8.2 Hybrid atomic orbitals  (Page 6/14)

Assignment of hybrid orbitals to central atoms

The hybridization of an atom is determined based on the number of regions of electron density that surround it. The geometrical arrangements characteristic of the various sets of hybrid orbitals are shown in [link] . These arrangements are identical to those of the electron-pair geometries predicted by VSEPR theory. VSEPR theory predicts the shapes of molecules, and hybrid orbital theory provides an explanation for how those shapes are formed. To find the hybridization of a central atom, we can use the following guidelines:

1. Determine the Lewis structure of the molecule.
2. Determine the number of regions of electron density around an atom using VSEPR theory, in which single bonds, multiple bonds, radicals, and lone pairs each count as one region.
3. Assign the set of hybridized orbitals from [link] that corresponds to this geometry.

It is important to remember that hybridization was devised to rationalize experimentally observed molecular geometries. The model works well for molecules containing small central atoms, in which the valence electron pairs are close together in space. However, for larger central atoms, the valence-shell electron pairs are farther from the nucleus, and there are fewer repulsions. Their compounds exhibit structures that are often not consistent with VSEPR theory, and hybridized orbitals are not necessary to explain the observed data. For example, we have discussed the H–O–H bond angle in H ₂ O, 104.5°, which is more consistent with sp ³ hybrid orbitals (109.5°) on the central atom than with 2 p orbitals (90°). Sulfur is in the same group as oxygen, and H ₂ S has a similar Lewis structure. However, it has a much smaller bond angle (92.1°), which indicates much less hybridization on sulfur than oxygen. Continuing down the group, tellurium is even larger than sulfur, and for H ₂ Te, the observed bond angle (90°) is consistent with overlap of the 5 p orbitals, without invoking hybridization. We invoke hybridization where it is necessary to explain the observed structures.

Assigning hybridization

Ammonium sulfate is important as a fertilizer. What is the hybridization of the sulfur atom in the sulfate ion, ${\text{SO}}_4{}^{\text{2−}}?$

Solution

The Lewis structure of sulfate shows there are four regions of electron density. The hybridization is sp ³ .

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What is the hybridization of the selenium atom in SeF ₄ ?

Answer:

The selenium atom is sp ³ d hybridized.

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Assigning hybridization

Urea, NH ₂ C(O)NH ₂ , is sometimes used as a source of nitrogen in fertilizers. What is the hybridization of each nitrogen and carbon atom in urea?

Solution

The Lewis structure of urea is

The nitrogen atoms are surrounded by four regions of electron density, which arrange themselves in a tetrahedral electron-pair geometry. The hybridization in a tetrahedral arrangement is sp ³ ( [link] ). This is the hybridization of the nitrogen atoms in urea.

The carbon atom is surrounded by three regions of electron density, positioned in a trigonal planar arrangement. The hybridization in a trigonal planar electron pair geometry is sp ² ( [link] ), which is the hybridization of the carbon atom in urea.

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Acetic acid, H ₃ CC(O)OH, is the molecule that gives vinegar its odor and sour taste. What is the hybridization of the two carbon atoms in acetic acid?

Answer:

H ₃ C , sp ³ ; C (O)OH, sp ²

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