MODULE-1

ELECTROCHEMISTRY AND ENERGY STORAGE SYSTEM

Electrochemistry: Use of free energy in chemical equilibria
Introduction:
Thermodynamics: the study of flow of energy between the system and its surrounding, as it
undergoes physical or chemical transformation, is known as thermodynamics.

First law states that: The energy neither be created nor be destroyed, only can transform from
one form to another form. Total energy of the isolated system remains
unchanged.
Second law states that: Any spontaneous reaction is accompanied by increase in total energy of
universe.

Spontaneous process: the process that takes place on its own without applying external energy.
Spontaneous process is irreversible one.

Free energy: It is the thermodynamic state, a part of a total energy of a system is converted into
work and the rest is unavailable. Any kind of energy which is converted into useful work is called
as (available) Free energy. Energy which cannot be converted into useful work is known as
unavailable energy which is represented as Entropy function. Isothermally available energy of a
system is known as free energy (Gibb’s Free energy)

Entropy: it is a measure of the molecular disorder or randomness of a system. (Because work is

obtained from ordered molecular motion)
ΔS=ΔQ/T
ΔS= Change in entropy, ΔQ=change in energy & T is the temperature.
∆S= 0 for reversible process
∆S>0 for irreversible process

Entropy change depends on system and surrounding. To study the above system a new
thermodynamics function is introduced- which is free energy. Free energy is a point function.

Free energy is a composite function that balances the influence of energy vs. entropy.

The Gibbs free energy G: G=H-TS ------------------1

Where G= Gibbs free energy, H= Enthalpy, T= Constant Temp, S= Entropy

Consider a change A B

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GA, HA, and SA are Gibb’s free energy, Enthalpy and Entropy of reactant A respectively.
GB, HB, and SB are Gibb’s free energy, Enthalpy and Entropy of product B respectively.
Calculation of change in free energy during a chemical change is given as follows:
∆G= GB-GA= (HB-HA) – T(SB-SA)
∆G=∆H-T∆S
Above change continue till equilibrium is attained. At equilibrium, the second Law states that
∆Q= T∆S
Under Constant temperature and pressure ∆H= T∆S
For a finite change ∆H=T∆S
at equilibrium ΔG=ΔH-TΔS=0
Significance of Free Energy
∆G= 0 Reaction at equilibrium
∆G= -ve spontaneous reaction
∆G= +ve non-spontaneous reaction
∆G= -nEF for work done in a redox reaction at a given temp
∆G˚= -nE˚F for work done in a redox reaction at 298˚ K

Electrodes: A metal is in contact with solution of its own ions is called electrode or a half cell.

Ex: Cu, Zn, Mg electrodes etc.

Single Electrode Potential (E):

The potential developed when metal is in equilibrium with its own ions in the solution.

Standard reduction potential (Eo):

“Standard electrode potential is the potential developed when metal is in equilibrium with its own
ions in the solution of unit concentration at STP”.

EMF of a cell: “Emf is the potential difference between the two electrodes of a galvanic cell,
which causes the flow of current from electrode having high reduction potential to the electrode
having lower reduction potential”
EMF=𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒 −𝐸𝐴𝑛𝑜𝑑𝑒
Derivation of Nernst equation for single electrode potential:

Nernst equation gives a quantitative relationship between electrode potential and concentration of
the electrolyte species involved at a particular temperature.
Consider the following reversible electrode reaction
𝑀𝑛+ + 𝑛𝑒 − 𝑀
[𝑀]
Equilibrium constant (𝐾𝑐 ) can be written as 𝐾𝑐 = 𝑛+
[𝑀 ]

According to thermodynamics, for reversible reactions there is relation between equilibrium

constant free energy changes is given by.
∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝐾𝑐 ………………………(1)
Substitute the value of Kc, we have
[𝑀]
∆𝐺 = ∆𝐺° + 𝑅𝑇 𝑙𝑛 𝑛+ ………(2)
[𝑀 ]

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 The decrease in free energy (−∆𝐺) for any reversible reaction is equal to maximum workdone by
the system.
−∆𝐺 =𝑊𝑚𝑎𝑥 ……………………………(3)

In case of galvanic cell, the max work available from a reversible electro chemical process is equal
to the maximum amount of electrical energy generated.

𝑊𝑚𝑎𝑥 = (Potential difference b/w two electrodes) x (total quantity of charges flows through the
cell)

If n moles of electrons flows from anode to cathode, then quantity of charges is nF

𝑊𝑚𝑎𝑥 = E × nF = nFE

Where, n= No of electrons, E=Electrode potential & F= Faraday constant.

