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Exercises · 3.20

Q.Which of the following pairs of elements would have a more negative electron gain enthalpy?

(i) O or F
(ii) F or Cl
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  1. F has a more negative electron gain enthalpy than O;
  2. Cl has a more negative electron gain enthalpy than F.

What makes electron gain enthalpy more negative?

Electron gain enthalpy is the energy change when a gaseous atom accepts an electron. A more negative value means more energy is released, i.e. the atom accepts the electron more readily. Two opposing factors decide the value:

  • Nuclear charge / effective attraction — a stronger pull on the incoming electron makes the process more exothermic (more negative).
  • Size and electron–electron repulsion — in a very small atom the incoming electron enters a compact subshell already crowded with electrons, so repulsion opposes the attraction and makes the value less negative than expected.

(i) O or F

Oxygen (Group 16) and fluorine (Group 17) are neighbours in Period 2. Fluorine has the higher nuclear charge (Z=9Z = 9 vs 88) and is slightly smaller, so it attracts the incoming electron more strongly. This nuclear-charge advantage outweighs the extra repulsion, so fluorine releases more energy.

  • ΔegH(O)≈−141 kJ mol−1\Delta_{eg}H(\text{O}) \approx -141\ \text{kJ mol}^{-1}
  • ΔegH(F)≈−328 kJ mol−1\Delta_{eg}H(\text{F}) \approx -328\ \text{kJ mol}^{-1}

Fluorine's value is more negative.

(ii) F or Cl …

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