic cell and cell reaction can be reversed.
 If emf of voltaic cell is more than that of external source current flows from voltaic cell
into external source.
At anode Zn(s)  Zn2+ (aq) + 2e– (oxidation)

At cathode Cu (aq) + 2e–  Cu(s) (reduction)
The overall voltaic cell reaction is the sum of these two half cell reactions.
Zn (s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s)
This voltaic cell can be represented as follows:
Zn (s)/Zn2+ (aq) 1M || Cu2+ (aq) 1M/Cu(s) E° =1.1 V
Note that reduction occurs at the copper electrode and oxidation occurs at the zinc
electrode. Sign || shows the presence of salt bridge.
Salt bridge
 It is glass tube having KCl, NH4Cl, NH4NO3 in gelation form.
 The gelation allows ionic movement but prevent any kind of mixing.
 A salt bridge acts as an electrical contact between two half cell.
 It prevent mechanical flow of solution but it provides free
path for migration of ions to maintain an electric current Note
through an electrolyte solution. If salt bridge is removed
 A salt bridge helps in maintaining the charge balance in the emf of cell drops to
two half cell. zero.
Difference between Galvanic cell & Electrolytic.

Galvanic or Voltaic Cell Electrolytic cell
 Spontaneous reaction produces electricity  Non-spontaneous reaction run by
 Cathode  +ve charge electricity
 Anode  –ve charge  Cathode  –ve charge
 Chemical energy converts into electrical  Anode  +ve charge
energy  Electrical energy converts into chemical
 Redox reaction take place in two separate energy
compartments  Redox reaction take place in single
 Need of Salt bridge compartment
 Used for measurement of electrode potential  No need of Salt bridge
 Generate Heat (Exothermic) e.g Ni-Cd cell,  Used for purification or extraction of
fuel cell. metals or electroplating or anodizing
 Consume Heat (Endothermic)
 e.g Nelson's cell, Down's cell
UHS-2013
Q.1. In the figure given below, the electrons flow in external circuit is from:
|Zn Cu
ZnSO4 CuSO4
Solution Solution
Porous Partition
A) Zinc to copper electrode C) Right to left
B) Copper to zinc electrode D) porous partition to zinc electrode
UHS-2008
Q.2.When CuSO4 is electrolyzed in aqueous solution using copper electrodes, then the
substance which deposits at cathode is:
(A) Copper metal (B) Copper ions (C) Hydrogen (D) Oxygen
UHS-2011
Q.3. In electrolytic cell, a salt bridge is used in order to:
(A) Pass the electric current (B) Prevent the flow of ions
(C) Mix solution of two half cells (D) Allow movement of ions b/w two half cells
Q.4. An electrochemical cell stops working after sometime because of:
A) Electrode potential of both the electrodes become equal
B) Electrode potential of both the electrodes become zero
C) Anode electrode is eaten away
D) Solution in half cell becomes neutral
An electrochemical cell stops working after sometime because of anode electrode is eaten
away.
UHS-2015
Q.5. Study the following facts:
Zn + Zn+2 + 2e– Eo = + 0.76V
Cu  Cu+2 + 2e– E° = – 0.34V
Which of the following redox reaction is feasible?
A) Cu + Zn+2  Cu+2 + Zn C) Cu+2 + Zn  Cu + Zn+2
B) Cu+2 + Zn+2  Cu + Zn D) Cu+2 + Zn+2  Cu + Zn+2
The following redox reaction is feasible
Cu+2 + Zn  Cu + Zn+2
Reason: Every top metal can displace lower one in the redox reaction because top metal
has comparatively less reduction potential value as compared to lower one.
UHS-2017
Q.6. Blue colour of CuSO4 solution disappears on the addition of Zn granules. It is because
of:
A) Oxidation Zn+2 C) Reduction of Zn
+2
B) Reduction of Cu D) Oxidation of Cu+2 and reduction Zn+2
Blue colour of CuSO4 solution disappears on the addition of Zn granules. It is because of
reduction of Cu+2.
CuSO4(aq) Cu+2 (aq) + SO4–2 (aq)
Zno (s) + Cu+2 (aq)  Zn+2 + Cuo
Q.7. Which of the following is correct representation of voltaic cell?
+2 +2
A) Zn(s) /Zn (aq) 1M|| Cu (aq) 1M / Cu(s)
B) Cu(s) /Cu (aq) 1M || Zn+2 (aq) 1M / Zn(s)
C) Zn+2 (aq) 1M / Zn(s) || Cu (aq) 1M / Cu(s)
D) Zn(s) /Zn (aq) 1M || Cu(s) / Cu (s)/Cu+2 (aq) 1M
The following is correct representation of voltaic cell:
Zn(s) /Zn+2 (aq) 1M|| Cu+2 (aq) 1M / Cu(s)
Q.8. Mark the incorrect statement about electrolytic cell and galvanic cell:
Options Electrolytic cell Galvanic cell
It is an electrochemical cell in It is an electrochemical cell in
A) which electric current is used which electric-current is produced
to drive a non-spontaneous from spontaneous reaction
reaction
B) Salt bridge is not used in this cell Salt bridge is used in this cell
In this cell anode is shown by In this cell anode is shown by
C) negative sign and cathode is positive sign and cathode is shown
shown by positive sign by negative sign
D) It involves redox reaction It involves redox reaction