Under standard conditions

−∆𝐺° = 𝑛𝐹𝐸°
Where, −∆𝐺°=Decrease free energy under standard condition, 𝐸°=Standard electrode potential

Substitute the value of −∆𝐺 &−∆𝐺° to equation (2)

[𝑀]
−nFE = −𝑛𝐹𝐸° + 𝑅𝑇 𝑙𝑛 [𝑀𝑛+ ]…………….4
Divide the equation (4) by – nF
𝑅𝑇 [𝑀]
E = 𝐸° − 𝑙𝑛 𝑛+
𝑛𝐹 [𝑀 ]

Under standard conditions, metal concentration is unity, so that [𝑀]=1

Then,
𝑅𝑇 1
E = 𝐸° − 𝑙𝑛 𝑛+
𝑛𝐹 [𝑀 ]
The above equation can be rewritten as
𝑅𝑇
E = 𝐸° + ln[𝑀𝑛+ ]
𝑛𝐹
2.303𝑅𝑇
E = 𝐸° + 𝑛𝐹 log[𝑀𝑛+ ]………. 5

Substitute the value of R=8.314 J/K/mol, T=298 K, F=96500 C/mol to the equ(5)
0.0591
E = 𝐸° + 𝑛 log[𝑀𝑛+ ]………6
Equation (6) is the Nernst equation for single electrode.

Nernst equation for cell:

Cell consists of two half cells. i.e cathode and anode

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

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 2.303𝑅𝑇
𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 + 𝑙𝑜𝑔[𝐶𝑎𝑡ℎ𝑜𝑑𝑒]
𝑛𝐹
2.303𝑅𝑇
𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸°𝑎𝑛𝑜𝑑𝑒 + 𝑙𝑜𝑔[𝐴𝑛𝑜𝑑𝑒]
𝑛𝐹
2.303𝑅𝑇 2.303𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = (𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸°𝑎𝑛𝑜𝑑𝑒 ) + 𝑙𝑜𝑔[𝐶𝑎𝑡ℎ𝑜𝑑𝑒] − 𝑙𝑜𝑔[𝐴𝑛𝑜𝑑𝑒]
𝑛𝐹 𝑛𝐹

The above equation can be rewritten as

2.303𝑅𝑇 [𝐶𝑎𝑡ℎ𝑜𝑑𝑒]
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 + 𝑙𝑜𝑔
𝑛𝐹 [𝐴𝑛𝑜𝑑𝑒]

∴ 𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝐶𝑎𝑡𝑜𝑑𝑒 − 𝐸°𝐴𝑛𝑜𝑑𝑒

Numerical Problems
1. Calculate the potential of Daniel cell at 25o C, given the electrode potentials of Cu and Zn are
0.34V and –0.76V respectively.
𝑜 𝑜
Given: 𝐸𝑍𝑛 = -0.76V; 𝐸𝐶𝑢 = 0.34V
w.k.t Ecell = Ecathode -Eanode
Ecell = 0.34-(-0.76)
Ecell = 1.1 V

2+ 2+
2. Calculate the voltage of the cell Mg𝑀𝑔(1𝑀)  𝐶𝑑(7×10−11 𝑀)  Cd(s), where E cell=1.97V.
0

𝑜
Given: 𝐸𝐶𝑒𝑙𝑙 = 1.97V
[Mg+2] =1M
[Cd+2] = 7x10-11M
𝑜
0.0591 [𝐶𝑑 2+ ]
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 + 𝑙𝑜𝑔
𝑛 [𝑀𝑔2+ ]

0.0591 [7 × 10−11 ]
𝐸𝑐𝑒𝑙𝑙 = 1.97 + 𝑙𝑜𝑔
2 [1]

0.0591
𝐸𝑐𝑒𝑙𝑙 = 1.97 + 𝑙𝑜𝑔 7 × 10−11
2

𝐸𝑐𝑒𝑙𝑙 = 1.97 − 0.3001

𝐸𝑐𝑒𝑙𝑙 = 1.6699𝑉

3. A cell is constructed by coupling Zn electrode in 0.5 M ZnSO4 and Ni electrode in 0.05M

NiSO4. Write the cell representation, cell reaction & calculate emf of the cell given SRPs
of Zn and Ni as -0.76 & -0.25 V respectively.
2+
Zn(s)𝑍𝑛(0.5𝑀) Ni2+(0.05M)  Ni(s)

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 At anode: Zn Zn2+ +2e-
At cathode Ni2+ + 2e- Ni

