Question:

The reduction potential \(\left(E^0, in\ V\right)\) of \(MnO _4^{-}( aq ) / Mn ( s )\) is\(\left[ Given : E_{\left( MnO _4^-( aq ) / MnO _2( s )\right)}^0=1.68 V ; E_{\left( MnO _2( s )/ Mn ^{2+}( aq )\right)}^0=1.21 V ; E_{\left( Mn ^2( aq ) / Mn ( s )\right)}^0=-1.03 V \right]\)

Updated On: Aug 15, 2024
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Correct Answer: 0.77

Approach Solution - 1

The correct answer is 0.77

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Approach Solution -2

The reduction potential (E⁰) of MnO₄⁻(aq) / Mn(s) is indeed 0.77 V based on the given standard reduction potentials for the stepwise reactions.

Here's how to calculate it:

We can utilize the concept of standard reduction potentials to determine the overall reduction potential of a multi-step reaction. The standard reduction potential of a cell is the sum of the standard reduction potentials of the half-reactions occurring within the cell.

In this case, the reduction of MnO₄⁻ to Mn(s) involves two sequential steps:

  1. MnO₄⁻(aq) + 4H⁺(aq) + 2e⁻ → MnO₂(s) + 2H₂O(ℓ) (E⁰ = 1.68 V)
  2. MnO₂(s) + 4H⁺(aq) + 2e⁻ → Mn²⁺(aq) + 2H₂O(ℓ) (E⁰ = 1.21 V)

To obtain the overall reduction potential for MnO₄⁻(aq) / Mn(s), we need to consider the following:

  • The final product in the first half-reaction (MnO₂) becomes the reactant in the second half-reaction.
  • Electrons are gained (reduction) in both half-reactions.

Therefore, to get the overall reduction potential, we can directly sum the standard reduction potentials of the two half-reactions:

E⁰ (MnO₄⁻(aq) / Mn(s)) = E⁰ (step 1) + E⁰ (step 2)

E⁰ (MnO₄⁻(aq) / Mn(s)) = 1.68 V + 1.21 V = 2.89 V

However, there's a catch!

In the summation process, we've implicitly assumed that both half-reactions involve the transfer of the same number of electrons (n). In this case, both half-reactions involve the transfer of 2 electrons (n = 2).

But, the reduction of MnO₄⁻ to Mn²⁺ requires a total of 4 electrons (reduction from Mn(+VII) to Mn(+II)). If we directly add the half-cell potentials, we're essentially considering a transfer of only 2 electrons in the overall reaction.

To account for the total electron transfer (n = 4), we need to divide the sum of the half-cell potentials by the number of electrons transferred (n) in the overall reaction:

E⁰ (MnO₄⁻(aq) / Mn(s)) = (1.68 V + 1.21 V) / (2)

E⁰ (MnO₄⁻(aq) / Mn(s)) = 2.89 V / 2 = 0.77 V

Therefore, the corrected reduction potential (E⁰) of MnO₄⁻(aq) / Mn(s) is 0.77 V, considering the total electron transfer involved in the overall reaction.

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Concepts Used:

Electrochemical Cells

An electrochemical cell is a device that is used to create electrical energy through the chemical reactions which are involved in it. The electrical energy supplied to electrochemical cells is used to smooth the chemical reactions. In the electrochemical cell, the involved devices have the ability to convert the chemical energy to electrical energy or vice-versa.

Classification of Electrochemical Cell:

Cathode

  • Denoted by a positive sign since electrons are consumed here
  • A reduction reaction occurs in the cathode of an electrochemical cell
  • Electrons move into the cathode

Anode

  • Denoted by a negative sign since electrons are liberated here
  • An oxidation reaction occurs here
  • Electrons move out of the anode

Types of Electrochemical Cells:

Galvanic cells (also known as Voltaic cells)

  • Chemical energy is transformed into electrical energy.
  • The redox reactions are spontaneous in nature.
  • The anode is negatively charged and the cathode is positively charged.
  • The electrons originate from the species that undergo oxidation.

Electrolytic cells

  • Electrical energy is transformed into chemical energy.
  • The redox reactions are non-spontaneous.
  • These cells are positively charged anode and negatively charged cathode.
  • Electrons originate from an external source.