SAMPLE EXERCISE 8.

3 Lewis Structure of a Compound

Given the Lewis symbols for the elements nitrogen and fluorine shown in Table 8.1, predict the formula of the
stable binary compound (a compound composed of two elements) formed when nitrogen reacts with fluorine,
and draw its Lewis structure.
Solution
Analyze: The Lewis symbols for nitrogen and fluorine reveal that nitrogen has five valence electrons and
fluorine has seven.
Plan: We need to find a combination of the two elements that results in an octet of electrons around each
atom in the compound. Nitrogen requires three additional electrons to complete its octet, whereas fluorine
requires but one. Sharing a pair of electrons between one N atom and one F atom will result in an octet of
electrons for fluorine but not for nitrogen. We therefore need to figure out a way to get two more electrons for
the N atom.
PRACTICE EXERCISE
Compare the Lewis symbol for neon with the Lewis structure for methane, CH
4
. In what important way are the
electron arrangements about neon and carbon alike? In what important respect are they different?
Answer: Both atoms have an octet of electrons about them. However, the electrons about neon are unshared
electron pairs, whereas those about carbon are shared with four hydrogen atoms.
Check: The Lewis structure on the left shows that each atom is surrounded by an octet of electrons. Once
you are accustomed to thinking of each line in a Lewis structure as representing two electrons, you can just as
easily use the structure on the right to check for octets.
Solve: Nitrogen must share a pair of electrons with three fluorine atoms to complete its octet. Thus, the
Lewis structure for the resulting compound, NF
3
, is
SAMPLE EXERCISE 8.4 Bond Polarity
In each case, which bond is more polar: (a) BCl or CCl, (b) PF or PCl? Indicate in each case which
atom has the partial negative charge.
Solution
Analyze: We are asked to determine relative bond polarities, given nothing but the atoms involved in the
bonds.
Plan: We need to know electronegativity values for all the atoms involved, which we can get from Figure 8.6.
Alternatively, because we are not asked for quantitative answers, we can use the periodic table and our
knowledge of electron-affinity trends to answer the question.
Solve: (a) Using Figure 8.6: The difference in the electronegativities of chlorine and boron is 3.0 2.0 = 1.0;
the difference between chlorine and carbon is 3.0 2.5 = 0.5. Consequently, the BCl bond is more polar; the
chlorine atom carries the partial negative charge because it has a higher electronegativity.
Using the periodic table: Because boron is to the left of carbon in the periodic table, we predict that boron
has the lower electronegativity. Chlorine, being on the right side of the table, has a higher electronegativity. The
more polar bond will be the one between the atoms having the lowest electronegativity (boron) and the highest
electronegativity (chlorine).
(b) The electronegativities are P = 2.1, F = 4.0, Cl = 3.0. Consequently, the PF bond will be more polar
than the PCl bond. You should compare the electronegativity differences for the two bonds to verify this
prediction. The fluorine atom carries the partial negative charge. We reach the same conclusion by noting that
fluorine is above chlorine in the periodic table, and so fluorine should be more electronegative and will form the
more polar bond with P.
PRACTICE EXERCISE
Which of the following bonds is most polar: SCl, SBr, SeCl, SeBr?
Answer: SeCl
SAMPLE EXERCISE 8.5 Dipole Moments of Diatomic Molecules
The bond length in the HCl molecule is 1.27 . (a) Calculate the dipole moment, in debyes, that would result if
the charges on the H and Cl atoms were 1+ and 1, respectively. (b) The experimentally measured dipole
moment of HCl(g) is 1.08 D. What magnitude of charge, in units of e, on the H and Cl atoms would lead to this
dipole moment?
Solution
Analyze and Plan: We are asked in (a) to calculate the dipole moment of HCl that would result if there
was a full charge transferred from H to Cl. We can use Equation 8.11 to obtain this result. In (b), we are given
the actual dipole moment for the molecule and will use that value to calculate the actual partial charges on the
H and Cl atoms.
Solve: (a) The charge on each atom is the electronic charge, e = 1.60 10
19
C. The separation is 1.27 . The
dipole moment is therefore
(b) We know the value of , 1.08 D, and the value of r, 1.27 , and we want to calculate the value of Q:
SAMPLE EXERCISE 8.5 continued
PRACTICE EXERCISE
The dipole moment of chlorine monofluoride, ClF(g), is 0.88 D. The bond length of the molecule is 1.63 . (a)
Which atom is expected to have the partial negative charge? (b) What is the charge on that atom, in units of e?
Because the experimental dipole moment is less than that calculated in part (a), the charges on the atoms are
less than a full electronic charge. We could have anticipated this because the HCl bond is polar covalent
rather than ionic.
We can readily convert this charge to units of e:
Thus, the experimental dipole moment indicates that the charge separation in the HCl molecule is
Answers: (a) F, (b) 0.11
SAMPLE EXERCISE 8.6 Drawing Lewis Structures
Draw the Lewis structure for phosphorus trichloride, PCl
3
.
Solve: First, we sum the valence electrons. Phosphorus (group 5A) has five valence electrons, and each
chlorine (group 7A) has seven. The total number of valence electrons is therefore

