Atkins_4e_Ch02_p57 4/24/07 2:14 PM Page 76

76 CHAPTER 2 CHEMICAL BONDS

F SELF-TEST 2.10A Write the Lewis structure for xenon tetrafluoride, XeF4, and give
the number of electrons in the expanded valence shell.
F Xe F [Answer: See (25); 12 electrons]
F
SELF-TEST 2.10B Write the Lewis structure for the I3 ion and give the number of
25 Xenon tetrafluoride, XeF4 electrons in the expanded valence shell.
When different resonance structures are possible, some giving the central atom
in a compound an octet and some an expanded valence shell, the dominant reso-
nance structure is likely to be the one with the lowest formal charges. However,
there are many exceptions and the selection of the best structure often depends on
a careful analysis of experimental data.

2 2
O
苶兩
O
苶兩 EXAMPLE 2.8 Selecting the dominant resonance structure for a molecule

O S O O S O The sulfate ion, SO42, is present in a number of important minerals, including gypsum
(CaSO42H2O), which is used in cement, and Epsom salts (MgSO47H2O), which is used
O O as a purgative. Determine the dominant resonance structure of a sulfate ion from the
three shown in (26) by calculating the formal charges on the atoms in each structure.
26a 26b
2
STRATEGY Follow the procedure in Toolbox 2.2. We need do only one calculation for
苶兩
O equivalent atoms, such as the oxygen atoms in the first diagram, because they all have
the same arrangement of electrons and hence the same formal charge.
O S O

O SOLUTION We draw up the following table, in accord with Toolbox 2.2.

26a 26b 26c

26c
Step 1 Count the valence O: 6 S: 6
electrons (V). Total: 24 electrons, which provide 12 pairs of
electrons

$ 兩 2 $ 兩 2 $ 兩 2
O 苶 O 苶 O 苶
$
$

$
$

$
$
$ ˚ $ $ ˚ $ $ ˚ $
Step 2 Draw the Lewis structure. O
$ ¬ S˚ ¬ O O
$ £ S˚ ¬ O O
$ £ S˚ £ O
$

$
$ $ $
O O O
$
$

$
$

$
$
$ $ $

$ 兩 2 $ 兩 2 $ 兩 2
O 7 苶 O 7 苶 O 7 苶
$
$

$
$

$
$
Step 3 Assign electron ownership, $ ˚4 $ $6 ˚ 5 $ $6 ˚ 6 $
O
$ ¬ S˚ ¬ O O
$ £ S˚ ¬ O O
$ £ S˚ £ O
$

$
(L  21 B). $ $ $
O O O
$
$

$
$

$
$
$ $ $

兩 2 $ 兩 2
O 1苶 兩 2
$ $
O 1苶 O 1苶
$
$
$
$

$
$
1 0
3 3 Step 4 Find the formal charge, $ ˚ 2 $ $ ˚ 1 $ $0 ˚ 0 $
苶兩 苶兩 O O
$ £ S˚ ¬ O
$ ¬ S˚ ¬ O O
$ £ S˚ £ O
$
$

O O V  (L  12B). $ $ $
O 1 O 1 O 0
1 1 1
$
$
$
$

$
$

O P O O P O $ $ $
O O
The individual formal charges are closest to zero in structure (26c); so that structure is
27 likely to make the biggest contribution to the resonance hybrid, even though the
valence shell on the S atom has expanded to hold 12 electrons.
兩 3 兩 3
−1 O 苶 −1 O 苶 SELF-TEST 2.11A Calculate the formal charges for the two Lewis structures of the
−1 phosphate ion shown in (27). Which structure is dominant?
+1 0
O P O O P O [Answer: See (28); the second structure.]
−1 0 −1
−1 O −1 O
SELF-TEST 2.11B Calculate the formal charges for the three oxygen atoms in one of
28 the Lewis structures of the ozone resonance structure (Example 2.5).

Octet expansion (expansion of the valence shell to more than eight electrons)
can occur in elements of Period 3 and later periods. These elements can exhibit
variable covalence and be hypervalent. Formal charge helps to identify the
dominant resonance structure.