It is incorrect statement. Correct statement is as follow:
Opt. Electrolytic cell Galvanic cell
In this cell anode is shown by In this cell anode is shown by
C) positive sign and cathode is negative sign and cathode is shown
shown by negative sign by positive sign
Electrode Potential
It is the tendency of an electrode to accept or to loose electrons.
 When a metal strip is placed in contact with solution of its own ions. The potential
difference is set up between the metal strip and solution due to either two tendencies
Oxidation M  M+ + 1e–
Reduction M+ + 1e–  M
This is called half cell electrode potential.
Facts
 Single electrode potential cannot be measured experimentally
 The potential difference between two single electrode can be measured by using
potentiometer.
o
 Tendency of oxidation is represented by oxidation potential Eoxi
o
 Tendency of reduction is represented by reduction potential ERed
 Both oxidation and reduction potential have same numerical value but opposite signs.

 The electrode potential at standard state condition (T = 298, P = 1atm Concentration = 1
o
molar) is called standard electrode potential E
o
 The absolute value E for an electrode can be determined with respect to standard
o
hydrogen electrode (S.H.E.) whose E is taken to be zero by convention.
Standard hydrogen electrode (S.H.E) and uses of electrodes
Pt, H2 1 atm HCl (1M) H2  2H+ + 2e– 0.0V (Anode)
Pt, H2 1 atm HCl (1M) 2H + 2e–  H2
+
0.0V (Cathode)
 The oxidation potential of zinc is 0.76V and that of Cu is 0.34 volt.
 Electrode potential depends upon :
 The surface in a cell at which oxidation or reduction take place are called electrode.
 The electrodes may or may not involve in redox reactions.
 The electrodes which do not involve in redox reactions are called inert electrode.
 Pt and Graphite is inert electrode while Zn and Pb are reactive electrode.
 Calomel electrode is better reference electrode than that S.H.E.
 Temperature
 Concentration of ions in solution
 Chemical nature of metals and non metals
 No of electrons transferred in half cell reaction
 Consist of Pt-foil (as catalyst), which is coated with finely divided Pt black to increase surface area
 • Pt-foil is suspended in 1 M solution of HCl.
 • Pt-foil act as electrical conductor & facilitates the attainment of equilibrium between H2 gas
&. H+ ions (H2(g) 2H+(aq) + Ze– )
• Potential of S.H.E is arbitrarily = zero
Single Electrode Potential
 Potential difference created between electrode & its ions in solution
 Equilibrium established between electrode atoms & its ions in solution
Q.1. Which of the following acts as inert electrode:
A) Cu C) Zn
B) Cd D) Pt
Pt acts as inert electrode.
Pt is commercially is the most important metal because it is used as an inert electrode in
electrochemistry.
UHS-2018
Q.2. The standard electrode potential of hydrogen is arbitrarily taken at 298K is:
A) 0.00volt C) 10.0volt
B) 0.10volt D) 1.00volt
The standard electrode potential of hydrogen is arbitrarily taken at 298K is 0.00volt.

Standard Electrode Potential
 Potential difference created between electrode
& 1 M solution of its own ion at 25°C (298K) & 1atm.
 Represented by E°
 Standard Electrode Potential can be determined
by comparing it with S.H.E
Electromotive force or emf of cell or cell voltage
Mathematically it is represented as
o o o
Ecell or emf = E(cathode) – ERP (anode)
Reductional potential (RP)
o o
 For cell reaction to occur Ecell should be positive this can happen only if ERP (cathode )
o
> ERP (anode)
o
 Ecell must be positive or spontaneous
 The rate of an electrolytic reaction is directly proportional to emf of the cell.
 The emf of the cell depends on the intensity of the reaction in the cell.
o o
 It causes of flow of current from higher value of E electrode to lower Evalue of electrode.
UHS-2009
Q.1. The emf produced by Galvanic Cell is known as:
(A) Redox Potential (B) Oxidation Potential
(C) Cell Potential.. (D) None of the above.
Measurement of Electrode Potential
In any measurement of electrode potential, the concerned electrode is joined
electrolytically with the standard hydrogen electrode (SHE) and a galvanic cell is established. The
two solutions are separated by a porous partition or a salt bridge containing a concentrated solution
of potassium chloride. The salt bridge is used to provide a highly conducting path between the two
electrolytic solutions. The potential difference is measured by a voltmeter which give the potential
of the electrode, as the potential of SHE is zero. An oxidation or reduction may take place at SHE
depending upon the nature of the electrode which is coupled with it.
Measurement of electrode potential of Zn electrode: v.v.Vimp-MDCAT.

