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Engineering Chemistry and Environmental Studies UNIT V

5. Electrochemistry
1) Define Conductor?
Ans:
Conductor:
Substances which allow the flow of electric current through them are called conductor.
Eg: Metals, fused salts, aqueous solutions of Acids, Bases and Salts
2) Define Insulator?
Ans:
Insulator:
Substances which do not allow the flow of electric current through them are called insulator.
Eg: All Non-metals except carbon, wood, rubber, paper.
3) Write about types of conductors?
Ans:
Types of conductors:
There are two types of conductors.
They are
1) Metallic conductors (or) electronic conductors
2) Electrolytic conductors (or) Ionic conductors.
4) Define Metallic conductors:
Ans:
1) Metallic conductors:
a) Conductors which allow flow of electric current through them due to movement of electrons
are called metallic conductors (or) Electronic conductors.
Eg: metals (Al, Cu, Fe), alloys
b) In these conductors conductivity of current by the flow of electrons from cathode to anode.
c) In metallic conductors no chemical reactions occur due to flow of current.
d) They do not involve the transfer of matter.
e) The conductivity decreases with the increase.

5) Define Electrolytic conductors (or) Ionic conductors?


Ans:
2) Electrolytic conductors (or) Ionic conductors:
a) Conductors which allow flow of electric current through them due to movement of ions in the
fused state (or) in solution are called electrolytic conductors (or) Ionic conductors.
Eg: Acids, Bases and Salts.
b) Electrolytic conductors conduct the current by movement of ions towards oppositely charged
electrodes.
c) In these conductors chemical reactions take place due to flow of current.
d) In these conductors transfer of matter occur.
e) The conductivity increases with the increase of temperature.
6) Write Differences between metallic conductors and electrolytic conductors?
Ans:
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

Metallic Conductors
a) Conductors which allow flow of electric
current through them due to movement of
electrons are called metallic conductors (or)
Electronic conductors.
Eg: metals (Al, Cu, Fe), alloys

Electrolytic conductors
a) Conductors which allow flow of electric
current through them due to movement of ions
in the fused state (or) in solution are called
electrolytic conductors (or) Ionic conductors.
Eg: Acids, Bases and Salts.

b) In these conductors conductivity of current


b) Electrolytic conductors conduct the current
by the flow of electrons from cathode to anode. by movement of ions towards oppositely
charged electrodes.
c) In metallic conductors no chemical reactions c) In these conductors chemical reactions take
occur due to flow of current.
place due to flow of current.
d) They do not involve the transfer of matter.

d) In these conductors transfer of matter occur.

e) The conductivity decreases with the


increase.

e) The conductivity increases with the increase


of temperature.

7) Define Non electrodes?


Ans:
Non electrodes:
The substances which do not permit flow of current in the molten state or in aqueous solution are
called non-electrodes.
Eg: sugar, urea, glucose, alchol.
8) How many Types of electrolytes?
Ans:
Types of electrolytes:
Based on extent of ionization, the electrolytes are divided into two types.
They are
(a) strong electrolytes
(b) Weak electrolytes
(a) Strong electrolytes:
The electrolytes which ionize completely even at moderate concentrations are called strong
electrolytes.
The conductivity of strong electrolytes is high due to containing of more ions.
Eg:
Strong acids: HCl, H2SO4
Strong Bases: NaOH, KOH
Salts NaCl, KNO3
(b) Weak electrolytes:
The electrolytes which ionize partially at moderate concentration and having low conductivity
are called as weak electrolytes.
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

Eg:

Weak Acids: CH3COOH


Weak Bases: NH4OH
Salts : AgCl

9) Write about Arrhenius theory of electrolytic dissociation?


Ans:
Arrhenius theory of electrolytic dissociation:
This theory was proposed by Arrhenius in 1887 to explain the behavior of electrolytes.
Postulates:
1. Electrolytes in solution (or) in molten state split into +ve and ve ions. This process is
called ionization (or) electrolytic dissociation.
2. +ve charged ions are called cataions.
-ve charged ions are called anions.
-ve charged ions are called anions.
3. The total charge of cations is equal to the total negative charge of anions. So electrolyte
is neutral.
4. The process of ionization is reversible. The ions and undissociated molecules are in
dynamic equilibrium.
AgNO3

Ag + N O 3
+

Undissociated
ions
Molecule
5. When electricity is passed through the electrolyte, cations moves towards cathode and
anions move towards anode
6. The ions discharge at cathode and anode.
No . of Molecules dissociated into ions
7. Degree of Ionization () =
Total No. of molecules
8. The properties an electrolyte in solution are the properties of ions.
10) Write about Electrolysis with figure?
Ans:
Electrolysis:
Electro = EMF and lysis = decomposition
The process of decomposition of an electrolyte by the passage of electricity is called electrolysis.
In this process electrical energy converted into chemical energy.
The vessel in which electrolysis is carried out is known as electrolytic cell.
The electrolyte is taken in the cell in the form of solution or in molten state.
Two metal plates are placed in electrolyte, which act as electrodes.
The electrodes are connected with copper wire to the two terminals of a battery.
When electricity is passed through the electrolyte the ions towards oppositely charged electrodes.
Chemical reactions occur at the electrodes and products are formed.
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

