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NCERT Exemplar · Q18

Q.Out of the following pairs of electrons, identify the pairs of electrons present in degenerate orbitals : (Note: more than one of the given options may be correct.)

(i)
(a) n = 3, l = 2, m_l = -2, m_s = -1/2
(b) n = 3, l = 2, m_l = -1, m_s = -1/2
(ii)
(a) n = 3, l = 1, m_l = 1, m_s = +1/2
(b) n = 3, l = 2, m_l = 1, m_s = +1/2
(iii)
(a) n = 4, l = 1, m_l = 1, m_s = +1/2
(b) n = 3, l = 2, m_l = 1, m_s = +1/2
(iv)
(a) n = 3, l = 2, m_l = +2, m_s = -1/2
(b) n = 3, l = 2, m_l = +2, m_s = +1/2
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Degenerate orbitals have the same energy. For a hydrogen-like atom, energy depends only on nn; for multi-electron atoms, it depends on n+ln + l. Here, we compare the (n,l)(n, l) pairs of each option — only electrons with identical (n,l)(n, l) values occupy degenerate orbitals. The correct pairs are (A) and (D).

The idea of degenerate orbitals is central to understanding atomic structure. Two orbitals are degenerate when they have exactly the same energy. In a hydrogen atom, energy depends only on the principal quantum number nn, so all orbitals with the same nn are degenerate. But in multi-electron atoms — which is what we deal with in most chemistry problems — the energy of an orbital depends on both nn and the azimuthal quantum number ll, because of electron-electron repulsion and shielding. The rule is: orbitals with the same (n,l)(n, l) pair have the same energy; orbitals with different (n,l)(n, l) pairs have different energies.

The magnetic quantum number mlm_l and the spin quantum number msm_s do not affect the orbital energy in the absence of an external magnetic field. So when we ask whether two electrons are in degenerate orbitals, we only need to check whether their (n,l)(n, l) values match.

Let’s go through each option.

  1. Option (A):

    Electron (a): n=3n = 3, l=2l = 2

    Electron (b): n=3n = 3, l=2l = 2

    Both have the same (n,l)=(3,2)(n, l) = (3, 2). They differ in mlm_l and msm_s, but that doesn’t change the energy. So these two electrons are in degenerate orbitals — in fact, they are in different dd orbitals of the same 3d3d subshell.

  2. Option (B):

    Electron (a): n=3n = 3, l=1l = 1

    Electron (b): n=3n = 3, l=2l = 2

    Here ll differs: one is a 3p3p orbital, the other is a 3d3d orbital. In a multi-electron atom, 3p3p and 3d3d have different energies (the 3p3p is lower). So these are not degenerate.

  3. Option (C):

    Electron (a): n=4n = 4, l=1l = 1

    Electron (b): n=3n = 3, l=2l = 2

    Both nn and ll differ. The first is a 4p4p orbital, the second is a 3d3d orbital. Their energies are different — in fact, in multi-electron atoms, 4p4p is higher than 3d3d. Not degenerate.

  4. Option (D): …

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