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Chapter 9: Problem 18

Would you expect the nonbonding electron-pair domain in \(\mathrm{NCl}_{3}\) to be greater or smaller in size than the corresponding one in $\mathrm{PCl}_{3} ?$

Short Answer

Expert verified
The nonbonding electron-pair domain (lone pair) in NCl₃ is smaller than the corresponding one in PCl₃. This is because Nitrogen has a smaller atomic size and a more covalent bond character with Chlorine (due to smaller electronegativity difference) than Phosphorus, resulting in a higher electron density around the central atom and a smaller electron-pair domain size.

Step by step solution

01

Identify the central atom and its electronegativity in each molecule

In NCl₃, Nitrogen is the central atom and has an electronegativity of 3.04. In PCl₃, Phosphorus is the central atom and has an electronegativity of 2.19.
02

Examine the atomic size of Nitrogen and Phosphorus

Both Nitrogen(N) and Phosphorus(P) are in Group 15 of the periodic table, but Phosphorus is in the third period, while Nitrogen is in the second period. As we move down a group, atomic size increases due to the addition of energy levels (shells). Therefore, Phosphorus has a larger atomic size than Nitrogen.
03

Compare the electronegativity difference between N-Cl and P-Cl bonds

To understand the size of the electron-pair domain, we need to examine the electronegativity difference of both molecules. The electronegativity of Chlorine is 3.16. So, the electronegativity difference for N-Cl bond is |3.04 - 3.16| = 0.12. And the electronegativity difference for P-Cl bond is |2.19 - 3.16| = 0.97. In NCl₃, the bond is more covalent due to the smaller electronegativity difference, which means electron-pair is more evenly shared between the Nitrogen and Chlorine atoms. In PCl₃, the bond is more polar as it has a larger electronegativity difference. Thus, the electron pair in P-Cl is more attracted to Chlorine atom.
04

Analyze the impact of atomic size and electronegativity on electron-pair domain size

In NCl₃, the smaller atomic size of Nitrogen and higher covalent bond character result in higher electron density around the central atom, which shrinks the nonbonding electron-pair domain size. In PCl₃, the larger atomic size of Phosphorus and higher polarity of the bond result in a less electron-dense central atom, leading to an increase in the nonbonding electron-pair domain size.
05

Conclusion

Based on the analysis of atomic size and electronegativity differences, we can conclude that the nonbonding electron-pair domain (lone pair) in NCl₃ is smaller than the corresponding one in PCl₃.

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Most popular questions from this chapter

(a) What is the difference between a localized \(\pi\) bond and a delocalized one? (b) How can you determine whether a molecule or ion will exhibit delocalized \(\pi\) bonding? (c) Is the \(\pi\) bond in \(\mathrm{NO}_{2}^{-}\) localized or delocalized?

(a) What does the term paramagnetism mean? (b) How can one determine experimentally whether a substance is paramagnetic? (c) Which of the following ions would you expect to be paramagnetic: $\mathrm{O}_{2}^{+}, \mathrm{N}_{2}{ }^{2-}, \mathrm{Li}_{2}^{+}, \mathrm{O}_{2}^{2-} ?$ For those ions that are paramagnetic, determine the number of unpaired electrons.

Give the electron-domain and molecular geometries for the following molecules and ions: (a) \(\mathrm{BeF}_{2}\), (b) \(\mathrm{AsCl}_{5}\), (c) \(\mathrm{NO}_{2}^{-}\), (e) \(\mathrm{SF}_{4},(\mathbf{f}) \mathrm{BrF}_{s-}\) (d) \(\mathrm{CS}_{2}\)

Consider the Lewis structure for acetic acid, which is known as vinegar: CCC(=O)O (a) What are the approximate bond angles about each of the two carbon atoms, and what are the hybridizations of the orbitals on each of them? (b) What are the hybridizations of the orbitals on the two oxygen atoms, and what are the approximate bond angles at the oxygen that is connected to carbon and hydrogen? (c) What is the total number of \(\sigma\) bonds in the entire molecule, and what is the total number of \(\pi\) bonds?

Consider the \(\mathrm{H}_{2}^{+}\) ion. (a) Sketch the molecular orbitals of the ion and draw its energy-level diagram. (b) How many electrons are there in the \(\mathrm{H}_{2}^{+}\) ion? (c) Write the electron configuration of the ion in terms of its MOs. (d) What is the bond order in \(\mathrm{H}_{2}^{+}\) ? (e) Suppose that the ion is excited by light so that an electron moves from a lower-energy to a higher- energy MO. Would you expect the excited-state \(\mathrm{H}_{2}^{+}\) ion to be stable or to fall apart? (f) Which of the following statements about part (e) is correct: (i) The light excites an electron from a bonding orbital to an antibonding orbital, (ii) The light excites an electron from an antibonding orbital to a bonding orbital, or (iii) In the excited state there are more bonding electrons than antibonding electrons?
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