Net cell reaction Zn + Ni2+ Zn2+ + Ni

𝑜 𝑜
0.0591 [𝑁𝑖 2+ ]
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 + 𝑙𝑜𝑔
𝑛 [𝑍𝑛2+ ]

0.0591 [0.05]
𝐸𝑐𝑒𝑙𝑙 = −0.25 − (−0.76) + 𝑙𝑜𝑔
2 [0.5]
𝐸𝑐𝑒𝑙𝑙 = 0.4804𝑉

4. Calculate the potential of Ag-Zn cell at 298 K, if the concentration of Ag+ and Zn2+ are
𝑜
5.2x10-6M and 1.3x10-3 M respectively. Eo of the cell at 298K is 1.5V given: T=298K; 𝐸𝑐𝑒𝑙𝑙 =
1.5V.
[Ag+] =5.2x10-6M
[Zn2+] = 1.3x10-3M
w.k.t
2.303𝑅𝑇 [𝐴𝑔+ ]2
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 + 𝑙𝑜𝑔
𝑛𝐹 [𝑍𝑛2+ ]
2.303 × 8.314 × 298 [5.2 × 10−6 ]2
𝐸𝑐𝑒𝑙𝑙 = 1.5 + 𝑙𝑜𝑔
2 × 96500 [1.3 × 10−3 ]

Ecell = 1.27 V
5. An electrochemical cell consists of iron electrode dipped in 0.1M FeSO4 and silver electrode in
0.05M AgNO3 . Write the cell representation cell reaction and calculate the emf of the cell at 298K.
(The standard reduction potentials of iron and silver are –0.44V and 0.8V respectively).
𝑜 𝑜
Given: T=298K; 𝐸𝐹𝑒 = -0.44V; 𝐸𝐴𝑔 = 0.8V
2+
[Fe ] =0.1M
[Ag+] = 0.05M
cell representation: Fe(s) FeSO4(0.1M)  AgNO3(0.05M)  Ag(s)
w.k.t. Ecell = Ecathode -Eanode

2.303𝑅𝑇 [𝐶𝑎𝑡ℎ𝑜𝑑𝑒]
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 + 𝑙𝑜𝑔
𝑛𝐹 [𝐴𝑛𝑜𝑑𝑒]

𝑜 𝑜
0.0591 [𝐴𝑔+ ]2
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐴𝑔 − 𝐸𝐹𝑒 + 𝑙𝑜𝑔
𝑛 [𝐹𝑒 2+ ]

0.0591 [0.05]2
𝐸𝑐𝑒𝑙𝑙 = 0.8 − (−0.44) + 𝑙𝑜𝑔
2 [0.1]

𝐸𝑐𝑒𝑙𝑙 = 1.19𝑉

5
6. An Electrochemical cell consists of a copper electrode dipped in 0.5 M CuSO4 and silver
electrode dipped in 0.25 M AgNO3. Write the cell scheme, half cell and net cell reactions. Also,
calculate the emf. Given, SRPs of Cu & Ag are 0.34 and 0.8V respectively.
cell representation: Cu(s) CuSO4(0.5M)  AgNO3(0.25M)  Ag(s)

At anode: Cu Cu2+ +2e-

At cathode 2Ag+ + 2e- 2Ag

Net cell reaction Cu + 2Ag+ Cu2+ + 2Ag

2.303𝑅𝑇 [𝐶𝑎𝑡ℎ𝑜𝑑𝑒]
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 + 𝑙𝑜𝑔
𝑛𝐹 [𝐴𝑛𝑜𝑑𝑒]

𝑜 𝑜
0.0591 [𝐴𝑔+ ]2
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐴𝑔 − 𝐸𝐶𝑢 + 𝑙𝑜𝑔
𝑛 [𝐶𝑢2+ ]

0.0591 [0.25]2
𝐸𝑐𝑒𝑙𝑙 = 0.8 − (−0.34) + 𝑙𝑜𝑔
2 [0.5]

𝐸𝑐𝑒𝑙𝑙 = 0.433𝑉
2+
7. The EMF of a cell, Mg(s)𝑀𝑔(0.02𝑀) Cu2+
(𝑥 M)  Cu(s) is measured to be 3.28V at 299 K, the
standard electrode potential of Mg is -2.417V, Calculate the electrode potential of Cu electrode.