To measure the electrode potential of zinc, a galvanic cell is established between zinc
electrode dipped in 1M solution of its ions and standard hydrogen electrode at 25 °C as shown in
Fig (10.5). Under the standard conditions, the voltmeter reads 0.76 volts and the deflection is in
such a direction as to indicate that zinc has a greater tendency to give off electrons than hydrogen
has. In other words, the half reaction Zn(s)  Zn2+ + 2e– has greater tendency to occur than H2(g)
 2H+ +2e– by 0.76 volts. The standard electrode potential of zinc is, therefore, 0.76 volts. It is
called oxidation potential of Zn and is given the positive sign. The reduction potential Zn-electrode
is -0.76 volt. The electrode reactions will be shown as follows.
At anode Zn(s)  Zn2+(aq) + 2e– (oxidation)

–
At cathode 2H+(aq) + 2e  H2(g) (reduction)
Measurement of electrode potential of Cu electrode:V.V.V.IMP-MDCAT
The electrode potential of copper era also be measured using the same type of galvanic cell
in which copper is an electrode dipped in 1M solution of its ions and connected with SHE Fig
(10.6). Under standard conditions, the voltmeter reads 0.34 volts and the deflection is in such a
direction, as to indicate that hydrogen has a greater tendency to give off electrons than copper has.
In other words, the half reaction H2(g)  2H+ + 2e– has a greater tendency to occur
than Cu(s)  Cu2+ + 2e– by 0.34 volt. So the standard electrode potential of Cu is 0.34 volts. It is
called reduction potential of Cu When the sign is reversed, then the –0.34 V is called oxidation
potential of Cu electrode. The reactions taking place at two electrodes will be shown as follows.
At anode : H (g)  2H+2e–
At cathode : Cu2+ + 2e–  Cu(s)
UHS-2016
Q.1. The diagram shows a galvanic cell. The current will flow from:
Figure. (Electrode potential of copper)

A) Hydrogen electrode to copper electrode
C) Hydrogen electrode to HCl solution
B) Copper electrode to hydrogen electrode
D) CuSO4 solution to hydrogen electrode
The diagram shows a galvanic cell. The current will flow from hydrogen electrode to
copper electrode.
 H2 acts as a anode H2 2H+  + 2e– 
Cu acts as a cathode Cu2+  + 2e– Cu
o
Q.2. The E value of standard copper half-cell is +0.34V, which is measured when it is
connected with SHE i.e. standard hydrogen electrode. In this case the half reaction
taking place at SHE is:
A) 2H+ + 2e–  H2(g) C) 2H– (aq) + 2e–  2H (g)
B) H2 (g) + 2H+ (aq) + 2e– D) H2 (g)  2H(g) + 2e–
o
The E value of standard copper half-cell is + 0.34V, which is measured when it is
connected with SHE i.e. standard hydrogen electrode. In this case oxidation half reaction
takes place at SHE is H2 (g)  2H(aq) + 2e– (oxidation half reaction).
Q.3. Mark the incorrect statement:
A) A porous plate or a slat bridge is not required in lead storage cell
B) Na and K can displace hydrogen from acids but Pt, Pd and Cu cannot
C) Impure Cu can be purified by electrolytic process
D) SHE acts as a anode when connected with Zn
It is incorrect statement. In fact, standard hydrogen electrode (SHE) acts as a cathode
when connected to Zn electrode because Zn is more electropositive than hydrogen.
Q.4. The cell voltage or emf measures the force with which electrons move in the external
circuit and therefore, measures the tendency of the cell reaction to takes place. If Zn /
Zn+2 = 0.76v, Cu+2 / Cu = 0.34V , then the value of Eored is:

A) +1.10 V C) +1.2 V
B) +1.5 V D) +1.4 V
If Zn / Zn+2 0.76v, Cu / Cu 0.34V , then the value of Eored is +1.10V.
+2
Q.5. The potential difference of an electrochemical cell is measured by:

A) Ammeter C) Galvanometer
B) Voltmeter D) Calorimeter
The potential difference of an electrochemical cell is measured by voltmeter.

Electrochemical Sereis
It is the arrangement of various electrodes or elements in the increasing order of their
standard reduction potential or decreasing order of oxidation potential in hydrogen scale.