5 + (3 7) = 26
Solution
Analyze and Plan: We are asked to draw a Lewis structure from a molecular formula. Our plan is to
follow the five-step procedure just described.
(It is not crucial to place the atoms in exactly this arrangement.)
Second, we arrange the atoms to show which atom is connected to which, and we draw a single bond between
them. There are various ways the atoms might be arranged. In binary (two-element) compounds, however, the
first element listed in the chemical formula is generally surrounded by the remaining atoms. Thus, we begin
with a skeleton structure that shows a single bond between the phosphorus atom and each chlorine atom:
Third, we complete the octets on the atoms bonded to the central atom. Placing octets around each Cl atom
accounts for 24 electrons (remember, each line in our structure represents two electrons):
SAMPLE EXERCISE 8.6 continued
Fourth, we place the remaining two electrons on the central atom, completing the octet around it:
PRACTICE EXERCISE
(a) How many valence electrons should appear in the Lewis structure for CH
2
Cl
2
?
(b) Draw the Lewis structure.
This structure gives each atom an octet, so we stop at this point. (Remember that in achieving an octet, the
bonding electrons are counted for both atoms.)
Answers: (a) 20, (b)
SAMPLE EXERCISE 8.7 Lewis Structures with Multiple Bonds
Draw the Lewis structure for HCN.
Solution Hydrogen has one valence electron, carbon (group 4A) has four, and nitrogen (group 5A) has five.
The total number of valence electrons is therefore 1 + 4 + 5 = 10. In principle, there are different ways in which
we might choose to arrange the atoms. Because hydrogen can accommodate only one electron pair, it always
has only one single bond associated with it in any compound. Therefore, CHN is an impossible
arrangement. The remaining two possibilities are HCN and HNC. The first is the arrangement found
experimentally. You might have guessed this to be the atomic arrangement because the formula is written with
the atoms in this order. Thus, we begin with a skeleton structure that shows single bonds between hydrogen,
carbon, and nitrogen:

HCN
We therefore try a double bond between C and N, using one of the unshared pairs of electrons we placed on N.
Again, there are fewer than eight electrons on C, and so we next try a triple bond. This structure gives an octet
around both C and N:
We see that the octet rule is satisfied for the C and N atoms, and the H atom has two electrons around it, so
this appears to be a correct Lewis structure.
These two bonds account for four electrons. If we then place the remaining six electrons around N to give it an
octet, we do not achieve an octet on C:
SAMPLE EXERCISE 8.7 continued
PRACTICE EXERCISE
Draw the Lewis structure for (a) NO
+
ion, (b) C
2
H
4
.
SAMPLE EXERCISE 8.8 Lewis Structure for a Polyatomic Ion
Draw the Lewis structure for the BrO
3

ion.
Notice here and elsewhere that the Lewis structure for an ion is written in brackets with the charge shown
outside the brackets at the upper right.
Solution Bromine (group 7A) has seven valence electrons, and oxygen (group 6A) has six. We must now
add one more electron to our sum to account for the 1 charge of the ion. The total number of valence
electrons is therefore 7 + (3 6) + 1 = 26. For oxyanions BrO
3