At anode: 𝑀𝑔 𝑀𝑔2+ + 2𝑒 −
At cathode: 𝐶𝑢 + 2𝑒 −
2+
𝐶𝑢

Net Cell reaction: 𝐶𝑢2+ + 𝑀𝑔 𝐶𝑢 + 𝑀𝑔2+

2.303𝑅𝑇
𝐸𝑀𝑔 = 𝐸°𝑀𝑔 + log[𝑀𝑔2+ ]
𝑛𝐹
2.303 × 8.314 × 299
𝐸𝑀𝑔 = −2.417 + log[0.02]
2 × 96500
5724.99
𝐸𝑀𝑔 = −2.417 + [−1.6989]
19300
𝐸𝑀𝑔 = −2.417 + (0.2966 × −1.6989)

𝐸𝑀𝑔 = −2.417 − 0.5038

𝐸𝑀𝑔 = −2.9208 𝑉

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 ,

𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐶𝑢 − 𝐸𝑀𝑔

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 𝐸𝐶𝑢 = 𝐸𝐶𝑒𝑙𝑙 + 𝐸𝑀𝑔

𝐸𝐶𝑢 = 3.28 + (−2.9208)

𝐸𝐶𝑢 = 0.3592 𝑉
Reference Electrode:

Reference electrodes are the electrodes, those potential already known, with respect to these
potential of any other electrodes potential can be measured.

SECONDARY REFERENCE ELECTRODES:

Secondary reference electrodes are the electrodes those potential already know by using SHE,
these electrodes can be used to measure any other electrodes potential.
1. Calomel electrode 2. Ag-AgCl electrode
Calomel electrode: this electrode is example for metal-metal ion electrode
It consists of glass tube in which mercury is placed at the bottom and it covered by paste of mercury
and mercurous chloride and a solution of KCl of known concentration. A platinum wire is
immersed into the mercury and used for electrical contact. There is porous disc at bottom of the
glass tube acts as salt bridge.

Calomel electrode can be represented as, 𝐻𝑔(𝑙) ⁄𝐻𝑔2 𝐶𝑙2 ⁄𝐾𝐶𝑙

The calomel electrode can acts as anode or cathode depending on the nature of the other electrode
in the cell.
When it acts as anode, the electrode reaction is,
2Hg + 2Cl- Hg2Cl2 + 2e-
2Hg Hg22+ + 2e-
Hg22+ + 2Cl- Hg2Cl2

When it acts as cathode, the electrode reaction is,

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 Hg2Cl2 + 2e- 2Hg + 2Cl-
+ -
2Hg + 2e 2Hg
Hg2Cl2 2Hg + 2Cl-
+

The net cell reversible electrode reaction is,

𝐻𝑔2 𝐶𝑙2(𝑠) + 2𝑒 − 2𝐻𝑔(𝑙) + 2𝐶𝑙 −

2.303 𝑅𝑇
Electrode potential, 𝐸𝐶𝐸 = 𝐸°𝐶𝐸 − 𝑛𝐹 log[𝐶𝑙 − ]2
The calomel electrode potential reversible with respect to Cl- concentration

Therefore electrode potential of calomel electrode is depending upon the concentration of KCl.
For saturated KCl, the potential is +0.2422V, for 1N and 0.1N KCl the values are 0.281V and
+0.334V respectively.

Applications:
1. It is used as secondary reference electrode to measure other electrode potential.
2. It is used as reference electrode in all potentiometer.
3. Used in determining whether the potential distribution in ship hulls and pipelines protected by
cathodic protection.
4. As a portable reference electrode for measuring the different depths of oil rigs anplatforms,
submerged oil pipelines etc.

Measurement of electrode potential using calomel electrode

To determine electrode potential of a given electrode calomel electrode is taken as reference

electrode. The potential of Saturated Calomel Electrode (SCE) is +0.241V. The electrode whose
potential has to be determined such as Zn electrode is coupled with SCE as shown below.

Salt bridge
+
-
Zinc
Anode
SCE
ZnSO4
Solution

2+
Cell representation: 𝑍𝑛/𝑍𝑛(1𝑀) //𝐾𝐶𝑙(𝑠𝑎𝑡) , 𝐻𝑔2 𝐶𝑙2 /𝐻𝑔
Therefore the electrode potential of Zn electrode can be calculated as follows
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑆𝐶𝐸 − 𝐸𝑍𝑛

1.001= 0.241- 𝐸°𝑍𝑛

𝐸°𝑍𝑛 = - 0.760V

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 Similarly the measurement of the electrode potential of copper can be done as follows: The copper
electrode is coupled with Calomel, to get a complete cell arrangement through the salt bridge and
voltmeter, as in figure.