Applications of Electrochemical Sereis (MCAT)

1 Prediction of the Feasibility of a Chemical reaction when we look at the
electrochemical series R is easy to predict whetehr a particular reaction will take place or not. For

Example, Cu2+ 2+
(aq) can oxidize solid zinc but Zn Cu(aq) cannot oxidize solid copper. Standard
reduction potential values of copper and zinc can explain this.
Cu2+ –  Cu(s) Eocell = +0.34 volt
(aq)+ 2e
Zn(q) + 2e–  Zn(s) E° = – 0.76 volt

Since zinc is being oxidized so the reverse reaction will be considered.
Zn(s)  Zn2+ – E° = +0.76 volt
(aq) + 2e
The overall reaction will thus be:
Cu2+
(aq) + Zn (s)  Cu(S) + Zn2+
(aq) Eocell = +1.1 volt
The overall positive value of the reaction potential suggests that the process is energetically
feasible. If the sum of Eo value of the two half cell reaction is negative then there reaction will not
be feasible.
Cu(S)  Cu2+ – E° = – 0.34 volt
(aq) + 2e
Zn2+ –  Zn(s) E° = – 0.76 volt
(aq) + 2e
(s) 
Cu(aq) + Zn2+ Cu2+ + Zn (s) E° = –1.1 volt
------------------------------------------------------------------------------------------------
Q.1. If Al3 / Al = – 1.66V , Cl2 / Cl = + 1.36V , then the value of Eo cell is:
A) +3.02 V C) +3.1 V
B) +3.0 V D) +2.9 V
If Al / Al = – 1.66V , Cl2 / Cl = + 1.36V then the value of Eo cell is +3.02V. The cell
+3
voltage or emf +3.02V can be calculated as. The cell voltage or emf of the cell is given by:
o o o o
Ecell = Eoxid + Ered (Cl2 + 2e  2Cl– Ered = 1.36V
o o
Ecell = Al/A;+3 + Cl2/Cl (Al+3 + 3e  Al Ered = –1.66V
o
(Al  Al+3 + 3e Eoxi = +1.66V
o
Ecell = 1.66 + +1.66
o
Ecell = + 3.02 V (reaction is feasible)
Q.2. Which of the following reaction is not feasible according to electrochemical series:
A) Zn + H2 SO4 (dil) ZnSO4 + H2 C) F2 + 2KCl  2KF Cl2 ..
B) Cu + H2SO4 (dil) CuSO4 + H2 D) Cl2 + NaBr  2NaCl Br2
Q.3. What is the standard emf of the cell?
Mg (s) / Mg2+ (aq) || Cu2+ / Cu Mg / Mg2+ (aq) = +2.37V Cu2+ / Cu = +0.34V
A) 2.71 V C) 2.53 V
B) 2.04 V D) 1.36 V
o o o o
Ecell = Eoxid + Ered (Cu2+ + 2e  2Cu Ered = + 0.34V

o o
Ecell = Mg/Mg+2 + Cu+2/Cu (Mg  Mg2+ + 3e– Eoxi = +2.37V
o
Ecell = +2.37 + + 0.34
o
Ecell = +2.71V (reaction is feasible)
Q.4. If Cr /Cr = – 0.74V , MnO2 / Mn+2 = + 1.28V then the value of Eo cell is:
+3 o
A) +2.02 V C) +1.5 V
B) +2.01 V D) +2.5 V
o o
Ecell = Eoxid + E o
(Cr+3 + 3e–  Cr
Eored = – 0.74V)
Eocell = Cr / Cr+3 + MnO2 / Mn+2 (Cr  Cr+3 + 3e– Eooxi = + 0.74V)
(MnO2 + 3e–  Mn+2 Eored = + 1.28V)
Eocell = +1.28 + +0.74
Eocell = + 2.02V) reaction is feasible
2. Calculation of the voltage or Electromotive Force (emf) of Cells In a galvanic cell,
the electrode occupying a higher position in the electrochemical series, will act as, anode an4
oxidation takes place on it. Similarly the electrode occupying the lower position in the series will
act, as a cathode and reduction will take place on it. Let us find out a cell potential of Cu – Zn cell.
Zn(s)  Zn2+
(aq) (Oxidation half reaction)
–
(aq) + 2e 
Cu2+ Cu(s) (Reduction half reaction)
(aq) + Zn (s) 

Cu2+ Cu (s) + Zn2+ (aq) (Net cell reaction)
The cell voltage or emf of the cell is given by:
Eocell = Eored + Eored
Eored = 0.76 + 0.34 = 1.10 volts
The cell voltage of emf measures the force with which electrons move in the external
circuit and therefore measures the tendency of the cell reaction to take place.
3) Comparison of Relative Tendency of Metals and Non-metals to get Oxidized or Reduced
The value of the reduction potential of a metal or a non-metal tells us the tendency to lose
electrons and act as a reducing agent. It also gives the information about the tendency of a
species to gain electrons and act as an oxidizing agent. Greater the value of standard
reduction potential of a given species, greater is its tendency to accept electrons to undergo
reduction and hence to act as an oxidizing agent. For example, ions like Au3+, Pt+2, Hg2+,
Ag+, Cu2+ and the non-metal elements like F2, Cl2, Br2 and I2 which lie below the SHE,
have a strong tendency to gain electrons and undergo reduction.
The series tell us that strong oxidizing agents have a large positive value of standard
reduction potential while strong reducing agents have a large negative value.

