Constructionand working of an electrochemical cell

Electrochemical cell (also known as Galvanic cell) is a device used to convert chemical
energy (produced in a redox reaction) into electrical energy.
If we take a Zn rod and place it in a container filled with CusO4 solution, heat will be
produced. This happens due a spontaneous redox reaction as given below:
Zn(solid) t CuSO(Aqueous) ZnSO4(AqueoUs) + Cu (Solid) deposited
As the reaction would proceed, Zn rod would get eroded, Cu particles get deposited and
solution would become warm.

Current (By sign conventon drection of curent is

opposte tothat of electons)
Zinc e
Copper
Rod
(Anode)
Salt Bridge
RSathode)
CuSO,
ZnSO, Solution
Solution t 2eCu
Zn ’ Zn?: + 2e
From the Into Wire
From the From Deposted nto
Zinc Rod Solution wiI copper rOd

An Electrochemical Cell

Oxidation reaction in Zn rod releases 2e and are taken by Cu?* ion in CusO4 solution. If these
two half reactions can be separated, then the electrons can be made to move through a wire.
In this manner, we can produce electrical energy from chemicalenergy. The salt bridge is a
concentrated solution of inert electrolytes. It is required for completing the circuit. It allows the
movement of ions from one solution to the other.

Applications: Electrochemical cellwould be useful to be able to convert this chemical energy

to electrical energy (in Battery) instead of heat energy. This process is also used in
electroplating industry to coat Fe metal with Zn/Al coatings.

10
Expt. No. Date:

Experiment Construction and working of an Zn-Cuelectrochemical cell

Problem definition Measurement of electrode potential and construction of a battery system
Single electrode potentials of Zn/Zn and C/Cu' system and Daniel
Methodology Cell
Solution Electromotive force measurement (EMF) as voltage
Students will learn to perform
Student learning a) Electrode potential relevant to battery
outcomes
b) Understanding of a normal battery system

Principle: The electromotive force (emf) of an electrochemical cell is measured by means of a

potentiometer. An electrochemical cell (Eea) is considered as a combination of two individualsingle
electrodes. The potential difference between the two single electrode potentials is a measure of emf of
the cell (Et). In order to measure the potential difference between electrodes in contact with electrolyte
containing the same cation, it is necessary to have another electrode in contact with electrolyte of same
cation, both the half-cells connected through a salt bridge. Saturated calomel electrode (SCE; Ealomel)
whose potential is known, is used as a reference electrode and it is coupled with the metal electrode for
which the potential is to be determined.

Hg/Hg;Cl (9), saturated KCI|(N/10) electrolyte of the metal/ Metal

From the emfof the cell involving saturated calomel electrode and metal electrode dipped in its solution
of 0.1 N electrolyte, electrode potential of the metal electrode is readily calculated using the standard
potential of calomel electrode as:
Ecell EMM- Ecalonel
EMM = Ecell + Ecalomel
Ecellis total emf of the cell. Electrode potential of the metal electrode is given by Nenst equation as;
EMM = E + RT In at
n

EMM =EMM- RT In a
nF

EMM =EMM*-0.0595 log a*

Requirements:
Reagents and solutions: CuSO, stock solution (0.IN), ZnSO4 stock solution (0.1N), KCI salt.
Apparatus: Digital potentiometer, copper electrode, zinc electrode, calomel electrode, 100 mL
beaker, burette, 50 ml standard flasks.

11
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0
9.S..So*o

Jbht'*
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Cr lathle

Procedure:
Calibrate the digital potentiometer with the help of the wires to display 1.018 V. The metal electrode
is sensitized by dipping in a small quantity of 1:1 nitric acid containing a small quantity of sodium
nitrite until effervescence occurs. Then the electrode is washed well with distilled water. 50 mL of the
given concentration of the electrolyte solution (0.01 N, 0.05 N and 0.1 N) is taken in a beaker and its
corresponding metal electrode is introduced. This is connected with the saturated calomel electrode
(half-cell) by means of a salt bridge. The metal electrode is connected to the positive terminal and the
calomel electrode is connected to the negative terminal of the potentiometer. EMF of the cell (Ecell) is
measured and noted in Table 1. Standard electrode potential [EMM1is computed using Nernst

equation (Eq. 1).

Ecalom 044V
Table 1: EMF mneasured for various concentrations of M/M system
Electrode/ Electrolyte EM/M+= E°MIM Average
Ecell (V) +

Electrolyte conc. (N) Ecell t Ecalomel [From Eq. (1)] EMIM

0.01 N -0866 622
Zn/Zn2t 0.0N ~066R to6l45
-061a4
0.N Lo-gt8-0434
0.01 N 0276 03392
C/Cut 0.0N 0«3446034rt
O3
Solution Temperature (T) ="C; Potential of SCE= 0.244 +0.0007 (25 °C)
E°MIM= EMIM-D.0595 log lYe x C] ------(1)
n ’
where, E is standard electrode potential of metal electrode; a* is activity of metal ions in solution
(an =yC); Y. is activity coefficient (Table 2) and Cis concentration of electrolyte solution.

Table 2:ndividual activity coefficients of Cu²* and Zn²* in water at 25 °C

Metal ion system 0.001 0.002 0.005 0.01 0.02 0.05 0.1 0.2
(Cu/Zn)
Activity coefficient (Y) 0.905 0.870 0.809 0.749 0.675 0.570 0.485 0.405

Us thisspace for detailed calculation

(2n
M /M
-0 622

= -06 22- o 02445 - a s s

0-622

- 0.sT88 12

-0.66&
 cellstConstruct The
he of reaction: respectively.
reaction: solutions:
immersed Cu/Zn of
Construction
Table At
(c). (b). Results:
(a). Copper
At thein theIn
the
overall the
EMF Zn/Znt Metal
Standard
Standard 3: cathode, anode, Daniel
EMF Table in Zns)
of andDaniel
reactionCu(aq)
the ’zinc cell, of
electrode
electrode of Zinc copper equimolar
constructed Daniel 3. cell Zn'ea) copper Daniel
Concentration is 2e’ t+
: is
solutions using oxidized
potential
potential 0.05 N0.02 N0.01 N Zngs is t cell
(N) Cell Cus) and
reduced 2e solution
Daniel the + zinc and
observed and Cu* as
following
of of measurement
per electrodes
c
cell ZinCopper record (aq) as of
per the
= from ’Zn?+ CuSO4
(E) concentrations
the following
(E) the
CWCuz+ Metal "(aq) and are
= three voltage following
+Cuis) ZnSO4 of
13 Ü" =
039S its
different half
6l of voltage
electrode
zinc
kate
Concentration conc.
vs. with
SCE vs. 0.05 N0.02 N0.01 N
23MC
0088 (N) of oxldatlon
anode three
SCE ( kons
zinc
Zn
12/3 Average
and
bridge
salt different
electrons
Cu
solutions sulfateions
observed
EMF reduction
cathode
(+)
concentrations
(Ecell/V)
copper() electrode
copper
Suiate