Which has the greater bond lengths: \(\mathrm{NO}_{2}^{-}\) or \(\mathrm{NO}_{3}^{-}\) ? Explain.

Short Answer

Expert verified
The ion with the greater bond length is \(\mathrm{NO}_{2}^{-}\) due to its lower average bond order of 1.5 compared to \(\mathrm{NO}_{3}^{-}\) with an average bond order of 2. Resonance in these ions results in different bond orders, affecting their bond lengths with lower bond orders corresponding to longer bond lengths.

Step by step solution

01

Determining the molecular structures of the ions

To determine the molecular structures, first, we will calculate the total number of valence electrons in each ion and draw their respective Lewis structures. For \(\mathrm{NO}_{2}^{-}\), the total number of valence electrons is 18 (5 from N, 12 from two O atoms, and 1 extra electron due to the negative charge). In the case of \(\mathrm{NO}_{3}^{-}\), the total number of valence electrons is 24 (5 from N, 18 from three O atoms, and 1 extra electron due to the negative charge). Now, let's draw the Lewis structures for the ions: \(\mathrm{NO}_{2}^{-}\): O - N = O N is bonded to two O atoms with one single bond and one double bond. The negative charge is placed on the O atom with the single bond. \(\mathrm{NO}_{3}^{-}\): O - N - O | O N is bonded to three O atoms with one single bond, and there are two double bonds between the O atoms. The negative charge will be distributed among the O atoms.
02

Identifying resonance structures

Both ions have resonance structures which have an effect on the distribution of electron pairs. In resonance structures, the electrons are shared among multiple bonds, resulting in an average of what these bonds might look like in reality. \(\mathrm{NO}_{2}^{-}\) resonance structures: O = N - O^(-) O^(-) - N = O \(\mathrm{NO}_{3}^{-}\) resonance structures: O = N - O | O^(-) O - N = O | O^(-) O^(-) - N - O | O
03

Analyzing average bond lengths

Resonance structures show that electrons are distributed among the bonds, and the bond length is an average of the localized single and double bonds in the different structures. In \(\mathrm{NO}_{2}^{-}\), the two N-O bonds alternate between single and double bonds in resonance structures, resulting in an average bond order of 1.5. In \(\mathrm{NO}_{3}^{-}\), the bonds between N and O atoms are always double in the different resonance structures, resulting in an average bond order of 2.
04

Determining the greater bond length

A higher bond order corresponds to a shorter bond length, and a lower bond order corresponds to a longer bond length. As the bond order of \(\mathrm{NO}_{2}^{-}\) is 1.5 (lower than the bond order of \(\mathrm{NO}_{3}^{-}\), which is 2), the bond length in \(\mathrm{NO}_{2}^{-}\) is greater than in \(\mathrm{NO}_{3}^{-}\). Therefore, the ion with the greater bond length is \(\mathrm{NO}_{2}^{-}\).

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Most popular questions from this chapter

Write Lewis structures that obey the octet rule for the following species. Assign the formal charge for each central atom. a. \(\mathrm{POCl}_{3}\) e. \(\mathrm{SO}_{2} \mathrm{Cl}_{2}\) b. \(\mathrm{SO}_{4}^{2-}\) f. \(\mathrm{XeO}_{4}\) c. \(\mathrm{ClO}_{4}^{-}\) g. \(\mathrm{ClO}_{3}^{-}\) d. \(\mathrm{PO}_{4}^{3-}\) h. \(\mathrm{NO}_{4}^{3-}\)

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What is the electronegativity trend? Where does hydrogen fit into the electronegativity trend for the other elements in the periodic table?

Which of the following incorrectly shows the bond polarity? Show the correct bond polarity for those that are incorrect. a. \(^{8+} \mathrm{H}-\mathrm{F}^{\delta-}\) d. \(^{\delta}+\mathrm{Br}-\mathrm{Br}^{8}\) b. \(^{\delta+} \mathrm{Cl}-\mathrm{I}^{8}-\) e. \(^{\delta+} \mathrm{O}-\mathrm{P}^{\delta-}\) c. \(^{\delta+} \mathrm{Si}-\mathrm{S}^{8-}\)

An alternative definition of electronegativity is Electronegativity \(=\) constant (I.E. \(-\) E.A.) where I.E. is the ionization energy and E.A. is the electron affinity using the sign conventions of this book. Use data in Chapter 7 to calculate the (I.E. \(-\) E.A.) term for \(\mathrm{F}, \mathrm{Cl}, \mathrm{Br}\), and \(\mathrm{I}\). Do these values show the same trend as the electronegativity values given in this chapter? The first ionization energies of the halogens are \(1678,1255,1138\), and \(1007 \mathrm{~kJ} / \mathrm{mol}\), respectively. (Hint: Choose a constant so that the electronegativity of fluorine equals 4.0. Using this constant, calculate relative electronegativities for the other halogens and compare to values given in the text.)

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