Notes Chem New

UNIT-3
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 nonspontaneous chemical transformations.
Electrochemical Cells OR Galvanic Cells OR voltaic cell
A galvanic cell is a device that converts the chemical energy of a spontaneous redox
reaction into electrical energy.
Uses:
1. 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.
2. Electrochemical cells are extensively used for determining the pH of solutions, solubility
product, equilibrium constant and other thermodynamic properties and for
potentiometric titrations
Example of galvanic cell :Daniel cell

1. Reaction: Zn(s) + Cu2+ (aq) Zn
2+ (aq) + Cu(s)
2. Electrical
potential
2+
to
2+
concentration of Zn and Cu
1.1
when
ions is unity).
3. In a galvanic cell, the half-cell in which oxidation

takes place is
called anode
and it has a
negative potential with respect to the solution.

4. The other half-cell in which reduction takes place
is called cathode and it has a positive potential
with respect to the solution.
5. These two portions of the cell are also called half-
cells or redox couples

(i) Cu2+ + 2e - Cu(s) (reduction half reaction)
(ii) Zn(s) Zn2+ + 2e (oxidation half reaction)
The net reaction is the sum of two half cell reactions.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
6. Electrons flow from anode to cathode in the external
circuit.
7. Inner circuit is completed by the flow of ions through
the salt bridge.Charge carriers in Inner circuit - ions
and in the external circuit- electrons
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Construction of Galvanic cell:

1. Each half cell consists of a metallic electrode dipped into an electrolyte.It is called
electrode
2. The two half-cells are connected by a metallic wire through a voltmeter and a switch
externally.
3. The electrolytes of the two half-cells are connected internally through a salt bridge
4. Sometimes, both the electrodes dip in the same electrolyte solution and in such cases
we dont require a salt bridge.
Function of Salt Bridge:

Salt bridge (inverted U tube contains an inert electrolytic solution -KCl, KNO3,
NH4NO3)
1. To maintain electrical neutrality of the solution in the two half cell.

2. To complete the electrical circuit by allowing the ions to flow from one
solution to the other with out mixing of the two solutions.
Representation of Galvanic cell:
----------------------------------------------------------------------------Left
Salt Bridge
Right
Anode
Cathode
Oxidation
Reduction
Loss of electrons
Gaining of electrons
Negative
Positive
M (S) | Mn+ (conc.) | | Mn+ (conc.) | M(S)

Q1.
Depict the galvanic cell in which the reaction

Zn(s)+2Ag+(aq)
. Zn2+(aq)+2Ag(s) takes place. Further show:
(i) Which of the electrode is negatively charged?

(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.
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(1) Zn is being oxidised , therefore it acts as anode , hence it is negatively charged .
Ans:
+2
(2) Zn and Ag
(3) Two half cell reactions are
Zn(s)
Zn+2 (aq) + 2e
2Ag+ (Aq) + 2e
Ag(s)
Electrode potential(E):
between the
potential.
electrode
and
The
the
potential difference developed

electrolyte is called electrode
M+n + ne M(s) EM+n/M(S) for metallic electrode

X2 + ne 2X- EX2/
X-
for non-metal electrode
Standard electrode potential(EO): The electrode potential of a

metal electrode as determined with respective to a standard or
normal hydrogen electrode when the concentrations of all the species
involved is unity.
NOTES :
According
to
IUPAC
rules
Reduction
potentials
is
taken
Standard electrode potential(E )

O
Oxidation potential and reduction potent numerical value is

equal but algebraic sign is different
E0 value does not change with react reaction quotient changes

with change in concentration and temperature
Electromotive force (emf) : The potential difference between the two electrodes of a
galvanic cell is called the cell potential when no current is drawn through the cell.
Cell Potential:
The potential difference between the two electrodes of a galvanic cell is called the cell
potential (Or) the difference between the electrode potentials (reduction potential) of
the cathode and anode.
It is measured in volts.
cell
=E
right
Eo cell = Eo (cathode) Eo (anode)