Salt bridge

SCE Cu metal

CuSO4 Solution

2+
The cell representation: 𝐻𝑔/𝐻𝑔2 𝐶𝑙2 //𝐾𝐶𝑙(𝑠𝑎𝑡) , 𝑍𝑛(1𝑀) /𝑍𝑛
Therefore 𝐸𝑐𝑒𝑙𝑙 =𝐸𝐶𝑎𝑡ℎ𝑜𝑑𝑒 −𝐸𝐴𝑛𝑜𝑑𝑒
𝐸𝑐𝑒𝑙𝑙 =𝐸𝐶𝑢 −𝐸𝑆𝐶𝐸
0.34 =𝐸𝐶𝑢 -0.241
𝐸𝐶𝑢 = 0.1V
Hence the potential of copper electrode is +ve.

Ion selective electrode: “Ion selective electrode is one which selectively responds to a particular
ion in a mixture of ions by neglecting other and the potential developed at the electrode is a
function of the concentration of ion in the solution”
These electrodes are used to measure concentration of particular cations or anions in the mixture,
these are sensitive upto 10-6 M concentration.
Glass electrode: A glass electrode is more selective towards H+ ions and potential depends upon
the concentration of H+ in the medium.
The glass electrode consists of silver electrode as internal reference, the glass membrane bulb made
of corning silicate is filled with a solution 0.1M HCl and Ag-AgCl electrode immersed to it, to
measure the boundary potential and for making electrical contact with other electrodes.
The electrode representation is, 𝐴𝑔/𝐴𝑔𝐶𝑙/𝐾𝐶𝑙⁄𝐺𝑙𝑎𝑠𝑠 𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒, 0.1𝑀 𝐻𝐶𝑙

Working
The potential of glass electrode is the sum of below three potential.
1. Boundary or membrane potential
2. Potential of Ag/AgCl electrode
3. Asymmetry potential
The boundary potential is given by Nernst equation at membrane Eb = E1 – E2
Due to change concentration of internal and external solution, we can write the equation by treating
as concentration cell.
Therefore 𝐸𝑏 = 0.0591 𝑙𝑜𝑔𝐶2 − 0.0591 𝑙𝑜𝑔𝐶1 since n=1 and C1=0.1M
𝐸𝑏 = K + 0.0591 𝑙𝑜𝑔𝐶2

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Where, K= - 0.0591 𝑙𝑜𝑔𝐶1 since 𝐶2 =[𝐻 + ] 𝑖𝑠 𝑢𝑛𝑘𝑛𝑜𝑤𝑛.

𝐸𝑏 = 𝐾 + 0.0591 𝑙𝑜𝑔[𝐻 + ]
∴ 𝑝𝐻 = −𝑙𝑜𝑔[𝐻 + ]
𝐸𝑏 = 𝐾 − 0.0591 𝑝𝐻

Asymmetry potential is potential exists across the membrane even when concentration of external
and internal solution becomes equal, i.e. C1=C2.
the potential value varies from time to time & also one electrode to other, its value can be
determined by using known concentration (buffer) solution.
The equation can be written as, 𝐸𝐺 = 𝐸𝑏 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦𝑚
Substitute the value of Eb,
∴ 𝐸𝐺 = 𝐾 − 0.0591 𝑝𝐻 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦𝑚
𝐸𝐺 = 𝐿 − 0.0591 𝑝𝐻
Where 𝐿 = 𝐾 + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝑎𝑠𝑦𝑚

Ag-AgCl
electrode Internal solution
concentration C1
0.1 M HCl
Glass bulb Layer of glass
membrane
H+ Ion Solution
Glass electrode External solution
concentration C2
Eb=E1-E2 concentration

Advantages
1. This electrode can be used to determine PH in the range 0-9, with special type of glass even up
to 12 can be calculated.
2. It can be used even in the case of strong oxidizing agents.
3. It is simple to operate, hence extensively used in various laboratories.

10
Limitations
1. The glass membrane though it is very thin, it offers high resistance. Therefore ordinary
potentiometers cannot be used; hence it is necessary to use electronic potentiometers.
2. This electrode cannot be used to determine the PH above 12

Determination of pH using glass electrode:

Principle: When a thin glass membrane is placed between two solutions of different pH values, a
potential difference arises across the membrane. The potential difference varies as the pH of these
solutions varies. In practice, one of these solutions pH is kept constant and therefore the electrode
potential depends on pH of the other solution.