, SO
4
2
, NO
3

, CO
3
2
, and so forththe oxygen
atoms surround the central nonmetal atoms. After following this format and then putting in the single bonds
and distributing the unshared electron pairs, we have
PRACTICE EXERCISE
Draw the Lewis structure for (a) ClO
2

ion, (b) PO
4
3
ion.
Answers:
SAMPLE EXERCISE 8.9 Lewis Structures and Formal Charges
(a) Determine the formal charges of the atoms in each structure. (b) Which Lewis structure is the preferred
one?
The following are three possible Lewis structures for the thiocyanate ion, NCS

:
Solution (a) Neutral N, C, and S atoms have five, four, and six valence electrons, respectively. We can
determine the following formal charges in the three structures by using the rules we just discussed:
As they must, the formal charges in all three structures sum to 1, the overall charge of the ion.
(b) We will use the guidelines for the best Lewis structure to determine which of the three structures is
likely the most correct. As discussed in Section 8.4, N is more electronegative than C or S. Therefore, we expect
that any negative formal charge will reside on the N atom (guideline 2). Further, we usually choose the Lewis
structure that produces the formal charges of smallest magnitude (guideline 1). For these two reasons, the middle
structure is the preferred Lewis structure of the NCS

ion.
SAMPLE EXERCISE 8.9 continued
PRACTICE EXERCISE
The cyanate ion (NCO

), like the thiocyanate ion, has three possible Lewis structures. (a) Draw these three
Lewis structures, and assign formal charges to the atoms in each structure. (b) Which Lewis structure is the
preferred one?
Answers: (a)
(b) Structure (iii), which places a negative charge on oxygen, the most electronegative of the three elements, is
the preferred Lewis structure.
SAMPLE EXERCISE 8.10 Resonance Structures
Which is predicted to have the shorter sulfuroxygen bonds, SO
3
or SO
3
2
?
Solution The sulfur atom has six valence electrons, as does oxygen. Thus, SO
3
contains 24 valence electrons.
In writing the Lewis structure, we see that three equivalent resonance structures can be drawn:
As was the case for NO
3

, the actual structure of SO

3
is an equal blend of all three. Thus, each SO bond
distance should be about one-third of the way between that of a single and that of a double bond (see the
immediately preceding Give It Some Thought exercise). That is, they should be shorter than single bonds but not
as short as double bonds.
There are no other reasonable Lewis structures for this ionit can be described quite well by a single Lewis
structure rather than by multiple resonance structures.
Our analysis of the Lewis structures leads us to conclude that SO
3
should have the shorter SO bonds and
SO
3
2
the longer ones. This conclusion is correct: The experimentally measured SO bond lengths are 1.42 in
SO
3
and 1.51 in SO
3
2
.
The SO
3
2
ion has 26 electrons, which leads to a Lewis structure in which all the SO bonds are single
bonds:
SAMPLE EXERCISE 8.10 continued
PRACTICE EXERCISE
Draw two equivalent resonance structures for the formate ion, HCO
2

.
Answer:
SAMPLE EXERCISE 8.11 Lewis Structure for an Ion with an Expanded Valence Shell
Draw the Lewis structure for ICl
4

.
Solution Iodine (group 7A) has seven valence electrons; each chlorine (group 7A) also has seven; an extra
electron is added to account for the 1 charge of the ion. Therefore, the total number of valence electrons is