left
Question: Write the half cell reactions and depict the cell for the cell reaction:
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Cu(s) + 2Ag+(aq) Cu2+(aq) + 2 Ag(s)
Half-cell reactions:
Cathode (reduction): 2Ag+ (aq) + 2e 2Ag(s)
Anode (oxidation): Cu(s) Cu2+ (aq) + 2e
Cu(s) |Cu2+ (aq) ||Ag+ (aq) |Ag(s)
Ecell = Eright Eleft = E (Ag+/Ag) E (Cu2+/Cu)
Measurement of Electrode Potential:
The potential of individual half-cell cannot be measured.
We can measure only the difference between the two half-cell potentials that gives the
emf of the cell.
If we arbitrarily choose the potential of one electrode (half- cell) then, that of the other
can be determined with respect to this.
For this purpose we use, a half-cell called standard hydrogen electrode, represented
by Pt(s)H2(g)/H+(aq). It is assigned a zero potential at all temperatures corresponding
to the reaction H+ (aq) + e H2 (g)
Construction of SHE / NHE:
The standard hydrogen electrode consists of a platinum electrode

coated with platinum black.
The electrode is dipped in an acidic solution and pure hydrogen gas

is bubbled through it.
The concentration of both the reduced and oxidised forms of hydrogen

is maintained at unity. (This implies that the pressure hydrogen gas is one bar
and the concentration of hydrogen ion in the solution is one molar.)
Measurement of electrode potential of Zn2+ / Zn

Electrode:
Construct a cell At 298 K and find the emf of the cell,
Standard hydrogen electrode | | Zn2+ / Zn is constructed by taking standard

hydrogen electrode as anode and Zn2+ / Zn as cathode, gives the reduction
potential of this half-cell.
If the concentrations of the oxidised and the reduced forms of Zn2+ / Zn, the species
in the right hand half-cell are unity, then the cell potential is equal to standard
electrode potential,
of the given half-cell.
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As
for standard hydrogen electrode is zero.
The measured emf of the cell: Pt(s) | H2 (g, 1 bar) | H+ (aq, 1 M) | | Zn2+ (aq, 1M) | Zn
is -0.76V
Measurement of electrode potential of Cu2+ / Cu

Electrode:
SHE is connected at the left (anode) and Cu2+/ Cu electrode at the right (cathode) gives
the reduction potential of this half-cell.
If the concentrations of the oxidized and the reduced forms of Cu2+ / Cu the species in
the right hand half-cell are unity, then the cell potential is equal to standard electrode
potential
of the given half-cell.
As
for standard hydrogen electrode is zero.
The measured emf of the cell: Pt(s) | H2 (g, 1 bar) | H+ (aq, 1 M) | |Cu2+ (aq, 1 M) | Cu
is
0.34 V
Different types of electrodes:

Sometimes metals like platinum or gold are used as inert electrodes. They do not
participate in the
reaction but provide their surface for oxidation or reduction
reactions and for the conduction of e electrons.
For example, Pt is used in the following half-cells:
Hydrogen electrode: Pt(s)| H2 (g) | H+ (aq) With half-cell reaction
H+ (aq) + e H2 (g)
Bromine electrode: Pt(s) | Br2 (aq) | Br(aq) With half-cell reaction:
Br2 (aq) + e Br(aq)
Electrochemical Series:
The arrangement of elements in order of increasing reduction potential values is known
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as electrochemical series(highest negative EO value placed at the top and highest

positive E O value is placed at the bottom)
Applications of electrochemical series:

1. Relative strengths of oxidizing and reducing agents:
Substances which have lower reduction potential (- ve E ) are stronger reducing

agents (at the bottom of the series) eg. Li is the strongest reducing agent. (Reacts by
lose of electrons-have least tendency to get reduced)
Substances which have higher reduction potential (+ve E ) are stronger oxidizing
agents (at the top of the series) eg. F2 is the strongest oxidizing agent. (Reacts by
gaining of electrons-have maximum tendency to get reduced).
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.
Q.
Ans:
Ag<Hg,Cr,Mg<,K
Potassium is the strongest reducing agent while silver is the weakest reducing
agent. Higher the oxidation potential, more easily it is oxidized, hence Greater is
the reducing power.
2.Comparison of reactivities of metals:

