Verified Solution • 2025–26 Session moderate

QJEEM24Chaff5: JEE Main 2024 Chemistry - Class 12 JEEM24Chaff5 Solution: The emf of cell is at . It could be increased by :

The emf of cell Tl∣Tl+(0.001M)∣Cu2+(0.01M)∣Cu\mathrm{Tl}\left|\underset{(0.001 \mathrm{M})}{\mathrm{Tl}^{+}}\right| \underset{(0.01 \mathrm{M})}{\mathrm{Cu}^{2+}} \mid \mathrm{Cu} is 0.83 V0.83 \mathrm{~V} at 298 K298 \mathrm{~K} . It could be increased by :

Multiple Choice Options

  • A increasing concentration of Tl+\mathrm{Tl}^{+} ions
  • B increasing concentration of Cu2+\mathrm{Cu}^{2+} ions
  • C increasing concentration of both Tl+\mathrm{Tl}^{+} and Cu2+\mathrm{Cu}^{2+} ions
  • D decreasing concentration of both Tl+\mathrm{Tl}^{+} and Cu2+\mathrm{Cu}^{2+} ions

Step-by-Step Verified Solution

To determine how the emf of the cell, Tl∣Tl+(0.001M)∣Cu2+(0.01M)∣Cu\mathrm{Tl}\left|\underset{(0.001 \mathrm{M})}{\mathrm{Tl}^{+}}\right| \underset{(0.01 \mathrm{M})}{\mathrm{Cu}^{2+}} \mid \mathrm{Cu} , can be increased, we can use the Nernst equation. The Nernst equation for this electrochemical cell is given by:

Ecell=Ecell∘−0.0591nlog⁡([Tl+][Cu2+])E_{\text{cell}} = E_{\text{cell}}^\circ - \frac{0.0591}{n} \log \left( \frac{[\mathrm{Tl}^{+}]}{[\mathrm{Cu}^{2+}]} \right)

where:

  • EcellE_{\text{cell}} is the emf of the cell.
  • Ecell∘E_{\text{cell}}^\circ is the standard emf of the cell.
  • nn is the number of moles of electrons transferred in the cell reaction; here, n=2n = 2 .
  • [Tl+][\mathrm{Tl}^{+}] is the concentration of thallium ions.
  • [Cu2+][\mathrm{Cu}^{2+}] is the concentration of copper ions.

Given that the emf of the cell can be expressed in terms of the concentration of the ions involved, we can see that increasing the concentration of [Cu2+][\mathrm{Cu}^{2+}] or decreasing the concentration of [Tl+][\mathrm{Tl}^{+}] will affect the logarithmic term in the Nernst equation:

Ecell=Ecell∘−0.05912log⁡(0.0010.01)E_{\text{cell}} = E_{\text{cell}}^\circ - \frac{0.0591}{2} \log \left( \frac{0.001}{0.01} \right)

To increase the emf ( EcellE_{\text{cell}} ) of the cell, it is beneficial to have a less negative (or more positive) correction term. This can be achieved by:

  • Increasing the concentration of [Cu2+][\mathrm{Cu}^{2+}] ions: This makes the term inside the logarithm smaller (since we are dividing by a larger number), which in turn makes the logarithmic term less negative.

Therefore, the correct answer is:

Option B: increasing concentration of Cu2+\mathrm{Cu}^{2+} ions

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