JEE Advance - Chemistry (2010 - Paper 1 Offline - No. 11)

The concentration of potassium ions inside a biological cell is at least twenty times higher than the outside. The resulting potential difference across the cell is important in several processes such as transmission of nerve impulses and maintaining the ion balance. A simple model for such a concentration cell involving a metal M is :
M(s) | M+ (aq ; 0.05 molar) || M+ (aq ; 1 molar) | M(s)
For the above electrolytic cell the magnitude of the cell potential | Ecell | = 70 mV.

If the 0.05 molar solution of M+ is replaced by a 0.0025 molar M+ solution, then the magnitude of the cell potential would be :
35 mV
70 mV
140 mV
700 mV

Explanation

To understand how the concentration of ions affects the cell potential, we will first use the Nernst equation. The Nernst equation gives us a way to calculate the potential of a cell under non-standard conditions and is represented as follows:

$$ E = E^0 - \frac{RT}{nF} \ln \frac{a_{\text{Red}}}{a_{\text{Ox}}} $$

In our case, we're analyzing a concentration cell where the metal M is the same in both the anode and the cathode but with different concentrations of M+. Here, the standard potential $ E^0 $ is zero because the same substance is used as both the anode and cathode.

The cell reaction becomes:

$$ \text{M}(s) | \text{M}^{+}(0.05 \text{ M at anode}) \Longrightarrow \text{M}(s) | \text{M}^{+}(1 \text{ M at cathode}) $$

Since $ E^0 = 0 $, the Nernst equation simplifies to:

$$ E = - \frac{RT}{nF} \ln \frac{[\text{M}^{+} \text{ (cathode)}]}{[\text{M}^{+} \text{ (anode)}]} $$

Which turns into:

$$ E = - \frac{RT}{nF} \ln \frac{1}{0.05} , $$

and we can further simplify using $ \ln(\frac{1}{0.05}) = -\ln(0.05) $. Assume the reaction involves the transfer of 1 mole of electrons (n=1), the value of F (Faraday constant) is approximately 96485 C/mol, and the temperature T is 298K (room temperature). The gas constant R is 8.314 J/(mol·K). Plugging in these values:

$$ E \approx - \frac{(8.314 \, \text{J/mol·K})(298 \, \text{K})}{(1)(96485 \, \text{C/mol})} \ln(0.05) $$

This equation can be used to find the potential in volts when the concentration at anode was 0.05 M and was resulting in 70 mV.

Now, switching the anode concentration to 0.0025 M, we reapply the Nernst equation:

$$ E = - \frac{RT}{nF} \ln \frac{1}{0.0025} $$

We can see the ratio of concentrations has changed, moving from 1/0.05 to 1/0.0025. Thus, the concentration difference across the membrane has increased, which should increase the voltage according to the Nernst equation. Specifically, the ratio changed by a factor of 0.05/0.0025 = 20 times.

Given that $\ln(\frac{1}{x})$ is proportional to the voltage, when the ratio of concentration changes by twenty-fold, and because $\ln(0.0025) = -\ln(400)$ which is twice the $\ln(20)$, the potential will double. Since the initial 70 mV doubles, the new cell potential will be:

$$ E \approx 2 \times 70 \, \text{mV} = 140 \, \text{mV}. $$

Therefore, the correct answer is:

Option C: 140 mV

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