A metal having smaller reduction potential (lower position) can displace metals having
larger reduction potential from the solution of their salts.
Q.
Arrange the following metals in the order in which they

displace each other from the solution of their salts. Al, Cu,
Fe, Mg and Zn.(PAGE NO:
Ans:
Any metal will be able to displace any other metal which is placed below it in the
electrochemical series.
Mg will displace all metals
Zn will displace all metals except Mg
Fe will displace Cu and Au
Cu will displace only Au
Au will displace none.
Q.
Knowing that :
Cu2+ (aq) + 2 e Cu (s)
E = + 0.34 V
2 Ag+ (aq) + 2 e 2 Ag (s) E = + 0.80 V
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Reason out whether, 1 M AgNO3 solution can be stored in Copper Vessel or
1 M CuSO4 solution in Silver Vessel.
3. Calculation of the E.M.F.of the cell:

Steps:
1. Write the two half cell reaction
2. Equalize the number of electrons in the two equations by multiplying the
equation by a suitable number. (E0 are not multiplied)
3. Use the formula :
4. Predicting feasibility/ spontaneity of a redox reaction:
1. In general a redox reaction is feasible only if the species which has higher
reduction potential is reduced .i.e. accepts the electron and the species which has
lower reduction potential is oxidized. i.e. loses the electron.
2. The emf of the cell based upon the given redox reaction is calculated.
3. If emf comes out to be negative the direction as given, cannot take place but the
reverse reaction may take place spontaneously.
Using the standard electrode potentials given in Table, predict if the
Reaction between the following is feasible:
EOFe+3/Fe+2
0.77v
EOI2/I0.54v
EOAg+/Ag
0.80v
EOCu+2/Cu
0.34v
EO Br2/Br1.o9v
(i) Fe3+(aq) and I(aq)

(ii) Ag+ (aq) and Cu(s)
(iii) Fe3+ (aq) and Br (aq)
(iv) Ag(s) and Fe 3+ (aq)
(v) Br2 (aq) and Fe2+ (aq).
5. Predicting whether a metal can liberate hydrogen from acid or not:

In order that a metal M may react with an acid to give H2 gas, the following reactions should
take place:
M(s) + H+-----M+ + H2
M--- M+ +e-(oxidation)
H+ +e---- H2 (reduction)
The metal should have the tendency to lose electrons (negative reduction potential-undergo
oxidation), with respect to hydrogen.
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Note: Cu does not dissolve in HCl. In Nitric acid it is oxidized by nitrate ion and not by
hydrogen ion.
1
How would you determine the standard electrode potential of the system Mg2+/Mg?
Can you store copper sulphate solutions in a zinc pot?
Consult the table of standard electrode potentials and suggest three substances that can oxidise
ferrous ions under suitable conditions. EOFe+2/Fe+3 = -0.77V
Arrange the following metals in the order in which they displace each other from the solution of their
salts. Al, Cu, Fe, Mg and Zn.
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.
Zn(s)+2Ag+(aq)
. Zn2+(aq)+2Ag(s) takes place. Further show:
(i) Which of the electrode is negatively charged?

(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.
Knowing that :
Cu2+ (aq) + 2 e Cu (s)
E = + 0.34 V
2 Ag+ (aq) + 2 e 2 Ag (s) E = + 0.80 V

Reason out whether, 1 M AgNO 3 solution can be stored in Copper Vessel or 1 M CuSO 4
solution in Silver Vessel.
8
Can a nickel spatula be used to stir a solution of Copper Sulphate ? Justify your answer.
(ENi+/Ni = 0.25 V
ECu+/Cu = 0.34 V)
9.
11
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13
Reversibility of cell by applying external opposite potential to Galvanic cell:
If an external opposite potential is applied and increased slowly, we find that the reaction
continues to take place
When the opposing voltage reaches the value 1.1 V then, the reaction stops altogether and
no current flows through the cell.
Further increase in the external potential again starts the reaction but in the opposite
direction. It now functions as an electrolytic cell, a device for using electrical energy to
carry non-spontaneous chemical reactions.
Consider the electrochemical cell :