4) Relative Chemical Reactivity of Metals Greater the value of standard reduction

potential of a metal, smaller is its tendency to lose electrons to change into a positive ion and hence
lower will be its reactivity. For example, metals like Li, Na, K and Rb are highly reactive. Coinage
metals, Cu, Ag and Au are the least reactive because they have positive reduction potentials.
Similarly, metals like Pb, Sn, Ni, Co and Cd which are very close to SHE react very slowly with
steam to liberate hydrogen gas, while the metals like Fe, Cr, Zn, Mn, A1 and Mg which have more
negative reduction potentials react with steam to produce the metallic oxides and hydrogen gas.
(5) Reaction of Metals with Dilute Acids Greater the value of standard reduction potential
of metal, lesser is its tendency to lose electrons to from metal ions and so weaker is its tendency to
displace H2. For example, metals like Au, Pt, and Cu which have sufficiently high positive values
of reduction potentials, do not liberate hydrogen from acids. While metals like Zn, Mg and Ca
which are close to the top of the series and have very low reduction potentials, liberate hydrogen
gas, when they react with acids.
Mg + 2HCl  MgCl2 + H2
Au + HC1  No reaction
Large negative value of reduction potential

Loose electron
Acts as reducing agent
Upper Elements Acts as anode
More reactive metals
Can replace lower metals
Make release of hydrogen gas from acid

Hydroxide of metals are strongly basic
Small negative value of reduction potential

Gains in electron
Acts as oxidizing agent
Lower Elements Acts as cathode
Less reactive metals
Can not replace upper metals
Not release of hydrogen gas from acid

Hydroxide of metals are weakly basic

Strength of oxidizing agents:

Alkaline KMnO4 (+1.71V) ˃ Acidified KMnO4 (+1.51V ) > Acidifeid K2Cr2O7 (+1.33V)
Q.1. All of the following are oxidizing agents EXCEPT:
A) KMnO4 C) CO2
B) K2Cr2O7 D) H2S
Q.2. All of the following are reducing agents EXCEPT:
A) H2S C) CO
B) H2 D) HNO3
HNO3 is oxidizing agent.
Q.3. Mark the incorrect statement about reducing agents and oxidizing agents:
Options Reducing Agents Oxidizing Agents
A) Reducing agents are those Oxidizing agents are those
substances which reduce the others substances which oxidize the
but itself they are oxidized others but itself they are reduced
B) They lose electron/electrons They gain electron/electrons
during redox reaction during redox reaction
C) Their oxidation number increases Their oxidation number decreases
during redox reaction during redox reaction
D) They help in oxidation They help in reduction
ANSWER EXPLANATION: (B) It is incorrect statement.
Option Reducing Agents Oxidizing Agents
They help in reduction They help in oxidation
oxidation Reduction
Nao (g)  Na+ (g) + e– Clo (g) + e–  Cl– (g)
D) R.A O.A
(oxidation number increases from (oxidation number decreases from
0 to 0 to
+1) -1)
Other Metals, Na, K, Zn, Ca, H2, H2S, Non-metals F2, Cl2, Br2, O2,
HF, CO2,
Examples HCl, HBr, HI, CO, FeSO4, HNO3, H2SO4, KMnO4, K2Cr2O7.
(COOH)2, KI.
Note: If the oxidation number of the central atom of a compound is equal to group number then
such substance always acts as an oxidizing agent in redox reaction.
e.g. C+4O2 (IVA), HN+5O3 (VA), H2S+6O4 (VIA).
Feasibility of reaction or cell :
o
 If Ecell > 0 the cell (reaction) is feasible
o
 If Ecell < 0 the cell (reaction) is not feasible
o
 If Ecell = 0 the cell is in equilibrium
Facts About Electrochemical Series
 A metal lower in series is replaced by an above it while one higher in the series is coated
by metal below:
Zn + H2SO4  Zn SO4 + H2
Metals above hydrogen can easily replace hydrogen from acid

Mg + H2SO4  MgSO4 + H2
Oxidation potential of Mg > H2
 Metals lower in the series can not do so as oxidation potential of H2 is higher that of
fallowing metal
C H A P A
| | | | |
Cu Mg Ag Pt Au Cu + H2SO4  No reaction
 Oxides of lower metal (C, H, A, P, A) are easily reduced by H2 or carbon
 Reducing property  Eoxidation potential
 Metals above hydrogen in electrochemical series have positive oxidation potential that is
they act as reducing agent Li is strongest reducing agent due to higher value of oxidation
potential.
 Metals (C H A P A) have high ERP so these are oxidizing agent
Oxidizing power  ERP
F2 > Cl2 > Br2 > I2