7 + 4(7) + 1 = 36
Iodine has 12 valence electrons around it, four more than needed for an octet.
PRACTICE EXERCISE
(a) Which of the following atoms is never found with more than an octet of valence electrons around it: S, C, P,
Br? (b) Draw the Lewis structure for XeF
2
.
The I atom is the central atom in the ion. Putting eight electrons around each Cl atom (including a pair of
electrons between I and each Cl to represent the single bond between these atoms) requires 8 4 = 32 electrons.
We are thus left with 36 32 = 4 electrons to be placed on the larger iodine:
Answers: (a) C, (b)
SAMPLE EXERCISE 8.12 Using Average Bond Enthalpies
Using Table 8.4, estimate H for the following reaction (where we explicitly show the bonds involved in the
reactants and products):
Solution
Analyze: We are asked to estimate the enthalpy change for a chemical process by using average bond
enthalpies for the bonds that are broken in the reactants and formed in the products.
Check: This estimate can be compared with the value of 1428 kJ calculated from more accurate
thermochemical data; the agreement is good.
Solve: Using Equation 8.12 and data from Table 8.4, we have
Plan: Among the reactants, we must break six CH bonds and a CC bond in C
2
H
6
; we also break
bonds. Among the products, we form four bonds (two in each CO
2
) and six OH bonds (two in each
H
2
O).
SAMPLE EXERCISE 8.12 continued
PRACTICE EXERCISE
Using Table 8.4, estimate H for the reaction
Answer: 86 kJ
SAMPLE INTEGRATIVE EXERCISE Putting Concepts Together
Phosgene, a substance used in poisonous gas warfare in World War I, is so named because it was first prepared
by the action of sunlight on a mixture of carbon monoxide and chlorine gases. Its name comes from the Greek
words phos (light) and genes (born of). Phosgene has the following elemental composition: 12.14% C, 16.17%
O, and 71.69% Cl by mass. Its molar mass is 98.9 g/mol. (a) Determine the molecular formula of this
compound. (b) Draw three Lewis structures for the molecule that satisfy the octet rule for each atom. (The Cl
and O atoms bond to C.) (c) Using formal charges, determine which Lewis structure is the most important one.
(d) Using average bond enthalpies, estimate H for the formation of gaseous phosgene from CO(g) and Cl
2
(g).
Solution (a) The empirical formula of phosgene can be determined from its elemental composition.
(Section 3.5) Assuming 100 g of the compound and calculating the number of moles of C, O, and Cl in this
sample, we have
The ratio of the number of moles of each element, obtained by dividing each number of moles by the smallest
quantity, indicates that there is one C and one O for each two Cl in the empirical formula, COCl
2
.
The molar mass of the empirical formula is 12.01 + 16.00 + 2(35.45) = 98.91 g/mol, the same as the molar
mass of the molecule. Thus, COCl
2
is the molecular formula.
Thus, the reaction involves breaking a bond and a ClCl bond and forming a bond and two
CCl bonds. Using bond enthalpies from Table 8.4, we have
SAMPLE INTEGRATIVE EXERCISE continued
(b) Carbon has four valence electrons, oxygen has six, and chlorine has seven, giving 4 + 6 + 2(7) = 24
electrons for the Lewis structures. Drawing a Lewis structure with all single bonds does not give the central
carbon atom an octet. Using multiple bonds, three structures satisfy the octet rule:
(c) Calculating the formal charges on each atom gives
The first structure is expected to be the most important one because it has the lowest formal charges on each
atom. Indeed, the molecule is usually represented by this Lewis structure.
(d) Writing the chemical equation in terms of the Lewis structures of the molecules, we have
Because of resonance, the bonds between the central O atom and the outer O atoms are of equal length. In
both resonance structures the central O atom is bonded to the two outer O atoms and has one nonbonding
pair. Thus, there are three electron domains about the central O atoms. (Remember that a double bond counts
as a single electron domain.) The best arrangement of three electron domains is trigonal planar (Table 9.1).
Two of the domains are from bonds, and one is due to a nonbonding pair, so the molecule has a bent shape
with an ideal bond angle of 120 (Table 9.2).
SAMPLE EXERCISE 9.1 Using the VSEPR Model
Use the VSEPR model to predict the molecular geometry of (a) O
3
, (b) SnCl
3