Zn (s) / Zn2+ (aq) // Cu2+ (aq) / Cu. It has an electrical potential of 1.1 V when
concentration of Zn2+ and Cu2+ ions is unity.
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State the direction of flow of electrones and also specify if Zinc and Copper are
deposited or dissolved at their respective electrodes. When :
(a)
an external opposite potential of 0.8 V is applied.
(b)
an external opposite potential of 1.1 V is applied
NERNST EQUATION
The standard electrode potentials (given in table) are measured when the
concentration of all the species involved in the electrode reaction is unity and
temperature is 298K.
This need not be always true. Nernst showed that the electrode potential depends on
the concentration of the electrolyte solution and temperature .
NERNST EQUATION FOR SINGLE ELECTRODE
For the electrode reaction:

M n+ (aq) + ne M(s)
The electrode potential at any concentration measured with respect to standard

hydrogen electrode can be: represented by since [M(s)] =1
(R is gas constant (8.314 JK1 mol1) F is Faraday constant (96,487 C mol1), T is

temperature in kelvin )and [Mn+] is the concentration of the species, Mn+.
1.
a) For the reaction Zn2+ (aq) +2e----- Zn(s) Write the Nernst equation
b) For the reaction Cu+2 + 2e Cu write the single electrode potential
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NERNST EQUATION FOR CELL

In Daniell cell, the electrode potential for any given concentration of Cu 2+and Zn2+ ions,
Zn(s)+2Cu+2(aq)
Zn2+(aq)+2Cu(s)
we write For cathode:
Converting the natural logarithm to the base 10 and substituting R, F and T=298K
We should use the same number of electrons (n) for both the electrodes.
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2+
2+
It can be seen that E (cell) depends on the concentration of both Cu and Zn ions.
It increases with increase in the concentration of Cu 2+ions and decrease in the concentration
of Zn2+ions.
1.
Write the Nernst equation for following cell
Solution
2.
solution
Equilibrium Constant from Nernst Equation:

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If the circuit in Daniell cell is closed then we note that the reaction:
Zn(s) + Cu2+ (aq) ----Zn2+ (aq) + Cu(s) takes place and as time passes
the concentration of Zn2+ keeps on increasing while the concentration of Cu 2+ keeps on

decreasing.
The voltage of the cell as read on the voltmeter keeps on decreasing. After some time,
there is no change in the concentration of Cu2+ and Zn2+ ions and at the same time,
voltmeter gives zero reading. (it means Ecell at this concentration zero)
This indicates that equilibrium has been attained. In this situation the Nernst equation
may be written as
1.
Electrochemical Cell and Gibbs Energy of the Reaction:
Gibbs Energy of the Reaction: It is the measure of the maximum

useful electrical work that can be obtained from a chemical reaction.
As reversible work is done by a galvanic cell it results in decrease in its Gibbs
energy.
Electrical work done = Decrease in Gibbs energy
Electrical work done in one second = Electrical potential X Total charge
passed.
If the emf of the cell is E and nF is the amount of charge passed and rG is
the Gibbs energy of the reaction, then
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E (cell) is an intensive parameter (independent on the amount of substance)

but rG is an extensive thermodynamic property and the value depends on n.
For the reaction Zn(s) + Cu2+ (aq) --Zn2+ (aq) + Cu(s)
rG = -2FE (cell)
But when we write the reaction 2 Zn (s) + 2Cu2+ (aq) ---2 Zn2+ (aq) +2Cu(s)
But when we write the reaction
2 Zn (s) + 2Cu2+ (aq) ---2 Zn2+ (aq) +2Cu(s)
If the concentration of all the reacting species is unity, then E (cell) =

