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Chemical Bonding and Molecular Structure question

2025 · Shift 1 · Q5
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Chemical Bonding and Molecular Structure question

2025 · Shift 1 · Q5

JEE AdvancedChemistryChemical Bonding and Molecular StructureMultiple correct+4 / −2
Regarding the molecular orbital (MO) energy levels for homonuclear diatomic molecules, the INCORRECT statement(s) is(are)
  1. A
    Bond order of Ne2Ne_2Ne2​ is zero.
  2. B
    The highest occupied molecular orbital (HOMO) of F2F_2F2​ is σ\sigmaσ-type.
  3. C
    Bond energy of O2+O_2^{+}O2+​ is smaller than the bond energy of O2O_2O2​.
  4. D
    Bond length of Li2Li_2Li2​ is larger than the bond length of B2B_2B2​.
View written solutionFree

Correct answer: B, C

The user wants me to identify the incorrect statements about the molecular orbital (MO) energy levels of homonuclear diatomic molecules.

Let's analyze each statement based on Molecular Orbital Theory.

The general order of MO energy levels for homonuclear diatomic molecules is:

  1. For Li2Li_2Li2​ to N2N_2N2​ (due to s-p mixing): σ1s<σ∗1s<σ2s<σ∗2s<(π2px=π2py)<σ2pz<(π∗2px=π∗2py)<σ∗2pz\sigma 1s < \sigma^* 1s < \sigma 2s < \sigma^* 2s < (\pi 2p_x = \pi 2p_y) < \sigma 2p_z < (\pi^* 2p_x = \pi^* 2p_y) < \sigma^* 2p_zσ1s<σ∗1s<σ2s<σ∗2s<(π2px​=π2py​)<σ2pz​<(π∗2px​=π∗2py​)<σ∗2pz​
  2. For O2O_2O2​, F2F_2F2​, Ne2Ne_2Ne2​ (s-p mixing is less significant): σ1s<σ∗1s<σ2s<σ∗2s<σ2pz<(π2px=π2py)<(π∗2px=π∗2py)<σ∗2pz\sigma 1s < \sigma^* 1s < \sigma 2s < \sigma^* 2s < \sigma 2p_z < (\pi 2p_x = \pi 2p_y) < (\pi^* 2p_x = \pi^* 2p_y) < \sigma^* 2p_zσ1s<σ∗1s<σ2s<σ∗2s<σ2pz​<(π2px​=π2py​)<(π∗2px​=π∗2py​)<σ∗2pz​

The bond order (B.O.) is calculated as: B.O.=12(Nb−Na)B.O. = \frac{1}{2} (N_b - N_a)B.O.=21​(Nb​−Na​) where NbN_bNb​ is the number of electrons in bonding molecular orbitals and NaN_aNa​ is the number of electrons in anti-bonding molecular orbitals.

Analysis of Statement A:

A: Bond order of Ne2Ne_2Ne2​ is zero.

  1. Neon (Ne) has an atomic number of 10. A Ne2Ne_2Ne2​ molecule has 2×10=202 \times 10 = 202×10=20 electrons.
  2. The electronic configuration of Ne2Ne_2Ne2​ is: (σ1s)2(σ∗1s)2(σ2s)2(σ∗2s)2(σ2pz)2(π2px)2(π2py)2(π∗2px)2(π∗2py)2(σ∗2pz)2(\sigma 1s)^2 (\sigma^* 1s)^2 (\sigma 2s)^2 (\sigma^* 2s)^2 (\sigma 2p_z)^2 (\pi 2p_x)^2 (\pi 2p_y)^2 (\pi^* 2p_x)^2 (\pi^* 2p_y)^2 (\sigma^* 2p_z)^2(σ1s)2(σ∗1s)2(σ2s)2(σ∗2s)2(σ2pz​)2(π2px​)2(π2py​)2(π∗2px​)2(π∗2py​)2(σ∗2pz​)2
  3. Number of bonding electrons (NbN_bNb​) = 2+2+2+2+2=102+2+2+2+2 = 102+2+2+2+2=10.
  4. Number of anti-bonding electrons (NaN_aNa​) = 2+2+2+2+2=102+2+2+2+2 = 102+2+2+2+2=10.
  5. Bond order = 12(10−10)=0\frac{1}{2} (10 - 10) = 021​(10−10)=0.
  6. A bond order of zero indicates that the molecule is not stable.
  7. Thus, the statement is CORRECT.

Analysis of Statement B:

B: The highest occupied molecular orbital (HOMO) of F2F_2F2​ is σ\sigmaσ-type.

