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NCERT Exemplar · Q27

Q.The arrangement of orbitals on the basis of energy is based upon their (n+l) value. Lower the value of (n+l), lower is the energy. For orbitals having same values of (n+l), the orbital with lower value of n will have lower energy.
I. Based upon the above information, arrange the following orbitals in the increasing order of energy.

(a) 1s, 2s, 3s, 2p
(b) 4s, 3s, 3p, 4d
(c) 5p, 4d, 5d, 4f, 6s
(d) 5f, 6d, 7s, 7p
II. Based upon the above information, solve the questions given below :
(a) Which of the following orbitals has the lowest energy?
4d, 4f, 5s, 5p
(b) Which of the following orbitals has the highest energy?
5p, 5d, 5f, 6s, 6p
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The energy of an orbital is determined by the (n+ℓ)(n+\ell) rule: lower (n+ℓ)(n+\ell) means lower energy; if (n+ℓ)(n+\ell) is equal, the orbital with the smaller nn has lower energy. Using this rule, we order the given orbitals and answer the comparison questions.

Why the (n+ℓ)(n+\ell) Rule Works

The energy of an orbital in a multi-electron atom depends not only on the principal quantum number nn but also on the azimuthal quantum number ℓ\ell. This is because electrons in orbitals with higher ℓ\ell experience more shielding from inner electrons, reducing the effective nuclear charge they feel. The (n+ℓ)(n+\ell) rule (also called the n+l rule or Aufbau principle) captures this: orbitals with a smaller (n+ℓ)(n+\ell) value are lower in energy. When two orbitals have the same (n+ℓ)(n+\ell), the one with the smaller nn is lower in energy because it is closer to the nucleus on average.

E∝(n+ℓ)(lower is lower energy)E \propto (n+\ell) \quad \text{(lower is lower energy)}

(n+ℓ) equal  ⟹  lower n gives lower energy(n+\ell) \text{ equal} \implies \text{lower } n \text{ gives lower energy}

Let’s apply this step by step.


I. Arranging orbitals in increasing order of energy

1. (a) 1s, 2s, 3s, 2p

Compute (n+ℓ)(n+\ell) for each:

  • 1s: n=1, ℓ=0  ⟹  1+0=1n=1,\ \ell=0 \implies 1+0 = 1
  • 2s: n=2, ℓ=0  ⟹  2+0=2n=2,\ \ell=0 \implies 2+0 = 2
  • 3s: n=3, ℓ=0  ⟹  3+0=3n=3,\ \ell=0 \implies 3+0 = 3
  • 2p: n=2, ℓ=1  ⟹  2+1=3n=2,\ \ell=1 \implies 2+1 = 3

Order by (n+ℓ)(n+\ell): 1s (1) < 2s (2) < 3s (3) and 2p (3). Since 3s and 2p both have (n+ℓ)=3(n+\ell)=3, compare nn: 2p has n=2n=2, 3s has n=3n=3, so 2p is lower.

Increasing order: 1s < 2s < 2p < 3s

Watch out

A common mistake is to forget that when (n+ℓ)(n+\ell) is equal, the orbital with smaller nn wins. Here 2p comes before 3s even though both have (n+ℓ)=3(n+\ell)=3.

2. (b) 4s, 3s, 3p, 4d

Compute (n+ℓ)(n+\ell):

  • 4s: 4+0=44+0 = 4
  • 3s: 3+0=33+0 = 3
  • 3p: 3+1=43+1 = 4
  • 4d: 4+2=64+2 = 6

Order by (n+ℓ)(n+\ell): 3s (3) < 4s (4) and 3p (4) < 4d (6). For 4s and 3p, both have (n+ℓ)=4(n+\ell)=4: 3p has n=3n=3, 4s has n=4n=4, so 3p is lower.

Increasing order: 3s < 3p < 4s < 4d

Tip

Notice that 4s (n+ℓ=4n+\ell=4) comes before 3d (n+ℓ=5n+\ell=5) in the Aufbau sequence, but here 3p is even lower because its nn is smaller.

3. (c) 5p, 4d, 5d, 4f, 6s

Compute (n+ℓ)(n+\ell):

  • 5p: 5+1=65+1 = 6
  • 4d: 4+2=64+2 = 6
  • 5d: 5+2=75+2 = 7
  • 4f: 4+3=74+3 = 7
  • 6s: 6+0=66+0 = 6

Group by (n+ℓ)(n+\ell):

  • (n+ℓ)=6(n+\ell)=6: 5p, 4d, 6s
  • (n+ℓ)=7(n+\ell)=7: 5d, 4f

Within (n+ℓ)=6(n+\ell)=6, compare nn: 4d (n=4n=4) < 5p (n=5n=5) < 6s (n=6n=6).

Within (n+ℓ)=7(n+\ell)=7, compare nn: 4f (n=4n=4) < 5d (n=5n=5).

Increasing order: 4d < 5p < 6s < 4f < 5d

Note

4f and 5d both have (n+ℓ)=7(n+\ell)=7, but 4f has smaller nn, so it is lower in energy. This is why the 4f subshell fills before 5d in the lanthanides.

4. (d) 5f, 6d, 7s, 7p

Compute (n+ℓ)(n+\ell):

  • 5f: 5+3=85+3 = 8
  • 6d: 6+2=86+2 = 8
  • 7s: 7+0=77+0 = 7
  • 7p: 7+1=87+1 = 8 …

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