Thus, from
reaction.
rG = 4FE (cell)
and we have
we can obtain the thermodynamic quantity, rG, standard Gibbs energy of the
From the latter we can calculate equilibrium constant by the equation:

rG = RT ln K.
rG = 2.303 RT log Kc
1.
a) Calculate the emf of the cell in which the following reaction takes place:
Ni(s) + 2Ag+ (0.002 M) Ni 2+ (0.160 M) + 2Ag(s)
Given that E (cell) = 1.05 V
b) The cell in which the following reaction occurs:
at 298 K.
Calculate the standard Gibbs energy and the equilibrium constant of the cell
reaction.
ELECTRO CHEMISTRY
CLASS:12( CBSE)
ASSIGNMENT :
TOPIC: GALVANIC CELL
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Cu(s)+2Ag+(aq)
Cu2+(aq)+2Ag(s) takes place.
Further show:
1. Write Individual reaction at each electrode
2. Which of the electrode is negatively charged?
3. The carriers of the current in the cell.
2.
Define following terms

1. Electrode potential
2. Standard electrode potential
3. Emf
4. Cell potential
5. SHE
6. Electro chemical series
How would you determine the standard electrode potential of the system Mg 2+/Mg?
Can you store copper sulphate solutions in a zinc pot?
Consult the table of standard electrode potentials and suggest three substances
that can oxidise ferrous ions under suitable conditions. EOFe+2/Fe+3 = -0.77V
Arrange the following metals in the order in which they displace each other from the
solution of their salts. Al, Cu, Fe, Mg and Zn.

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.
Knowing that :
Cu2+ (aq) + 2 e Cu (s)
9
E = + 0.34 V
2 Ag+ (aq) + 2 e 2 Ag (s) E = + 0.80 V

Reason out whether, 1 M AgNO3 solution can be stored in Copper Vessel or 1 M
CuSO4 solution in Silver Vessel.
10
Can a nickel spatula be used to stir a solution of Copper Sulphate ? Justify your answer.
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(ENi+/Ni = 0.25 V
ECu+/Cu = 0.34 V)
Using the standard electrode potentials given in Table, predict if the

Reaction between the following is feasible:
EOFe+3/Fe+2
0.77v
11
EOI2/I0.54v
EOAg+/Ag
0.80v
EOCu+2/Cu
0.34v
EO Br2/Br1.o9v
(i) Fe3+(aq) and I(aq)

(ii) Ag+ (aq) and Cu(s)
(iii) Fe3+ (aq) and Br (aq)
(iv) Ag(s) and Fe 3+ (aq)
(v) Br2 (aq) and Fe2+ (aq).
Consider the electrochemical cell :
12
Zn (s) / Zn2+ (aq) // Cu2+ (aq) / Cu. It has an electrical potential of 1.1 V when
concentration of Zn2+ and Cu2+ ions is unity.
State the direction of flow of electrones and also specify if Zinc and Copper are
deposited or dissolved at their respective electrodes. When :
(a)
an external opposite potential of 0.8 V is applied.
(b)
an external opposite potential of 1.1 V is applied
13
14
The standard electrode potential for the Zn+2/Zn is o.76v .Write the reactions occurring at
Electrodes when coupled with standard hydrogen electrode (SHE)
NERNST EQUATION:
EOFe+3/Fe+2
0.77v
ELECTRODES
Mg2+ /Mg(s)
Cu2+/Cu
Fe2+/ Fe(s)
Sn2+/ Sn(s)
EOI2/I0.54v
EOAg+/Ag
0.80v
EOCu+2/Cu
0.34v
EO Br2/Br1.o9v
EO
-2.37v
0.34v
-0.44
-0.40v
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Br2(l)/Br
Cr3+/Cr
Cd2+/Cd
Zn+2/Zn
Ag+ /Ag
1
0.74
-0.40
-0.76v
0.80v
a. Find the zinc electrode potential when Zn+2 concentration is

0.1latM
b. Calculate the single electrode potential of Pt,Cl2/Cl-(0.01m)
Write the Nernst equation and emf of the following cells at 298 K:
(i) Mg(s)|Mg2+(0.001M)||Cu2+(0.0001 M)|Cu(s)
(ii) Fe(s)|Fe2+(0.001M)||H+(1M)|H2(g)(1bar)| Pt(s)

