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Exercises · 3.36

Q.The size of isoelectronic species — F−F^-, Ne and Na+Na^+ is affected by

(a) nuclear charge (Z)
(b) valence principal quantum number (n)
(c) electron-electron interaction in the outer orbitals
(d) none of the factors because their size is the same.
Telangana TsbieTextbookSubjective· 1mImportance★★★★★est
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For isoelectronic species, the ionic/atomic radius is determined solely by the effective nuclear charge (ZeffZ_{\text{eff}}) — the higher the nuclear charge, the more strongly the electrons are pulled in, making the radius smaller. Among F−F^-, Ne, and Na+Na^+, the order of decreasing size is F−>Ne>Na+F^- > \text{Ne} > Na^+, so option (a) is correct.

Why effective nuclear charge is the key

When two or more species have the same number of electrons (isoelectronic), the electron-electron repulsion is identical in each case — the same number of electrons occupy the same set of orbitals. The only thing that changes is the nuclear charge ZZ (the number of protons). A higher ZZ pulls the electron cloud inward more strongly, shrinking the radius. The valence principal quantum number nn is the same for all three (they all have electrons in the n=2n=2 shell), so it cannot explain the size difference. Electron-electron interaction is also identical because the electron count is the same. Therefore, the deciding factor is nuclear charge.

For isoelectronic species, radius ∝1Zeff\propto \frac{1}{Z_{\text{eff}}}, where Zeff=Z−σZ_{\text{eff}} = Z - \sigma (Slater’s rules). Since σ\sigma is nearly constant for the same electron configuration, ZeffZ_{\text{eff}} increases with ZZ.

Step-by-step reasoning

  1. Identify the electron configuration.

    F−F^- has 9 protons and 10 electrons. Ne has 10 protons and 10 electrons. Na+Na^+ has 11 protons and 10 electrons. All three have the same electron configuration: 1s2 2s2 2p61s^2\,2s^2\,2p^6 (the neon core). They are isoelectronic.

  2. Compare nuclear charges.

    • F−F^-: Z=9Z = 9
    • Ne: Z=10Z = 10
    • Na+Na^+: Z=11Z = 11

    The number of electrons is fixed at 10, so the shielding constant σ\sigma (from the 1s and 2s/2p electrons) is essentially the same for all three. Hence ZeffZ_{\text{eff}} increases directly with ZZ.

  3. Relate ZeffZ_{\text{eff}} to size.

    A higher ZeffZ_{\text{eff}} means a stronger pull on the valence electrons, reducing the atomic/ionic radius. So the species with the smallest ZZ (least pull) will be the largest, and the one with the largest ZZ (strongest pull) will be the smallest.

    • F−F^- (Z=9Z=9): lowest ZeffZ_{\text{eff}} → largest radius
    • Ne (Z=10Z=10): intermediate ZeffZ_{\text{eff}} → intermediate radius
    • Na+Na^+ (Z=11Z=11): highest ZeffZ_{\text{eff}} → smallest radius …

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