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Chapter 20: Problem 100

Many structures of phosphorus-containing compounds are drawn with some \(\mathrm{P}=\mathrm{O}\) bonds. These bonds are not the typical \(\pi\) bonds we've considered, which involve the overlap of two \(p\) orbitals. Instead, they result from the overlap of a \(d\) orbital on the phosphorus atom with a \(p\) orbital on oxygen. This type of \(\pi\) bonding is sometimes used as an explanation for why \(\mathrm{H}_{3} \mathrm{PO}_{3}\) has the first structure below rather than the second: Draw a picture showing how a \(d\) orbital and a \(p\) orbital overlap to form a \(\pi\) bond.

Short Answer

Expert verified
To draw the overlap between a phosphorus d-orbital and an oxygen p-orbital forming a pi bond, first, draw the phosphorus d_xy-orbital with four lobes along the x and y axes. Then, draw the oxygen p-orbital with its lobes aligned parallel to any of the four lobes of the phosphorus d_xy-orbital. The overlap will occur between an aligned pair of lobes from the d-orbital and the p-orbital, which can be represented with shaded regions showing where the electron density between the atoms is forming the pi bond. Finally, label the phosphorus d_xy-orbital, the oxygen p-orbital, and the area of overlap that forms the pi bond between the atoms.

Step by step solution

01

Understanding phosphorus d-orbital and oxygen p-orbital

We need to know the shape of the d-orbital and the p-orbital to be able to draw them. A d-orbital can have different shapes, but the most common one is a dumbbell shape between two lobes. The p-orbital also has a dumbbell shape; it is simpler and more symmetrical than the d-orbital.
02

Identifying the orientation of d-orbital and p-orbital

For the d-orbital and p-orbital to overlap and form a pi bond, their orientations should be in a parallel plane. In this case, we'll consider the most common d-orbital orientation (d_xy), with its lobes and nodes lying along the x and y axes. The oxygen p-orbital would overlap when its lobes are parallel to these axes as well.
03

Drawing the overlap between d-orbital and p-orbital

Draw the phosphorus d_xy-orbital with four lobes along the x and y axes. Then draw the oxygen p-orbital with its lobes aligned parallel to any of the four lobes of the phosphorus d_xy-orbital. The overlap will occur between an aligned pair of lobes from the d-orbital and the p-orbital. You can represent this overlap with shaded regions showing where the electron density between the atoms is forming the pi bond.
04

Labeling the diagram

Finally, label the phosphorus d_xy-orbital and the oxygen p-orbital in the diagram. Also, label the area of overlap that forms the pi bond between the atoms.

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Most popular questions from this chapter

Write the Lewis structure for \(\mathrm{O}_{2} \mathrm{~F}_{2}\). Predict the bond angles and hybridization of the two central oxygen atoms. Assign oxidation states and formal charges to the atoms in \(\mathrm{O}_{2} \mathrm{~F}_{2}\). The compound \(\mathrm{O}_{2} \mathrm{~F}_{2}\) is a vigorous and potent oxidizing and fluorinating agent. Are oxidation states or formal charges more useful in accounting for these properties of \(\mathrm{O}_{2} \mathrm{~F}_{2}\) ?

From the information on the temperature stability of white and gray tin given in this chapter, which form would you expect to have the more ordered structure (have the smaller positional probability)?

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Phosphate buffers are important in regulating the \(\mathrm{pH}\) of intracellular fluids. If the concentration ratio of \(\mathrm{H}_{2} \mathrm{PO}_{4}^{-} / \mathrm{HPO}_{4}^{2-}\) in a sample of intracellular fluid is \(1.1: 1\), what is the \(\mathrm{pH}\) of this sample of intracullular fluid? \(\mathrm{H}_{2} \mathrm{PO}_{4}^{-}(a q) \rightleftharpoons \mathrm{HPO}_{4}^{2-}(a q)+\mathrm{H}^{+}(a q) \quad K_{\mathrm{a}}=6.2 \times 10^{-\mathrm{s}}\)

Besides the central atom, what are the differences between \(\mathrm{CO}_{2}\) and \(\mathrm{SiO}_{2} ?\)
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