(iii) Sn(s)|Sn2+(0.050 M)||H+(0.020 M)|H2(g) (1 bar)|Pt(s)
(iv) Pt(s)|Br2(l)|Br(0.010 M)||H+(0.030 M)| H2(g) (1 bar)|Pt(s).
3
Calculate the standard cell potentials of galvanic cell in which

the following
Reactions take place:
(i) 2Cr(s) + 3Cd2+(aq)
2Cr3+(aq) + 3Cd
(ii) Fe2+(aq) + Ag+(aq)

Fe3+(aq) + Ag(s)
Calculate the . rG and equilibrium constant of the reactions
4
5
Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10

Calculate the emf of the cell in which the following reaction takes place:
Ni(s) + 2Ag+ (0.002 M) Ni
2+ (0.160 M) + 2Ag(s)
Given that E (cell) = 1.05 V
The cell in which the following reaction occurs:

at 298 K.
Calculate the standard Gibbs energy and the equilibrium constant of the cell reaction.
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UNIT-3

Example of galvanic cell :Daniel cell

3. In a galvanic cell, the half-cell in which oxidation

negative potential with respect to the solution.

cells or redox couples

Construction of Galvanic cell:

Function of Salt Bridge:

1. To maintain electrical neutrality of the solution in the two half cell.

M (S) | Mn+ (conc.) | | Mn+ (conc.) | M(S)

Depict the galvanic cell in which the reaction

. Zn2+(aq)+2Ag(s) takes place. Further show:

(i) Which of the electrode is negatively charged?

potential difference developed

M+n + ne M(s) EM+n/M(S) for metallic electrode

for non-metal electrode

Standard electrode potential(EO): The electrode potential of a

Standard electrode potential(E )

Oxidation potential and reduction potent numerical value is

E0 value does not change with react reaction quotient changes

Eo cell = Eo (cathode) Eo (anode)

Measurement of Electrode Potential:

The potential of individual half-cell cannot be measured.

Construction of SHE / NHE:

The standard hydrogen electrode consists of a platinum electrode

The electrode is dipped in an acidic solution and pure hydrogen gas

The concentration of both the reduced and oxidised forms of hydrogen

Measurement of electrode potential of Zn2+ / Zn

Construct a cell At 298 K and find the emf of the cell,

Standard hydrogen electrode | | Zn2+ / Zn is constructed by taking standard

for standard hydrogen electrode is zero.

Measurement of electrode potential of Cu2+ / Cu

of the given half-cell.

for standard hydrogen electrode is zero.

Different types of electrodes:

as electrochemical series(highest negative EO value placed at the top and highest

Applications of electrochemical series:

Substances which have lower reduction potential (- ve E ) are stronger reducing

Given the standard electrode potentials,

2.Comparison of reactivities of metals:

Arrange the following metals in the order in which they

2 Ag+ (aq) + 2 e 2 Ag (s) E = + 0.80 V

3. Calculation of the E.M.F.of the cell:

(i) Fe3+(aq) and I(aq)

5. Predicting whether a metal can liberate hydrogen from acid or not:

Can you store copper sulphate solutions in a zinc pot?

. Zn2+(aq)+2Ag(s) takes place. Further show:

(i) Which of the electrode is negatively charged?

2 Ag+ (aq) + 2 e 2 Ag (s) E = + 0.80 V

Reversibility of cell by applying external opposite potential to Galvanic cell:

Consider the electrochemical cell :

an external opposite potential of 0.8 V is applied.

an external opposite potential of 1.1 V is applied

NERNST EQUATION FOR SINGLE ELECTRODE

For the electrode reaction:

The electrode potential at any concentration measured with respect to standard

(R is gas constant (8.314 JK1 mol1) F is Faraday constant (96,487 C mol1), T is

NERNST EQUATION FOR CELL

we write For cathode:

Write the Nernst equation for following cell

Equilibrium Constant from Nernst Equation:

the concentration of Zn2+ keeps on increasing while the concentration of Cu 2+ keeps on

Electrochemical Cell and Gibbs Energy of the Reaction:

Gibbs Energy of the Reaction: It is the measure of the maximum

E (cell) is an intensive parameter (independent on the amount of substance)