.
Solution
Analyze: We are given the molecular formulas of a molecule and a polyatomic ion, both conforming to the
general formula AB
n
and both having a central atom from the p block of the periodic table.
Plan: To predict the molecular geometries of these species, we first draw their Lewis structures and then
count the number of electron domains around the central atom. The number of electron domains gives the
electron-domain geometry. We then obtain the molecular geometry from the arrangement of the domains that
are due to bonds.
Solve: (a) We can draw two resonance structures for O
3
:
As this example illustrates, when a molecule exhibits resonance, any one of the resonance structures can be
used to predict the molecular geometry.
The central Sn atom is bonded to the three Cl atoms and has one nonbonding pair. Therefore, the Sn atom has
four electron domains around it. The resulting electron-domain geometry is tetrahedral (Table 9.1) with one of
the corners occupied by a nonbonding pair of electrons. The molecular geometry is thus trigonal pyramidal
(Table 9.2), like that of NH
3
.
Answers: (a) tetrahedral, bent; (b) trigonal planar, trigonal planar
PRACTICE EXERCISE
Predict the electron-domain geometry and the molecular geometry for (a) SeCl
2
, (b) CO
3
2
.
SAMPLE EXERCISE 9.1 continued
(b) The Lewis structure for the SnCl
3

ion is
SAMPLE EXERCISE 9.2 Molecular Geometries of Molecules with Expanded Valence Shells
Use the VSEPR model to predict the molecular geometry of (a) SF
4
, (b) IF
5
.
Solution
Analyze: The molecules are of the AB
n
type with a central atom from the p block of the periodic table.
Plan: We can predict their structures by first drawing Lewis structures and then using the VSEPR model to
determine the electron-domain geometry and molecular geometry.
Solve: (a) The Lewis structure for SF
4
is
The sulfur has five electron domains around it: four from the SF bonds and one from the nonbonding pair.
Each domain points toward a vertex of a trigonal bipyramid. The domain from the nonbonding pair will point
toward an equatorial position. The four bonds point toward the remaining four positions, resulting in a
molecular geometry that is described as seesaw-shaped:
The iodine has six electron domains around it, one of which is from a nonbonding pair. The electron-domain
geometry is therefore octahedral, with one position occupied by the nonbonding electron pair. The resulting
molecular geometry is therefore square pyramidal (Table 9.3):
SAMPLE EXERCISE 9.2 continued
Comment: The experimentally observed structure is shown on the previous slide on the right, and we can
infer that the nonbonding electron domain occupies an equatorial position, as predicted. The axial and
equatorial SF bonds are slightly bent back away from the nonbonding domain, suggesting that the bonding
domains are pushed by the nonbonding domain, which is larger and has greater repulsion (Figure 9.7).
(b) The Lewis structure of IF
5
is
Comment: Because the domain for the nonbonding pair is larger than the other domains, the four F atoms
in the base of the pyramid are tipped up slightly toward the F atom on top. Experimentally, it is found that the
angle between the base and top F atoms is 82, smaller than the ideal 90 angle of an octahedron.
(There are three lone pairs on each of the F atoms, but they are not shown.)
SAMPLE EXERCISE 9.2 continued
PRACTICE EXERCISE
Predict the electron-domain geometry and molecular geometry of (a) ClF
3
, (b) ICl
4

