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NEET CHEMISTRYMedium

In which of the following reactions, the standard reaction entropy change (ΔS\Delta S^{\circ}) is positive, and standard Gibb's energy change (ΔG\Delta G^{\circ}) decreases sharply with increasing temperature?

A

C(graphite)+12O2(g)CO(g)\text{C(graphite)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \text{CO(g)}

B

CO(g)+12O2(g)CO2(g)\text{CO(g)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \text{CO}_2\text{(g)}

C

Mg(s)+12O2(g)MgO(s)\text{Mg(s)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \text{MgO(s)}

D

12C(graphite)+12O2(g)12CO2(g)\frac{1}{2}\text{C(graphite)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \frac{1}{2}\text{CO}_2\text{(g)}

Step-by-Step Solution

The standard Gibbs free energy change is related to the standard enthalpy and entropy changes by the equation ΔG=ΔHTΔS\Delta G^{\circ} = \Delta H^{\circ} - T\Delta S^{\circ}. For ΔG\Delta G^{\circ} to decrease sharply with an increase in temperature (TT), the entropy change of the reaction (ΔS\Delta S^{\circ}) must be positive. The sign of ΔS\Delta S^{\circ} can be predicted by looking at the change in the number of moles of gaseous species (Δng\Delta n_g). Let's analyze the given reactions:

  1. C(graphite)+12O2(g)CO(g)\text{C(graphite)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \text{CO(g)}: Here, Δng=10.5=+0.5\Delta n_g = 1 - 0.5 = +0.5. Since Δng>0\Delta n_g > 0, the entropy increases (ΔS>0\Delta S^{\circ} > 0).
  2. CO(g)+12O2(g)CO2(g)\text{CO(g)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \text{CO}_2\text{(g)}: Here, Δng=11.5=0.5\Delta n_g = 1 - 1.5 = -0.5. Since Δng<0\Delta n_g < 0, the entropy decreases (ΔS<0\Delta S^{\circ} < 0).
  3. Mg(s)+12O2(g)MgO(s)\text{Mg(s)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \text{MgO(s)}: Here, Δng=00.5=0.5\Delta n_g = 0 - 0.5 = -0.5. Since Δng<0\Delta n_g < 0, the entropy decreases (ΔS<0\Delta S^{\circ} < 0).
  4. 12C(graphite)+12O2(g)12CO2(g)\frac{1}{2}\text{C(graphite)} + \frac{1}{2}\text{O}_2\text{(g)} \rightarrow \frac{1}{2}\text{CO}_2\text{(g)}: Here, Δng=0.50.5=0\Delta n_g = 0.5 - 0.5 = 0. Since Δng=0\Delta n_g = 0, the entropy change is almost zero (ΔS0\Delta S^{\circ} \approx 0). Thus, only in the first reaction is ΔS\Delta S^{\circ} positive, causing ΔG\Delta G^{\circ} to decrease as the temperature increases.
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