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Exercises · 2.62

Q.The quantum numbers of six electrons are given below. Arrange them in order of increasing energies. If any of these combination(s) has/have the same energy list them: 1. n = 4, l = 2, mlm_l = -2, msm_s = −12-\tfrac{1}{2}; 2. n = 3, l = 2, mlm_l = 1, msm_s = +12+\tfrac{1}{2}; 3. n = 4, l = 1, mlm_l = 0, msm_s = +12+\tfrac{1}{2}; 4. n = 3, l = 2, mlm_l = -2, msm_s = −12-\tfrac{1}{2}; 5. n = 3, l = 1, mlm_l = -1, msm_s = +12+\tfrac{1}{2}; 6. n = 4, l = 1, mlm_l = 0, msm_s = +12+\tfrac{1}{2}.

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The energy of an electron in a multi-electron atom depends primarily on the principal quantum number nn and the azimuthal quantum number ll via the (n+l)(n+l) rule. For equal (n+l)(n+l), the lower nn gives lower energy. Applying this rule, the increasing order of energies is: 5 < 2 = 4 < 3 = 6 < 1. Electrons 2 and 4 have the same energy; electrons 3 and 6 have the same energy.

The key idea here is that in multi-electron atoms, the simple hydrogen-like energy ordering (where energy depends only on nn) breaks down due to electron-electron repulsion and shielding. The (n+l)(n+l) rule (also called the Aufbau principle or Madelung rule) gives the correct ordering for filling orbitals: lower (n+l)(n+l) means lower energy; if (n+l)(n+l) is equal, lower nn means lower energy.

Let’s apply this step by step.

  1. Identify the (n+l)(n+l) value for each electron.

    For electron 1: n=4n=4, l=2l=2 → n+l=4+2=6n+l = 4+2 = 6.

    For electron 2: n=3n=3, l=2l=2 → n+l=3+2=5n+l = 3+2 = 5.

    For electron 3: n=4n=4, l=1l=1 → n+l=4+1=5n+l = 4+1 = 5.

    For electron 4: n=3n=3, l=2l=2 → n+l=3+2=5n+l = 3+2 = 5.

    For electron 5: n=3n=3, l=1l=1 → n+l=3+1=4n+l = 3+1 = 4.

    For electron 6: n=4n=4, l=1l=1 → n+l=4+1=5n+l = 4+1 = 5.

  2. Order by (n+l)(n+l) first.

    The smallest (n+l)(n+l) is 4 (electron 5). Next comes (n+l)=5(n+l)=5 (electrons 2, 3, 4, 6). The largest is (n+l)=6(n+l)=6 (electron 1). So electron 5 has the lowest energy, and electron 1 has the highest.

  3. Resolve ties using nn.

    Among electrons with (n+l)=5(n+l)=5, we compare nn:

    • Electrons 2 and 4 have n=3n=3.
    • Electrons 3 and 6 have n=4n=4. Since lower nn gives lower energy when (n+l)(n+l) is equal, electrons 2 and 4 are lower in energy than electrons 3 and 6.
  4. Check for identical energies. …

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