Oxidation potential decreases
 Elements with more positive ERP are discharged before the one with less positive ERP.
Discharging tendency increases from Li to F.
1
 In case of anion, discharging order  Value of E
RP
 Reactivity of metal  EOP then Li is more reactive than Mg.
 Reactivity of non metal  ERP reactivity order F2 > Cl2 > Br2 > I2
 Hydroxides of metals higher in series are strongly basic.
And their salt do not undergo hydrolysis. While a hydroxides of metal lower in series are weakly
acidic and their salts undergo hydrolysis.
Industrial importance of electrolysis
. (i) Na is produced in Down's cell commercially by the electrolysis of fused NaCl .
Iron – cathode and graphite – anode .
(ii) Caustic soda is produced by electrolysis of an aq. solution of NaCl .
Nelson cell or Hg-cell
Anode – Ti and cathode mercury or steel
(iii) Mg and Ca metals are extracted by the electrolysis of their fused chlorides.
(iv) Al is extracted by the electrolysis of fused Bauxite (Al2O3.2H2O).
(v) Anodized Al is prepared by making it an anode in an electrolytic cell.
(vi) Cu is made pure in an electrolytic cell.
(vii) Copper, Silver, Nickel or Chromium plating is done by various types of electrolytic
cells.
Q.1. Select the metal which is extracted from bauxite?

A. Al C. Mg
B. Ca D. Cu
UHS-2014
Q.2. Coinage metals Cu, Ag and Au are the least reactive because they have:
A) Negative reduction potential C) Negative oxidation potential
B) Positive reduction potential D) Positive oxidation potential
UHS-2015
Q. 3. Keeping in mind the electrode potential, which one of the following reactions is feasible?
A) Zn+2 + Cu  Cu+2 + Zn C) Ca + CuSO4  CaSO4 + Cu
B) Zn + MgSO4  ZnSO4 + Mg D) Cd + MgSO4  CdSO4 + Mg
UHS-2016
Q.4. Study the following redox reaction:
10Clˉ +16H+ + 2MnO4ˉ  5Cl2 + 2Mn+2 + 8H2O
A) Manganese is oxidized from +7 to +2
B) Chlorine ions are reduced from –1 to zero
C) Chlorine is reduced from zero to –1
D) Manganese is reduced from +7 to +2
UHS-2010
Q.5. In an electrochemical series, standard electrode potentials are arranged on the basis of:
(A) pH scale (B) pOH scale (C) Hydrogen Scale . (D)pKa scale
UHS-2015
Q.7.On the basis of oxidizing power of halogens, which reaction is possible?
(A) I2 + 2Cl–  Cl2 + 2I– (B) Br2 + 2I–  I2 + 2Br –
(C) Cl2 + 2F  F2 + 2Cl– (D) I2 + 2Br–  Br2 + 2I–
UHS-2015
Q.8. Keeping in mind the electrode potential, which one of the,,..., following reactions is
feasible?
(A) Zn2+ + Cu  Cu+2 + Zn (B) Fe + CuSO4  FeSO4 + Cu
(C) Zn + MgSO4  ZnSO4 + Mg (D) Cd + MgSS4  CdSO4 + Mg
Q.9. Which one of the following elements is more electropositive according to
standard reduction potential (Eored) at 298K and 1atm in the electrochemical series?
A) Cu (II) C) Ni (II)
B) Fe (II) D) Cd (II)
By comparing standard reduction potential (Eored) values of elements, it is clear that iron is
more electropositive.
Options Elements Reaction at electrode Eored
A) Cu (II) Cu +2 + 2e Cu +0.34V
B) Fe (II) Fe +2 + 2e Fe -0.44V
C) Ni (II) Ni +2 + 2e  Ni -0.25V
D) Cd (II) Cd +2 + 2e  Cd -0.403V
Smaller is the reduction potential value, greater is the electropositive character of the
metal.
UHS -2009
Q.10. The emf produced by Galvanic Cell is known as:
(A) Redox Potential (B) Oxidation Potential
(C) Cell Potential (D) None of the above
SOME IMP- TABLE:
Differentiate between a primary and a secondary cell.
PRIMARY CELLS SECONDARY CELLS
1 They cannot be recharged 1. They can be recharged
2 They contain electrolyte in an adsorbent or- 2. They usually contain free-flowing liquid
separator. Thus these are called dry cells. electrolyte in larger amount. Thus these 1 may be
called wet cells.
3 They are generally smaller in size 3. They are generally larger in size.
4 They are disposable 4. They require regular maintenance and recharging
5 Examples: 5.Examples:
Alkaline battery, Silver-oxide battery. Lead Accumulator
What is the difference between a cell and a battery
CELL BATTERY
1. It is a single unit that converts chemical energy into 1 A collection of cells is called battery

