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Consider the half-cell reaction for the reduction of solid manganese dioxide:

MnO₂(s) + 4H⁺(aq) + 2e⁻ → Mn²⁺(aq) + 2H₂O(l) E° = +1.23 V
Determine the electrochemical potential and the free-energy change for a system where a solution of 0.1 M Mn²⁺ at pH 1 is shaken in air at 0.2 bar pressure of O₂, resulting in the production of MnO₂ (s), with the reduction of oxygen to water. If the pH is held constant at 1 and the oxygen pressure at 0.2 bar, what will be the equilibrium concentration of Mn²⁺ in the presence of excess MnO₂?

User Danny Mor
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Final answer:

The electrochemical potential and free-energy change for the given conditions can be determined using the reduction half-reaction for MnO₂ and the Nernst equation. The equilibrium concentration of Mn²⁺ can be calculated based on the equilibrium condition of zero cell potential.

Step-by-step explanation:

To determine the electrochemical potential and the free-energy change for a system where a 0.1 M Mn²⁺ solution at pH 1 is shaken in air at 0.2 bar pressure of O₂, resulting in the production of MnO₂ (s), we must first look at the half-reactions for each species involved.

We consider the reduction half-reaction for manganese dioxide as given:

  • MnO₂(s) + 4H⁺(aq) + 2e⁻ → Mn²⁺(aq) + 2H₂O(l)

The cell potential can then be estimated using the Nernst equation to account for the non-standard conditions of Mn²⁺ concentration, pH, and O₂ pressure. The equilibrium concentration of Mn⁻²⁺ in the presence of excess MnO₂ and under the specified pH and O₂ pressure can be determined based on the requirement that the electrochemical potential of this reaction under equilibrium is zero.

To find the free-energy change, ΔG°, we use the equation:

ΔG° = -nFE°, where

  • n is the number of electrons transferred in the reaction,
  • F is the Faraday constant,
  • E° is the standard cell potential.

Considering the electrochemical cell potential at equilibrium is zero, we can then calculate the concentration at which the system will be at equilibrium.

User Tom Yeh
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