  1. Fluorine (F) has an atomic number of 9. An F2F_2F2​ molecule has 2×9=182 \times 9 = 182×9=18 electrons.
  2. The electronic configuration of F2F_2F2​ is: (σ1s)2(σ∗1s)2(σ2s)2(σ∗2s)2(σ2pz)2(π2px)2(π2py)2(π∗2px)2(π∗2py)2(\sigma 1s)^2 (\sigma^* 1s)^2 (\sigma 2s)^2 (\sigma^* 2s)^2 (\sigma 2p_z)^2 (\pi 2p_x)^2 (\pi 2p_y)^2 (\pi^* 2p_x)^2 (\pi^* 2p_y)^2(σ1s)2(σ∗1s)2(σ2s)2(σ∗2s)2(σ2pz​)2(π2px​)2(π2py​)2(π∗2px​)2(π∗2py​)2
  3. The highest occupied molecular orbitals (HOMO) are the degenerate π∗2px\pi^* 2p_xπ∗2px​ and π∗2py\pi^* 2p_yπ∗2py​ orbitals.
  4. These are π\piπ-type orbitals, not σ\sigmaσ-type.
  5. Thus, the statement is INCORRECT.

Analysis of Statement C:

C: Bond energy of O2+O_2^{+}O2+​ is smaller than the bond energy of O2O_2O2​.

  1. Bond energy is directly proportional to bond order. Higher bond order implies higher bond energy.
  2. For O2O_2O2​ (16 electrons): The electronic configuration is ...(σ2pz)2(π2px)2(π2py)2(π∗2px)1(π∗2py)1(\sigma 2p_z)^2 (\pi 2p_x)^2 (\pi 2p_y)^2 (\pi^* 2p_x)^1 (\pi^* 2p_y)^1(σ2pz​)2(π2px​)2(π2py​)2(π∗2px​)1(π∗2py​)1. Nb=10N_b = 10Nb​=10, Na=6N_a = 6Na​=6. Bond order = 12(10−6)=2.0\frac{1}{2}(10-6) = 2.021​(10−6)=2.0.
  3. For O2+O_2^{+}O2+​ (15 electrons): One electron is removed from the highest energy orbital of O2O_2O2​, which is an anti-bonding π∗\pi^*π∗ orbital. The configuration is ...(σ2pz)2(π2px)2(π2py)2(π∗2px)1(\sigma 2p_z)^2 (\pi 2p_x)^2 (\pi 2p_y)^2 (\pi^* 2p_x)^1(σ2pz​)2(π2px​)2(π2py​)2(π∗2px​)1. Nb=10N_b = 10Nb​=10, Na=5N_a = 5Na​=5. Bond order = 12(10−5)=2.5\frac{1}{2}(10-5) = 2.521​(10−5)=2.5.
  4. Since the bond order of O2+O_2^{+}O2+​ (2.5) is greater than the bond order of O2O_2O2​ (2.0), the bond energy of O2+O_2^{+}O2+​ is larger than the bond energy of O2O_2O2​.
  5. The statement claims the opposite.
  6. Thus, the statement is INCORRECT.

Analysis of Statement D:

D: Bond length of Li2Li_2Li2​ is larger than the bond length of B2B_2B2​.

  1. Bond length is inversely proportional to bond order.
  2. For Li2Li_2Li2​ (6 electrons): The electronic configuration is (σ1s)2(σ∗1s)2(σ2s)2(\sigma 1s)^2 (\sigma^* 1s)^2 (\sigma 2s)^2(σ1s)2(σ∗1s)2(σ2s)2. Nb=4N_b = 4Nb​=4, Na=2N_a = 2Na​=2. Bond order = 12(4−2)=1\frac{1}{2}(4-2) = 121​(4−2)=1.
  3. For B2B_2B2​ (10 electrons): The electronic configuration is (σ1s)2(σ∗1s)2(σ2s)2(σ∗2s)2(π2px)1(π2py)1(\sigma 1s)^2 (\sigma^* 1s)^2 (\sigma 2s)^2 (\sigma^* 2s)^2 (\pi 2p_x)^1 (\pi 2p_y)^1(σ1s)2(σ∗1s)2(σ2s)2(σ∗2s)2(π2px​)1(π2py​)1. Nb=6N_b = 6Nb​=6, Na=4N_a = 4Na​=4. Bond order = 12(6−4)=1\frac{1}{2}(6-4) = 121​(6−4)=1.
  4. Both Li2Li_2Li2​ and B2B_2B2​ have a bond order of 1. When bond orders are the same, bond length is determined by the atomic size of the constituent atoms.
  5. Lithium (Li) and Boron (B) are in the same period (Period 2). Atomic radius decreases across a period from left to right. Therefore, the atomic radius of Li is larger than that of B.
  6. Consequently, the bond length of Li2Li_2Li2​ will be larger than the bond length of B2B_2B2​.
  7. Thus, the statement is CORRECT.

The question asks for the INCORRECT statements, which are B and C.

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