electrical energy
2. The cell gives a smaller voltage 2 The battery gives a higher voltage.
3. The cell is generally smaller in size 3 The battery is generally larger in size.
4. They are disposable 4 They require regular maintenance and
recharging
5. Examples: Dry cell, 5 Examples: Lead Accumulator, Nickle-
Cadmium battery etc.
Difference between single electrode potential and standard electrode potential
SINGLE ELECTRODE POTENTIAL STANDARD ELECTRODE
POTENTIAL
(1) The potential set up when an electrode is (1) The potential set up when an electrode is
in contact with solution of its own ion is in contact with one molar solution of its
called Single Electrode Potential. own ion at 298 K is called Standard
Electrode potential.
(2) It is measured at any condition of (2) It is measured under standard conditions,
temperature, pressure and concentration, i.e., 25°C, 1 molar solution and 1 atm
• pressure of gas used.
(3) It is denoted by E. (3) It is denoted by E°.
(4) The electrochemical series is not based (4) The electrochemical series is based upon
upon single electrode potential standard electrode potential
Difference between ionization and electrolysis:
IONIZATION ELECTROLYSIS
(1) The process in which ionic compounds (1) The process in which electricity is used
when fused or dissolved in Water split to carry out a non-spontaneous reaction
up into charged particles called ions. is called electrolysis.
(2) Electrodes are not needed (2) Electrodes are required
(3) Electricity is not needed (3) Electricity is required
(4) Since there are no electrodes, therefore, (4) Ions moves towards their respective
ions do not move towards electrodes electrodes
(5) After ionization, ions are not discharged (5) Ions are discharged at electrodes to give
neutral products.
Difference between oxidation number and valency:
Oxidation number Valency
1 It is defined as the number that represents an 1 It is the number of hydrogen atoms, or chlorine
electric charge which an atom has or appears to atoms or double the number of oxygen atoms
have when combined with other atoms. which combine with one atom of the element.
Actually it is the combining capacity of an

element.
2 Oxidation number of an element may be 2 Valency of an element is usually fixed.
different in different compounds
3 Oxidation number of may have a positive, zero 3 Valency of an element docs not have positive
value. or negative sign.
4 Oxidation number of an element may be 4 Valency of an element is always a whole
fractional. number.
5 Example: Oxidation number of Fe in Fe3O4 5 Example:
(magnetic oxide) is +2.67. Valency of Fe in FeCl3 is 3 and in FeCl2 is
Modern Batteries and Fuel Cells

Primary Cell "The voltaic or Galvanic cell which cannot be recharged is called primary cell."
Secondary Cell "The voltaic or Galvanic cell which can be recharged is called secondary." For
example lead storage battery.
GOLDEN POINTS (STRIKING INFORMATIONS) -MDCAT
(1) The conversion of electrical energy into chemical energy in the electrolytic cell and the
conversion of chemical energy into the electrical energy in the galvanic or voltaic cell is
called electrochemistry.
(2) The substance in which electricity can pass is called conductor.
(3) The flow of charge in an electronic conductor is due to the flow of electrons.
(4) The flow of charge in the electrolytic conductor is due to the movement of ions.
(5) Oxidation state of O in OF2 is +2.
(6) Oxidation state of O in peroxides (Na2O2, H2O2) is –1.
1
(7) Oxidation state (fractional O.S.)of O in super oxides (KO2) is – .
2
(8) Oxidation is due to loss of electrons.
(8) Reduction is due to the gain of electrons.
10) Oxidation takes place at the anode.
11) Reduction takes place at the cathode.
(12) An electrochemical cell in which electric current is used to drive a non-spontaneous redox
reaction is called electrolytic cell. For example: Down's cell, Nelson's cell.
13) An electrochemical cell in which electric current is produced as a result of spontaneous
redox reaction is called galvanic cell or voltaic cell. For example: Lead storage battery
dry cell, Daniel cell (Zn - Cu cell).
(14) Lead storage battery has usually six cell, the voltage of each cell is 2 and the total voltage
is 12 V.
(15) 30% H2S04 having density of 1.25 g cm–3 is used as electrolyte in the lead storage battery.
(16) The electrolyte in fuel cell is KOH.
(17) In the NICAD battery, anode is composed of cadmium.
(18) In the silver oxide battery, cathode is Ag2O and anode is made of zinc.

