Electro - 2

Electrode potential

When a metal is put into the solution of its ions,

electrode potential is established because of the
following equilibrium.

2+
Cu + 2e ⇌ Cu (s)

Standard Hydrogen Electrode (S.H.E)

Standard conditions used are,

+ -3
 [H ] = 1 moldm
 Pressure = 1 atm/ 101kPa
 Temperature = 298K

Electrode potential of S.H.E is 0V. Therefore we use this as a

reference electrode to measure potential of other electrodes.

2+
Cu + 2e ⇌ Cu (s)

Standard Electrode Potential

What is standard electrode potential?

Standard electrode potential is the potential of an electrode compared to that of S.H.E electrode,
-3
measured using 1 moldm concentration, 1 atm pressure and 298 K temperature.

All the standard electrode potential data is available and these are measured using standard conditions,

-3
 Concentration = 1 moldm
 Pressure = 1 atm/ 101kPa
 Temperature = 298K

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Let’s look at how standard potentials of different types of electrodes are measured using S.H.E

1. Metal/Metal ion electrode

2+
Eg: Cu /Cu

Reaction

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2. Non metal/non metal ion

-
Eg: Cl2/Cl

Reaction

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3. Metal ion/metal ion

2+ 3+
Eg: Fe /Fe

Reaction

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 0 0
E values are useful in many ways. Using E values,

1. Predicting Ecell (cell potential)

Remember,

0
 Electrode with highest positive E value, always get reduced.

Ecell = E0 reduction – E0 oxidation

2+ 2+
Q) Draw a diagram and Calculate Ecell of a cell containing Cu /Cu and Zn /Zn electrodes. (Write down
complete cell reaction using half cell reactions)

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 2. Deciding cathode and anode of a given cell

Anode – always oxidation occur at anode

Cathode – always reduction occur at cathode

2+ 3+ -
Q) Decide which is the cathode and anode of a cell containing Fe /Fe and Cl2/Cl electrodes.

3. Deciding electron flow

Electrons are given out during oxidation. Therefore

electrons will flow from anode to cathode.

2+ 3+ -
Q) Explain electron flow of a cell containing Fe /Fe and Cl2/Cl electrodes.

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 4. Deciding feasibility of a given redox reaction

If Ecell is a positive (+) value, reaction is feasible

-
Q) Calculate and explain whether reduction of Cl2 using F is feasible or not.

-
Q) Calculate and explain whether reduction of F2 using I is feasible or not.

2+
Q) Calculate and explain whether reduction of Cr to Cr, using K is feasible or not.

Q) Cu(II) aqueous solution is blue colour, Cu(NH3)4 is a dark blue solution, Fe(II) is a pale green solution
and Fe(III) aqueous solution is pale brown in colour.

When CuSO4 was reacted with Fe, the solution turned from blue to pale brown. But when Cu(NH 3)4 was
reacted with Fe, the solution turned dark blue to pale green.

Write the redox reactions to explain these observations and then explain why Cu(NH 3)4 did not produce a
pale brown solution.

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 -3
Remember that the electrode potentials are measured using solutions containing 1 moldm
concentration.

What if we change the concentration? Then the potential will change.

We can use,

 Le Chatelier’s principle to understand this qualitatively

 Nernst’s equation to understand this quantitatively

1. Using Le Chatelier’s principle

0
 Explain the change in the position of the equilibrium for the following reaction and the E value if
-3 2+
0.001 moldm Cu is used.

0
 Explain the change in the position of the equilibrium for the following reaction and to the E value
more ammonia was added to the solution.

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 2. Using Nernst’s equation

0
E = E + RT ln [oxidized form]
ZF [reduced form]

At room temperature,

0
E = E + 0.059 log [oxidized form]
Z [reduced form]

2+ 2+ -3
 Calculate electrode potential of Cu / Cu electrode if concentration of Cu used is 0.001 moldm .
(note that the concentration of solids are taken as 1)

+ + -3
 Calculate electrode potential of H / H2 electrode if concentration of H used is 0.001 moldm . (note
that the concentration of gasses are taken as 1)

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2015/Oct/43

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Cells and Batteries

 Rechargeable cells

4+
Car battery is a secondary cell. It contains Pb and Pb (PbO2) electrode immersed in H2SO4. There are 6
cells and each cell has a voltage of 2 V therefore total voltage is 12 V.

When sulfuric concentration is decreased we need to refill sulfuric. Formation of PbSO 4 during the redox
reaction is an issue in car battery because PbSO4 covers electrodes and interfere transfer of electrons.

 Solid state cells

Ex : button cells

Li or Zn is the (-)ve pole and I2 or MnO2 is (+)ve pole

Q) Write down half cell reactions for Li/I2 button cell and find cell potential

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  Hydrogen oxygen fuel cell

Fuel cell – electro chemical cell in which a fuel gives up an electron at one electrode.

2015/Oct/43

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