MA M+n + A-n
M+n + neM (Reduction at cathode)
-n
A
A + ne- (oxidation at anode)
Electrolysis of fused Sodium Chloride (NaCl):
Fused NaCl is taken as an electrolyte in an electrolytic cell.
Two platinum rods are dipped in it, act as electrodes.
They are connected to the two terminals of a battery.
The electrode connected to the +ve terminal is called anode and the electrode connected to the
ve terminal is called cathode.
When electricity is passed through the electrolyte, the Na+ ions move towards cathode, get
discharged forming Na atoms.
The Na atoms deposited on the cathode.
Similarly Cl- ions move towards anode, get discharged forming Cl atoms.
Two Cl atoms combine and liberates Cl2 gas
Reactions in the cell
NaCl
Na+ + ClNa+ + eCl-Cl + e
2Cl

Na (at cathode)
(at anode)
Cl2 (at anode)

Faradays laws of electrolysis:


11) Define Faradays first laws of electrolysis:
Ans:
Faradays first laws of electrolysis:
The mass of a substance deposited at an electrode is directly proportional to the quantity of
electricity passing through the electrolyte.
This can be expressed mathematically as
mQ
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

m Ct But Q = Ct
m eCt
Where m = mass of substance deposited
Q = Quantity of electricity in coulombs = ampere/second
t = time in seconds
e = electro chemical equivalent
c = current in amperes.
E
ct
m = 96500
Where E = Chemical equivalent.
Electro chemical equivalent (e):
The mass of an element deposited at an electrode by passing one coloumb of electricity is called
electro chemical equivalent.
m
m = eQ (or) e = Q (or) e =

m
Ct

If c =1 amp t =1 sec i.e., e = w.


12) Define Chemical equivalent (E)?
Ans:
Chemical equivalent (E):
The mass of a substance deposited at an electrode y the passage of one faraday of current during
the electrolysis is called chemical equivalent.
The chemical equivalent of an element is ratio of atomic weight to the valency.
Atomic weight
E=
Valency
The relation between chemical equivalent (E) and electro chemical equivalent (e) is
E
e = F (or)
E = e.F
Where F = faraday = 96500 coulombs.
13) Define Faradays second laws of electrolysis?
Ans;
Faradays second laws of electrolysis:
When the same quantity of electricity is passed through different electrolytes, the amount of
various substances deposited at an electrodes are directly proportional to their chemical
equivalents.
This can be expressed mathematically as
m E (or)
m
E = constant (or)
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

m1 m2
=
E 1 E2
Where m1 = mass of first element
m2 = mass of second element
E1 = chemical equivalent of first element
E2 = chemical equivalent of second element
Explanation:
If the same quantity of current passed through three electrolytes cells connected in series,
containing dilute H2SO4, CuSO4, and AgNO3 solutions then the masses of H2, Cu and Ag
deposited at the cathode will be in the ratio of their chemical equivalents.
M H : M Cu : M Ag=E H : E Cu : E Ag
2

= 1: 31.75: 108

14) Define Faraday (F):


Ans:
Faraday (F):
The quantity of electricity in coulombs required to deposit one gm of a substance is called
Faraday (or)
Charge of one mole electrons N e- = 6.023 10-23 1.6 10-19
1 Faraday = 96500 coulombs.
15) Write about Galvanic cell?
Ans:
Galvanic cell:
A cell in which electricity generates due to spontaneous cell.
In Galvanic cells chemical energy is converted into electrical energy. Hence these are called
electrochemical cells.
Construction:
A Galvanic cell consists of two half cell.
One half cell consists of a Zinc electrode dipped in ZnSO4 solution.
The other half cell consists of a copper electrode dipped in CuSO4 solution.
The two half cells are connected by a salt bridge.
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

The salt bridge is a U shaped tube containing agar agar gel saturated with an electrolyte KCl
or KNO3 or NH4NO3.
Working of the cell:
1. Whenever Zn and Cu electrodes are connected with a copper wire through a voltmeter, an
oxidation takes place at Zn half-cell and reduction takes place at Cu half-cell.
2. Zn undergoes oxidation, hence Zn electrode is anode. It is indicated ve sign.
Zn
Zn+2 + 2e- (oxidation at anode)
3. Cu electrode undergoes reduction, hence Cu electrode is cathode. It is indicated + ve
sign.
Cu+2 + 2eCu (Reduction at anode)
4. The voltmeter measures the emf of the cell.
5. Salt bridge prevents the accumulation of charges at the electrodes and proceed the
reactions spontaneously.
Cell is represented as Zn/Zn+2(1m)//Cu+2(1m)/Cu

16) Define Salt Bridge and write their uses?