.
Answers: (a) trigonal bipyramidal, T-shaped; (b) octahedral, square planar
Predict the approximate values for the HOC and OCC bond angles in vinyl alcohol.
SAMPLE EXERCISE 9.3 Predicting Bond Angles
Eyedrops for dry eyes usually contain a water-soluble polymer called poly(vinyl alcohol), which is based on the
unstable organic molecule called vinyl alcohol:
Solution
Analyze: We are given a molecular structure and asked to determine two bond angles in the structure.
Plan: To predict a particular bond angle, we consider the middle atom of the angle and determine the
number of electron domains surrounding that atom. The ideal angle corresponds to the electron-domain
geometry around the atom. The angle will be compressed somewhat by nonbonding electrons or multiple
bonds.
Solve: For the HOC bond angle, there are four electron domains around the middle O atom (two bonding
and two nonbonding). The electron-domain geometry around O is therefore tetrahedral, which gives an ideal
angle of 109.5. The HOC angle will be compressed somewhat by the nonbonding pairs, so we expect this
angle to be slightly less than 109.5.
To predict the OCC bond angle, we must examine the leftmost C atom, which is the central atom for
this angle. There are three atoms bonded to this C atom and no nonbonding pairs, and so it has three electron
domains about it. The predicted electron-domain geometry is trigonal planar, resulting in an ideal bond angle
of 120. Because of the larger size of the domain, however, the OCC bond angle should be slightly
greater than 120.
SAMPLE EXERCISE 9.3 continued
Answers: 109.5, 180
PRACTICE EXERCISE
Predict the HCH and CCC bond angles in the following molecule, called propyne:
SAMPLE EXERCISE 9.4 Polarity of Molecules
Predict whether the following molecules are polar or nonpolar: (a) BrCl, (b) SO
2
, (c) SF
6
.
Solution
Analyze: We are given the molecular formulas of several substances and asked to predict whether the
molecules are polar.
Plan: If the molecule contains only two atoms, it will be polar if the atoms differ in electronegativity. If it
contains three or more atoms, its polarity depends on both its molecular geometry and the polarity of its bonds.
Thus, we must draw a Lewis structure for each molecule containing three or more atoms and determine its
molecular geometry. We then use the relative electronegativities of the atoms in each bond to determine the
direction of the bond dipoles. Finally, we see if the bond dipoles cancel each other to give a nonpolar molecule
or reinforce each other to give a polar one.
Solve: (a) Chlorine is more electronegative than bromine. All diatomic molecules with polar bonds are polar
molecules. Consequently, BrCl will be polar, with chlorine carrying the partial negative charge:
The actual dipole moment of BrCl, as determined by experimental measurement, is = 0.57 D.
(b) Because oxygen is more electronegative than sulfur, SO
2
has polar bonds. Three resonance forms can be
written for SO
2
:
Answers: (a) polar because polar bonds are arranged in a trigonal-pyramidal geometry, (b) nonpolar because
polar bonds are arranged in a trigonal-planar geometry
SAMPLE EXERCISE 9.4 continued
For each of these, the VSEPR model predicts a bent geometry. Because the molecule is bent, the bond dipoles do
not cancel and the molecule is polar:
Experimentally, the dipole moment of SO
2
is = 1.63 D.
PRACTICE EXERCISE
Determine whether the following molecules are polar or nonpolar: (a) NF
3
, (b) BCl
3
.
(c) Fluorine is more electronegative than sulfur, so the bond dipoles point toward fluorine. The six SF
bonds are arranged octahedrally around the central sulfur:
Because the octahedral geometry is symmetrical, the bond dipoles cancel, and the molecule is nonpolar,
meaning that = 0.
SAMPLE EXERCISE 9.5 Hybridization
Indicate the hybridization of orbitals employed by the central atom in (a) NH
2