(19) The voltage of alkaline battery is 1.5.
(20) The oxidation and reduction potential of SHE is arbitrarily taken as zero.
(21) In electrolytic cell, cathode is negatively charged and anode is positively charged.
(22) In Galvanic cell, cathode is positively charged and anode is n
“Disproportionation reactions VIMP-MDCAT
A reaction in which a species (molecule, atom or ion)is simultaneously oxidized and reduced,
is called a "disproportionation reaction".
Cold (15°C) state (-1 , +1)
chlorine will react with NaOH (aq) to form hypochlorite and a halide.
15oC
2NaOH(aq) + Cl2(g) —— NaCl(aq) + NaClO(aq) + H2O(aq)
Sod. hypochlorite
The reaction is a disproportionation reaction, because the zero oxidation state of chlorine
atom in Cl2 is converted to -1 in chloride and +1 in hypochlorite
Hot state( -1 , +5 )
6NaOH(aq) + 3Cl2(g) — 5NaCl(aq) + NaC1O3(aq) + 3H2O
1. When Cl2 is passed through NaOH solution cold state (15°C), it - produces
(a)  NaCl + NaClO (b) NaCl + NaC1O3
(c) NaCl + NaC1O2 (d) NaCl + H2O
2. When Cl2 is passed through NaOH solution in hot state (70°C), it produces
(a) NaCl + NaClO (b) NaCl + NaClO3
(c) NaCl + NaClO2 (d)  NaCl + H2O
3. Which statement is correct about the given reaction?
2NaOH + Cl2  NaCl + NaClO + H2O
(a) Cl is oxidized & 0 is reduced
(b) Cl is reduced & 0 is oxidized
(c) neither Cl nor O is reduced or oxidized
(d)  Cl is oxidized as well as reduced
4. Which statement is correct about the given reaction?
70oC
NaClO (aq)  2NaCl + NaClOs
(a) It is an oxidation reaction (b) It is an reduction reaction
(c)  it is disproportionation reaction (d) none of the above
Q.5. All of the following statements about electrochemical series are correct EXCEPT:
A) With the increase of Eored
B) With the increase of Eored electropositive character of a metal decreases oxidizing power
of an element increases
C) Every top metal can displace lower one

D) Silver can displace copper in redox reaction
It is incorrect statement. In fact, Cu can displace in redox reaction because Cu is more
electropositive than silver and it is present at higher level than that of silver in the electrochemical
series
Q.6. Mark the incorrect statement about applications of electrochemical series:
A) It helps to calculate cell voltage
B) It helps to predict the feasibility of redox reaction
C) It predicts relative reducing strength of a substance
D) Eored values shows that F2 is weaker oxidizing agent and Li is stronger reducing agent
It is incorrect statement. Eored value shows that F2 is stronger oxidizing agent and Li is
stronger reducing agent.
Q.7 If strip of Cu-metal is placed in a solution of FeSO4:
A) Cu will be deposited C) Cu and Fe both dissolve
B) Fe is precipitated only D) No reaction takes place
If strip of Cu-metal is placed in a solution of FeSO4, no reaction takes place.
UHS-2015
Q.8. Keeping in mind the electrode potential, which one of the following reactions is
feasible? 2015
A) Zn + Cu  Cu + Zn
+2 +2
C) Ca + CuSO4  CaSO4 + Cu
B) Zn + MgSO4  ZnSO4 + Mg D) Cd + MgSO4  CdSO4 + Mg
The following reaction is feasible as shown in the equation.
Ca + CuSO4  CaSO4 + Cu
Note: Calcium can displace copper from solution as a result of reduction of copper
because calcium is more electropositive than that of copper.

LECTURE 17 Electrochemistry 2025 OK UPDATE OK OK

Uploaded by

Copyright:

Available Formats

LECTURE 17 Electrochemistry 2025 OK UPDATE OK OK

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

LECTURE 17 Electrochemistry 2025 OK UPDATE OK OK

Uploaded by

Copyright:

Available Formats

LECTURE-17 PROF-ASHFAQ-ANSARI-MDCAT-0345-78-38-112 1

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

Oxidizing and Reducing Agent

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

2(MnO4–1 + 8H+ +5e–  Mn+2 + 4H2O)

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

ANSWER EXPLANATION: (C)

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

D) Eored develops on it Eored develops on it

ANSWER EXPLANATION: (B)

Cu+2 more reduction potential > H2O

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

H2O  O2 + 4H+ + 4e–

Weak Incompletely ionized less

Electrochemical cell Electrolytic cell

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

At anode Zn(s)  Zn2+ (aq) + 2e– (oxidation)

Difference between Galvanic cell & Electrolytic.

ANSWER EXPLANATION: (C)

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

Figure. (Electrode potential of copper)

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

Q.5. The potential difference of an electrochemical cell is measured by:

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

Applications of Electrochemical Sereis (MCAT)

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

Zn(q) + 2e–  Zn(s) E° = – 0.76 volt

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

(aq) + Zn (s) 

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

4) Relative Chemical Reactivity of Metals Greater the value of standard reduction

Large negative value of reduction potential

Upper Elements Acts as anode

More reactive metals

Can replace lower metals

Make release of hydrogen gas from acid

Small negative value of reduction potential

Lower Elements Acts as cathode

Less reactive metals

Can not replace upper metals

Not release of hydrogen gas from acid

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

Strength of oxidizing agents:

Zn + H2SO4  Zn SO4 + H2

Metals above hydrogen can easily replace hydrogen from acid

Q.1. Select the metal which is extracted from bauxite?

4 They are disposable 4. They require regular maintenance and recharging

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112

MDCAT PROF-ASHFAQ-ANSARI-MDCAT 0345-7838112