Procedure: In order to measure the pH of given solution, a galvanic cell is constructed by using
glass and calomel electrodes. When both the electrodes are immersed to solution pH to be
determined.
The cell assembly is represented as,
Hg/ Hg2Cl2//KCl//Solution of unknown pH/glass membrane, 0.1M HCl /AgCl/Ag

The emf of the above cell (Ecell) is measured using unknown pH solution.
it is given by
𝐸𝐶𝑒𝑙𝑙(𝑢𝑛) = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝐴𝑛𝑜𝑑𝑒
𝐸𝑐𝑒𝑙𝑙(𝑢𝑛) = 𝐸𝐺 − 𝐸𝑆𝐶𝐸
Substitute EG value to the above equation
𝐸𝑐𝑒𝑙𝑙(𝑢𝑛) = 𝐿 − 0.0591𝑝𝐻(𝑢𝑛) − 𝐸𝑆𝐶𝐸
𝐸𝑆𝐶𝐸 is constant at saturated KCl solution, above equation we can write as
𝐸𝑐𝑒𝑙𝑙(𝑢𝑛) = 𝑀 − 0.0591𝑝𝐻(𝑢𝑛) ……….(1)
Where, 𝑀 = 𝐿 − 𝐸𝑆𝐶𝐸
The M value can be determined by measuring emf of the cell (Ecell) using buffer solution.
it is given by
𝐸𝐶𝑒𝑙𝑙(𝑏) = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝐴𝑛𝑜𝑑𝑒
𝐸𝑐𝑒𝑙𝑙(𝑏) = 𝐸𝐺 − 𝐸𝑆𝐶𝐸
Rewrite above equation using all the terms
𝐸𝑐𝑒𝑙𝑙(𝑏) = 𝑀 − 0.0591𝑝𝐻(𝑏)
Therefore we know the pH of buffer solution, 𝐸𝑆𝐶𝐸 is constant for saturated KCl and 𝐸𝑐𝑒𝑙𝑙(𝑏) is
got from the voltmeter.
So, 𝑀 = 𝐸𝑐𝑒𝑙𝑙(𝑏) + 0.0591𝑝𝐻(𝑏) ……….(2)
Substitute M value to the equation (1)
𝐸𝑐𝑒𝑙𝑙(𝑢𝑛) = 𝐸𝑐𝑒𝑙𝑙(𝑏) + 0.0591𝑝𝐻(𝑏) − 0.0591𝑝𝐻(𝑢𝑛)

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 Rearrange the above equation after dividing by 0.0591
𝐸𝑐𝑒𝑙𝑙(𝑏) −𝐸𝑐𝑒𝑙𝑙(𝑢𝑛)
∴ 𝑝𝐻 = + 𝑝𝐻(𝑏) at 298K
0.0591

We can get the 𝐸𝑐𝑒𝑙𝑙(𝑏) , 𝐸𝑐𝑒𝑙𝑙(𝑢𝑛) value from the voltmeter

pH Meter

Glass
Calomel electrode
electrode

Solution of
unknown pH

Concentration cells:” A concentration cell is type of galvanic cell, in which metal and metal salt
solution present in both half cells are same but only concentration of salt solutions are different.
A typical example of Zinc concentration cell is shown below.
𝑛+ 𝑛+
Generally concentration cells are represented as 𝑀⁄𝑀(𝐶 1)
//𝑀(𝐶2)
⁄𝑀
Where, 𝐶2 > 𝐶1,
Metal immersed in dilute solution is acts as anode and oxidation reaction occurs
𝑀 𝑀𝑛+ + 𝑛𝑒 −
Whereas metal immersed in concentrated solution acts as cathode and reduction reaction occurs
𝑀𝑛+ + 𝑛𝑒 − 𝑀
Net cell reaction is represented only by change in concentration of solution
𝑀𝐶𝑛+
2
𝑀𝐶𝑛+1
Concentration of the metal ions increases at anode due to oxidation consequently decreases at
cathode due to reduction
Cell reaction is change in concentration as a result of current flows, this will take place till the
concentrations in the two half cells becomes equal.
Emf of concentration cell:
We know that electrode potential depends upon the concentration of the electrolyte. By
convention, the potential of the cell is
𝐸𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝐴𝑛𝑜𝑑𝑒 ……..1

𝑜 0.0591 𝑜 0.0591
𝐸𝐶.𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 + 𝑙𝑜𝑔[𝐶2 ] − 𝐸𝑎𝑛𝑜𝑑𝑒 − 𝑙𝑜𝑔[𝐶1 ] ………2
𝑛 𝑛

𝑜 𝑜
0.0591
𝐸𝐶.𝑐𝑒𝑙𝑙 = (𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 )+ {𝑙𝑜𝑔[𝐶2 ] − 𝑙𝑜𝑔[𝐶1 ]}
𝑛

12
 𝑜 𝑜
𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 0, due to both the electrodes made by same metal

0.0591 [𝐶 ]
𝐸𝐶.𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 [𝐶2 ] at 298K …………….3
𝑛 1

From equation (3) following conclusions may be drawn.