, (b) SF
4
(see Sample Exercise
9.2).
Solution
Analyze: We are given two chemical formulasone for a polyatomic anion and one for a molecular
compoundand asked to describe the type of hybrid orbitals surrounding the central atom in each case.
Plan: To determine the hybrid orbitals used by an atom in bonding, we must know the electron-domain
geometry around the atom. Thus, we first draw the Lewis structure to determine the number of electron
domains around the central atom. The hybridization conforms to the number and geometry of electron
domains around the central atom as predicted by the VSEPR model.
Answers: (a) tetrahedral, sp
3
; (b) octahedral, sp
3
d
2
(b) The Lewis structure and electron-domain geometry of SF
4
are shown in Sample Exercise 9.2. There are
five electron domains around S, giving rise to a trigonal-bipyramidal electron-domain geometry. With an
expanded octet of ten electrons, a d orbital on the sulfur must be used. The trigonal-bipyramidal electron-domain
geometry corresponds to sp
3
d hybridization (Table 9.4). One of the hybrid orbitals that points in an equatorial
direction contains a nonbonding pair of electrons; the other four are used to form the SF bonds.
Solve: (a) The Lewis structure of NH
2

is
Because there are four electron domains around N, the electron-domain geometry is tetrahedral. The
hybridization that gives a tetrahedral electron-domain geometry is sp
3
(Table 9.4). Two of the sp
3
hybrid orbitals
contain nonbonding pairs of electrons, and the other two are used to make two-electron bonds with the hydrogen
atoms.
PRACTICE EXERCISE
Predict the electron-domain geometry and the hybridization of the central atom in (a) SO
3
2
, (b) SF
6
.
SAMPLE EXERCISE 9.6 Describing and Bonds in a Molecule
Formaldehyde has the Lewis structure
Describe how the bonds in formaldehyde are formed in terms of overlaps of appropriate hybridized and
unhybridized orbitals.
Solve: The C atom has three electron domains around it, which suggests a trigonal-planar geometry with bond
angles of about 120. This geometry implies sp
2
hybrid orbitals on C (Table 9.4). These hybrids are used to
make the two CH and one CO bonds to C. There remains an unhybridized 2p orbital on carbon,
perpendicular to the plane of the three sp
2
hybrids.
Solution
Analyze: We are asked to describe the bonding in formaldehyde in terms of orbital overlaps.
Plan: Single bonds will be of the type, whereas double bonds will consist of one bond and one bond.
The ways in which these bonds form can be deduced from the geometry of the molecule, which we predict
using the VSEPR model.
SAMPLE EXERCISE 9.6 continued
The O atom also has three electron domains around it, and so we will assume that it has sp
2
hybridization as
well. One of these hybrids participates in the CO bond, while the other two hybrids hold the two
nonbonding electron pairs of the O atom. Like the C atom, therefore, the O atom has an unhybridized 2p orbital
that is perpendicular to the plane of the molecule. The unhybridized 2p orbitals on the C and O atoms overlap to
form a CO bond, as illustrated in Figure 9.27.
Answers: (a) approximately 109 around the left C and 180 on the right C; (b) sp
3
, sp; (c) five bonds and two
bonds
PRACTICE EXERCISE
Consider the acetonitrile molecule:
(a) Predict the bond angles around each carbon atom; (b) describe the hybridization at each of the carbon atoms;
(c) determine the total number of and bonds in the molecule.
Figure 9.27 Formation
of and bonds in
formaldehyde, H
2
CO.
SAMPLE EXERCISE 9.7 Delocalized Bonding
Describe the bonding in the nitrate ion, NO
3

. Does this ion have delocalized bonds?

Solution
Analyze: Given the chemical formula for a polyatomic anion, we are asked to describe the bonding and
determine whether the ion has delocalized bonds.
Plan: Our first step in describing the bonding in NO
3

is to construct appropriate Lewis structures. If there

are multiple resonance structures that involve the placement of the double bonds in different locations, that
suggests that the component of the double bonds is delocalized.
In each of these structures the electron-domain geometry at nitrogen is trigonal planar, which implies sp
2

hybridization of the N atom. The sp
2
hybrid orbitals are used to construct the three NO bonds that are
present in each of the resonance structures.
Solve: In Section 8.6 we saw that NO
3

has three resonance structures:

SAMPLE EXERCISE 9.7 continued
The unhybridized 2p orbital on the N atom can be used to make bonds. For any one of the three resonance
structures shown, we might imagine a single localized NO bond formed by the overlap of the unhybridized
2p orbital on N and a 2p orbital on one of the O atoms, as shown in Figure 9.30(a). Because each resonance
structure contributes equally to the observed structure of NO
3

