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P Block Elements question

2018 · Shift 1 · Q4
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P Block Elements question

2018 · Shift 1 · Q4

JEE AdvancedChemistryP Block ElementsMultiple correct+4 / −1
Based on the compounds of group 151515 elements, the correct statement(s) is (are)
  1. A
    Bi2O5B{i_2}{O_5}Bi2​O5​ is more basic than N2O5{N_2}{O_5}N2​O5​
  2. B
    NF3N{F_3}NF3​ is more covalent than BiF3Bi{F_3}BiF3​
  3. C
    PH3P{H_3}PH3​ boils at lower temperature than NH3N{H_3}NH3​
  4. D
    The N−NN-NN−N single bond is stronger than the P−PP-PP−P single bond
View written solutionFree

Correct answer: B, C, A

This is a multiple-correct-answer question where we need to evaluate each statement about Group 15 elements.

Statement A: Bi2O5B{i_2}{O_5}Bi2​O5​ is more basic than N2O5{N_2}{O_5}N2​O5​

  1. Analyze the elements: Nitrogen (N) and Bismuth (Bi) are both in Group 15. Nitrogen is at the top of the group, and Bismuth is at the bottom.
  2. Trend in properties: As we move down a group in the p-block, the metallic character of the elements increases. Nitrogen is a non-metal, while Bismuth is a metal.
  3. Nature of oxides: Oxides of non-metals are typically acidic, while oxides of metals are typically basic. For oxides of elements in the same group and the same oxidation state (+5 in this case), the acidic character decreases and the basic character increases as we move down the group.
  4. Comparison: N2O5N_2O_5N2​O5​ is the oxide of a non-metal and is strongly acidic. Bi2O5Bi_2O_5Bi2​O5​ is the oxide of a metal. Following the trend, Bi2O5Bi_2O_5Bi2​O5​ is significantly less acidic than N2O5N_2O_5N2​O5​. Being less acidic implies it is relatively more basic. The order of acidity is N2O5>P2O5>As2O5>Sb2O5>Bi2O5N_2O_5 > P_2O_5 > As_2O_5 > Sb_2O_5 > Bi_2O_5N2​O5​>P2​O5​>As2​O5​>Sb2​O5​>Bi2​O5​. Therefore, the statement that Bi2O5Bi_2O_5Bi2​O5​ is more basic than N2O5N_2O_5N2​O5​ is correct.

Statement B: NF3N{F_3}NF3​ is more covalent than BiF3Bi{F_3}BiF3​

  1. Analyze the compounds: We are comparing the covalent character of nitrogen trifluoride (NF3NF_3NF3​) and bismuth trifluoride (BiF3BiF_3BiF3​).
  2. Apply Fajan's Rules: Covalent character is favored by a small cation and a large anion. Here, the anion is the same (F−F^-F−). The cations are N3+N^{3+}N3+ and Bi3+Bi^{3+}Bi3+.
  3. Cation size: Atomic size increases down the group, so the ionic radius of N3+N^{3+}N3+ is much smaller than that of Bi3+Bi^{3+}Bi3+.
  4. Polarizing power: A smaller cation has a higher charge density and thus greater polarizing power. N3+N^{3+}N3+ will polarize the electron cloud of the fluoride ion more effectively than Bi3+Bi^{3+}Bi3+. Greater polarization leads to a higher degree of covalent character.
  5. Conclusion: Therefore, NF3NF_3NF3​ is more covalent than BiF3BiF_3BiF3​. This statement is correct.

Statement C: PH3P{H_3}PH3​ boils at lower temperature than NH3N{H_3}NH3​

  1. Analyze the compounds: We are comparing the boiling points of ammonia (NH3NH_3NH3​) and phosphine (PH3PH_3PH3​).
  2. Intermolecular forces: Boiling point is determined by the strength of intermolecular forces.
  3. Hydrogen Bonding in NH3NH_3NH3​: Due to the high electronegativity and small size of the nitrogen atom, NH3NH_3NH3​ molecules can form strong intermolecular hydrogen bonds.
  4. Forces in PH3PH_3PH3​: Phosphorus is less electronegative and larger than nitrogen. The P-H bond is not polar enough for hydrogen bonding. The dominant intermolecular forces in PH3PH_3PH3​ are weaker van der Waals forces (dipole-dipole and dispersion forces).
  5. Comparison: The hydrogen bonds in NH3NH_3NH3​ are much stronger than the van der Waals forces in PH3PH_3PH3​. Consequently, more energy is required to overcome these forces in NH3NH_3NH3​, resulting in a significantly higher boiling point. The boiling point of NH3NH_3NH3​ is −33.34∘C-33.34 ^\circ C−33.34∘C, while that of PH3PH_3PH3​ is −87.7∘C-87.7 ^\circ C−87.7∘C.
  6. Conclusion: PH3PH_3PH3​ boils at a lower temperature than NH3NH_3NH3​. This statement is correct.

Statement D: The N−NN-NN−N single bond is stronger than the P−PP-PP−P single bond

  1. Analyze the bonds: We are comparing the bond strength of a nitrogen-nitrogen single bond and a phosphorus-phosphorus single bond.
  2. Lone Pair Repulsion: The nitrogen atom is very small. In an N-N single bond, the lone pair of electrons on each adjacent nitrogen atom are close to each other. This results in significant lone pair-lone pair repulsion, which weakens the bond.
  3. Comparison with P-P bond: The phosphorus atom is larger than the nitrogen atom. The distance between the lone pairs on adjacent phosphorus atoms in a P-P single bond is greater, leading to much weaker lone pair-lone pair repulsion.
  4. Bond Enthalpy Data: The experimental bond enthalpy of the N-N single bond is approximately 160 kJ/mol, whereas the bond enthalpy of the P-P single bond is approximately 200 kJ/mol.
  5. Conclusion: The P-P single bond is stronger than the N-N single bond. This is a known anomaly in Group 15. Therefore, the statement is incorrect.

Final Result: The correct statements are A, B, and C.

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