1. When the two solutions are of the same concentration, then log
C 2  and no electricity flows.
C1 
Hence, Ecell=0
2. When C2/C1>1 i.e C2>C1, log C2/C1 is positive & electrode potential is positive, due to
spontaneous reaction.
3. Higher the ratio of C2/C1, higher is the value of cell potential.

Examples: Zinc metal concentration cell

Salt bridge

+
- Zinc
Zinc
Anode Cathode

ZnSO4 C1 C2 ZnSO4
Solution Solution

It consists of two zinc electrodes are immersed in two different concentration of ZnSO4
solutions. These two electrodes are externally connected by metallic wire and internally by a salt
bridge. The cell can be represented as,
2+ 2+
𝑍𝑛⁄𝑍𝑛(𝐶 1)
//𝑍𝑛(𝐶2)
⁄𝑍𝑛
By convention left hand electrode is the anode and right hand electrode is cathode.
2+
At anode: Zn 𝑍𝑛(𝐶 1)
+ 2𝑒 −
2+
At cathode: 𝑍𝑛(𝐶 2)
+ 2𝑒 − Zn

2+ 2+
Net cell reaction: 𝑍𝑛(𝐶2)
𝑍𝑛(𝐶1)

The net cell reaction is merely the change in concentration as a result of current flow.

Numerical Problems:

1. Calculate the emf of Copper concentration cell at 250 C, where the copper ions ratio in the cell
is 10.

13
 [𝐶𝑢2+ ]𝑐𝑎𝑡ℎ𝑜𝑑𝑒 𝐶2
Given:
[𝐶𝑢2+ ]𝑎𝑛𝑜𝑑𝑒
= = 10
𝐶1

0.0591 [𝐶 ]
w.k.t 𝐸𝐶.𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 [𝐶2 ]; at 298 K
𝑛 1

0.0591
𝐸𝐶.𝑐𝑒𝑙𝑙 = log(10)
2
𝐸𝐶.𝑐𝑒𝑙𝑙 = 0.0296 V.

2. A concentration cell was constructed by immersing two silver electrode in 0.05M and 1M
AgNO3 solution. Write the cell representation, cell reactions and calculate the EMF of the cell.
+ +
Cell representation: 𝐴𝑔⁄𝐴𝑔(0.05𝑀) //𝐴𝑔(1𝑀) ⁄𝐴𝑔

0.0591 [𝐶2 ]
𝐸𝐶.𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 [𝐶1 ]
+
At anode: 𝐴𝑔(0.05𝑀) 𝐴𝑔(0.05𝑀) + 𝑒−
+
At cathode: 𝐴𝑔(1𝑀) + 𝑒− 𝐴𝑔(1𝑀)

+ +
Net cell reaction: 𝐴𝑔(1𝑀) 𝐴𝑔(0.05𝑀)

0.0591 1
𝐸𝐶.𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 ( )
1 0.05

𝐸𝐶.𝑐𝑒𝑙𝑙 = 0.0768𝑉
𝑛+ 𝑛+
4. The spontaneous galvanic cell 𝑆𝑛⁄𝑆𝑛(0.024𝑀) //𝑆𝑛(0.064𝑀) ⁄𝑆𝑛 develop an emf of 0.0126 V at
o
25 C, Calculate the Valency of Tin.

0.0591 𝐶2
𝐸𝐶.𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 ( )
𝑛 𝐶1

0.0591 𝐶2
𝑛= 𝑙𝑜𝑔 ( )
𝐸𝐶.𝑐𝑒𝑙𝑙 𝐶1

0.0591 0.064
𝑛= 𝑙𝑜𝑔 ( )
0.0126 0.024

𝑛 = 2 (𝑣𝑎𝑙𝑒𝑛𝑐𝑦)

14
ENERGY STORAGE SYSTEM

Definition: A battery is a compact device used to store chemical energy using two or more
cells connecting in series or parallel, it can covert on demand.
Components of battery:
The basic unit in battery is electrochemical cell, it consists of four major components.
1. Anode: electrode undergoes oxidation by releasing the electrons to the external circuit.
2. Cathode: the electrode undergoes reduction by accepting electrons from the external circuit.
3. Electrolyte: it is present in both cathode and anode compartments, the solution of acid, alkali
and high conductivity ionic salts are commonly used electrolytes.
4. Separator: it is used to avoid the internal short circuiting and also helps to transfer the ions
from anode to cathode or vice versa. Usually separators are organic polymers. Ex: cellulose,
polyolefins and nafion membranes.