Ans:
Salt Bridge:
The salt bridge is a U shaped tube containing agar agar gel saturated with an electrolyte KCl
or KNO3 or NH4NO3
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

It performs the following function


a)
b)
c)
d)

It allows flow of current by completing the circuit.


It prevents accumulation of charges around the electrodes
It maintains the electrical neutrality of the solution.
It prevents the physical mixing of solutions in the two half cells and allows the flow of
ions.

17) Write the Differences between electrolytic cell and Galvanic Cell:
Electrolytic cell
1). Chemical reaction takes place by the

Galvanic Cell
1). Electricity is generated due to the chemical

passage of electricity is called electrolytic cell.


2). It requires a source of external energy.
3). In this cell, anode had +ve sign and cathode

reactions is called Galvanic cell.


2). It is a source of energy.
3). In this cell, anode had ve sign and cathode

has -ve sign.


4). Current flows from anode to cathode.
5). Flow of electrons takes place from cathode

has +ve sign.


4). Current flows from cathode to anode.
5). Flow of electrons takes place from anode to

to anode.
6). A salt bridge is not required.

cathode.
6). A salt bridge is required.

18) Define Electrolytic potential (E)?


Ans:
Electrolytic potential (E):
Potential difference at the surface of separation of metal and metal ions phases is called electrode
potential (or)
The tendency of an electrode to lose or gain electrons when it is contact with its own ions in
solution is called electrode potential.
19) Define Reduction potential?
Ans:
Reduction potential:
The tendency of an electrode to gain electrons when it is in contact with its own solution is called
reduction potential.
M+n + ne-

20) Define Oxidation potential?


Ans:
Oxidation potential:
The tendency of an electrolyte to lose electrons when it is in contact with its own solution is
called oxidation potential.
M
M+n + neOxidation potential = - reduction potential.
21) Define Standard electrode potential (SEP)?
Ans:
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

Standard electrode potential (SEP):


The potential of electrode at 250 c with 1M concentration of electrolyte is called standard
electrode potential.
It is denoted by E0
Representation of electrodes:
According to IUPAC
a) Metal electrodes:
M+n/M
Zn+2/Zn : Zn+2 + 2eCu+2/Cu : Cu+2 + 2ePt, 2H+/H2 ; 2H+ + 2e-

Zn
Cu
H2

b) Non Metal electrodes:


Pt, Cl2/ClPt, Br2/BrPt, F2/F22) Write about Normal Hydrogen Electrode (or) Standard Hydrogen Electrode (NHE or
SHE)?
Ans:
Normal Hydrogen Electrode (or) Standard Hydrogen Electrode (NHE or SHE):
NHE or SHE contains 1M HCl in a vessel Pt plate is partially dipped in a solution.
Pt plate acts as conductor H2 gas at 1 atm pressure bubbled into the solution at 250 c.
The potential of NHE or SHE is Zero.
NHE (or) SHE represented as Pt, H2 (1 atm)/H+

EMF of the cell:


EMF of the cell can be measured directly with voltmeter.
Ecell = Oxidation potential of anode + Reduction potential of cathode
= Ecathode - Eanode
Prepared by V Naga Surendra Reddy
Lecturer in chemistry

Electrochemistry

Engineering Chemistry and Environmental Studies UNIT V

= Eright ELeft
23) Define Electro Chemical series and write about the significance?
Ans:
Electro Chemical series:
The arrangement of electrodes in the increasing order of their standard reduction potentials is
called Electro Chemical series.
In this series the top most electrode is Li and the bottom electrode is fluorine.
Significance of Electro Chemical Series:
1) The metal which is higher in electro chemical series acts as reducing agent (or) anode and
undergoes corrosion first.
2) Metals above hydrogen are called active metals, which candisplace hydrogen from dilute
acids and water
Eg: Zn + 2HCl
ZnCl2 + H2
3) The metals below Hydrogen are less reactive.
They do not liberate H2 from dilute acids and water.
4) The metal with higher negative potential displaces a metal with lower negative potential
or positive potential from the salt solution of the metal.
Eg:Zn + CdSO
ZnSO + Cd
4

(aq)
(aq)
5) The reactivity (or) reducing character decreases from top to bottom
Li is strongest reducing agent.
F is strongest oxidizing agent.
Series:
Li+/Li
K+/K
Ca+2/Ca
Na+/Na
Zn+2/Zn
Fe+2/Fe
Cd+2/Cd
CO+2/CO
Ni+2/Ni
Sn+2/Sn
Pb+2/Pb
H+/H2
Cu+2/Cu
O2/OHI2/IAg2/AgBr2/BrCl2/Cl-

- Ve Values

0 (Zero)

+ Ve Values

F2/FPrepared by V Naga Surendra Reddy


Lecturer in chemistry

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Electrochemistry