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Nernst Equation: Cell Potential Under Nonstandard Conditions

Using the nernst equation at \(25^\circ\mathrm{C}\), what is the cell potential for \(\mathrm{Zn(s)\,|\,Zn^{2+}(0.010\,M)\,||\,Cu^{2+}(1.00\,M)\,|\,Cu(s)}\) given \(E^\circ(\mathrm{Cu^{2+}/Cu})=+0.34\,\mathrm{V}\) and \(E^\circ(\mathrm{Zn^{2+}/Zn})=-0.76\,\mathrm{V}\)?

Subject: General Chemistry Chapter: Electrochemistry Topic: Electrode Potential at Nonstandard Conditions Answer included
nernst equation Nernst equation electrochemistry cell potential electrode potential nonstandard conditions reaction quotient Q galvanic cell
Accepted answer Answer included

Problem

Consider the galvanic cell \(\mathrm{Zn(s)\,|\,Zn^{2+}(0.010\,M)\,||\,Cu^{2+}(1.00\,M)\,|\,Cu(s)}\) at \(25^\circ\mathrm{C}\). Using the nernst equation, determine the cell potential \(E\) given \(E^\circ(\mathrm{Cu^{2+}/Cu})=+0.34\,\mathrm{V}\) and \(E^\circ(\mathrm{Zn^{2+}/Zn})=-0.76\,\mathrm{V}\).

What “nonstandard” means: concentrations are not always \(1.00\,\mathrm{M}\), thus \(E \neq E^\circ\).

Concentration Effect: Since \([\mathrm{Zn^{2+}}]\) is low, Le Chatelier’s principle suggests a higher driving force for oxidation, increasing the cell potential.

Solution

1) Write the overall redox reaction and identify \(n\)

The half-reactions for this cell are:

  • Anode (Oxidation): \(\mathrm{Zn(s) \rightarrow Zn^{2+}(aq) + 2e^-}\)
  • Cathode (Reduction): \(\mathrm{Cu^{2+}(aq) + 2e^- \rightarrow Cu(s)}\)

Adding these gives the net reaction:

\[ \mathrm{Zn(s) + Cu^{2+}(aq) \rightarrow Zn^{2+}(aq) + Cu(s)} \]

The number of electrons transferred is \(n=2\).

2) Compute the standard cell potential \(E^\circ_{\text{cell}}\)

Use \(E^\circ_{\text{cell}} = E^\circ_{\text{cathode}} - E^\circ_{\text{anode}}\):

\[ E^\circ_{\text{cell}} = (+0.34\,\mathrm{V}) - (-0.76\,\mathrm{V}) = 1.10\,\mathrm{V} \]

3) Determine the reaction quotient \(Q\)

Solids (Zn and Cu) are excluded from the mass-action expression:

\[ Q = \frac{[\mathrm{Zn^{2+}}]}{[\mathrm{Cu^{2+}}]} = \frac{0.010}{1.00} = 0.010 \]

Calculating the base-10 logarithm:

\[ \log_{10}(Q) = \log_{10}(0.010) = -2.00 \]

4) Apply the Nernst Equation

At \(25^\circ\mathrm{C}\) (standard lab temperature), we use the simplified form:

\[ E = E^\circ - \frac{0.0592}{n}\log_{10}(Q) \]

Inserting the values:

\[ E = 1.10 - \frac{0.0592}{2}(-2.00) = 1.10 + 0.0592 = 1.1592\,\mathrm{V} \]

Result: \(E \approx 1.16\,\mathrm{V}\). The potential is increased by roughly \(60\,\mathrm{mV}\) due to the low zinc concentration.

Visualization: Nernst Equation Dashboard

Nernst Equation Dashboard A premium visualization showing the Zn-Cu cell schematic and the relationship between cell potential and concentration. Galvanic Cell: Zn | Cu Anode: Zn [Zn²⁺] = 0.01M Cathode: Cu [Cu²⁺] = 1.0M 2e⁻ flow Sensitivity to \(\log_{10}Q\) \(\log_{10}Q\) Potential \(E\) (V) -4 -2 0 2 4 1.00 1.10 1.20 E° = 1.10V Q = 0.010 E ≈ 1.16V \(E = E^\circ - \frac{0.0592}{n} \log_{10} Q \quad \rightarrow \quad 1.10 - \frac{0.0592}{2}(-2) = 1.159\,\mathrm{V}\)
Integrated Nernst Equation dashboard: The left panel shows the physical setup of the Zn-Cu cell with unequal concentrations. The right panel tracks how the cell potential (\(E\)) linearly scales with the logarithm of the reaction quotient (\(Q\)), increasing the voltage as the zinc ion concentration drops.

Summary Table

Quantity Meaning Value
\(E^\circ_{\text{cell}}\) Standard cell potential \(1.10\,\mathrm{V}\)
\(n\) Electrons transferred \(2\)
\(Q\) Reaction quotient \(0.010\)
\(\log_{10}(Q)\) Base-10 logarithm of \(Q\) \(-2.00\)
\(E\) Nonstandard potential \(\approx 1.16\,\mathrm{V}\)

Final Answer

Using the Nernst equation at \(25^\circ\mathrm{C}\) with \(E^\circ_{\text{cell}}=1.10\,\mathrm{V}\), \(n=2\), and \(Q=\frac{0.010}{1.00}=0.010\), the resulting cell potential is \(E \approx 1.16\,\mathrm{V}\).

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