Classification:
Batteries are classified into three types
1) Primary batteries: In this batteries, the chemical reactions in the cells are not reversible, so
these are not rechargeable. Ex: Zn-MnO2, Li-MnO2 batteries
2) Secondary batteries: these are the storage batteries, the chemical reactions in the cells are
reversible, so used batteries can be charged by passing current, the external current makes
redox reaction gets reversed during charging. That electrical energy is stored in the form
of chemical energy and utilized whenever needed. Therefore secondary batteries are also
known as storage batteries.
Ex. Lead-acid, Ni-Cd batteries
3) Reserve batteries: the components of the battery were stored in isolated within the cells and
make them to contact, whenever energy required. Usually electrolytes were stored separately.
The materials are stored in an inactive state, use of those after activating them are known as
reserve batteries. These are used for long term storage.
Ex. Ag-MnO2

Nickel- Metal Hydride (Ni-MH) battery:

In Ni-MH battery, the active material at the cathode is Ni(OH)2 and at anode is a metal hydrides
(VH2, ZrH2 & TiH2) or hydrogen storage metal alloy (LaNi5). Electrodes are made of porous
nickel foil on which active materials are coated, both electrodes are separated by using
polypropylene as separator and aqueous solution of KOH used as electrolyte. The anode and
cathode stacked in stainless steel container and are connected in series to get desired output
voltage.
The anode material should has good storage with adsorption and desorption capability of hydrogen
on charging and discharging respectively.

The battery Representation:

Representation: 𝑀𝐻/𝐾𝑂𝐻/𝑁𝑖(𝑂𝐻)2 , 𝑁𝑖𝑂(𝑂𝐻)
Potential values varies from 1.25V to 1.35V

15
The reactions occurring during charging and discharging
Charging
MH2 +2OH- 2H2O+ M + +2e-
Discharging
Anode:

Charging
2NiO(OH) + H2O + 2e- 2Ni(OH)2+ 2OH-
Discharging
Cathode:

Charging
2NiO(OH) + MH2 2Ni(OH)2+ M
Discharging
Overall:

While constructing the Ni-MH battery, cathode is in the discharged form Ni(OH)2.
Uses: It is used in Computers, Cellular Phones, camcorders, electric vehicles.
Advantages: High capacity, long cycle life, shelf life, less environmental problems

Advantages: High capacity, sealed construction and compact, eco-friendly due to Cd free, rapid
recharge, long cycle life and shelf life.
Applications: electrical vehicles, computers, camcorders and other electronic device application.

Lithium-ion battery: During the charge and discharge processes, lithium ions are
inserted or extracted from interstitial space between atomic layers within the active
material of the battery.
Simply, the Li-ion is transfers between anode and cathode through lithium Electrolyte.
Since neither the anode nor the cathode materials essentially change, the operation is safer than
that of a Lithium metal battery.

Lithium-ion battery:
Construction:
Anode: Lithium incorporated in graphite layer (Intercalated).

16
Cathode: Lithium incorporated in transition metal oxide like CoO2 or MnO2 (Intercalated) with a
conductor and binder.
Electrolyte: Lithium salt (LiPF6) in propylene carbonate- ethylene carbonate (pc-ec)
Separator: micro porous polythene film

Reactions
Charging
LixC6 6C+ xLi+ +xe-
Discharging
Anode:

Charging
LiMnO2 x Li+ + xe- + Li1-xMnO2
Discharging
Cathode:

Charging
LiMnO2 + C6 Li1-xMnO2 + C6Lix
Discharging
Overall:

Battery Representation:
LixC6 / Li+, C / LiPF6 in pc-ec / Li(y)MnO2

In Li+ battery, Li is inserted into the layered structure of both graphite (anode) and metal oxide
(cathode).
During discharge, Li+ ions are generated at anode by oxidation and inserted into the layer of metal
oxide by reduction.
During charging, Li+ ions are generated at cathode and inserted into the layer of graphite,
Thus in lithium ion battery, the cell reaction is merely the transfer of Li+ ions between the
electrodes.
It produces a potential of 3.6 – 3.7 v.

Advantages: High energy density, High voltage and less weight, more resistance to overcharge
and fast charging rate.
Applications: Li-ion batteries are used in cameras, calculators, cardiac pacemakers,
telecommunication equipment, portable radios and TVs, laptop computers, mobile phones and
aerospace application.

Dr.Venkatesha
Assistant Professor,
Dept. of Chemistry, BIT, Bengaluru-04

17