, however, we represent the bonding as spread

out, or delocalized, over the three NO bonds, as shown in Figure 9.30(b).
Figure 9.30
Localized and delocalized
bonds in NO
3

.
SAMPLE EXERCISE 9.7 continued
Answer: SO
3
and O
3
, as indicated by the presence of two or more resonance structures involving bonding for
each of these molecules
PRACTICE EXERCISE
Which of the following molecules or ions will exhibit delocalized bonding: SO
3
, SO
3
2
, H
2
CO, O
3
, NH
4
+
?
SAMPLE EXERCISE 9.8 Bond Order
What is the bond order of the He
2
+
ion? Would you expect this ion to be stable relative to the separated He atom
and He
+
ion?
Solution
Analyze: We will determine the bond order for the He
2
+
ion and use it to predict whether the ion is stable.
Plan: To determine the bond order, we must determine the number of electrons in the molecule and how these
electrons populate the available MOs. The valence electrons of He are in the 1s orbital, and the 1s orbitals
combine to give an MO diagram like that for H
2
or He
2
(Figure 9.35).
If the bond order is greater than 0, we expect a bond to exist and the ion is stable.
Solve: The energy-level diagram for the He
2
+
ion is shown in Figure 9.36 . This ion has three electrons. Two
are placed in the bonding orbital, the third in the antibonding orbital. Thus, the bond order is
SAMPLE EXERCISE 9.8 continued
Because the bond order is greater than 0, the He
2
+
ion is predicted to be stable relative to the separated He and
He
+
. Formation of He
2
+
in the gas phase has been demonstrated in laboratory experiments.
PRACTICE EXERCISE
Determine the bond order of the H
2

ion.
Figure 9.36 Energy-
level diagram for the
He
2
+
ion.
SAMPLE EXERCISE 9.9 Molecular Orbitals of a Second-Row Diatomic Ion
Predict the following properties of O
2
+
: (a) number of unpaired electrons, (b) bond order, (c) bond enthalpy and
bond length.
Solution
Analyze: Our task is to predict several properties of the cation O
2
+
.
Plan: We will use the MO description of O
2
+
to determine the desired properties. We must first determine
the number of electrons in O
2
+
and then draw its MO energy diagram. The unpaired electrons are those
without a partner of opposite spin. The bond order is one-half the difference between the number of bonding
and antibonding electrons. After calculating the bond order, we can use the data in Figure 9.45 to estimate the
bond enthalpy and bond length.
Solve: (a) The O
2
+
ion has 11 valence electrons, one fewer than O
2
. The electron removed from O
2
to form
O
2
+
is one of the two unpaired * electrons (see Figure 9.45). Therefore, O
2
+
has just one unpaired electron.
Answers: (a) diamagnetic, 1; (b) diamagnetic, 3
(c) The bond order of O
2
+
is between that for O
2
(bond order 2) and N
2
(bond order 3). Thus, the bond
enthalpy and bond length should be about midway between those for O
2
and N
2
, approximately 700 kJ/mol and
1.15 , respectively. The experimental bond enthalpy and bond length of the ion are 625 kJ/mol and 1.123 ,
respectively.
(b) The molecule has eight bonding electrons (the same as O
2
) and three antibonding electrons (one fewer
than O
2
). Thus, its bond order is
PRACTICE EXERCISE
Predict the magnetic properties and bond orders of (a) the peroxide ion, O
2
2
; (b) the acetylide ion, C
2
2
.
(a) With respect to electronic structure, which element in the second row of the periodic table is most similar
to sulfur? (b) Use the VSEPR model to predict the SSS bond angles in S
8
and the hybridization at S in S
8
. (c)
Use MO theory to predict the sulfursulfur bond order in S
2
. Is the molecule expected to be diamagnetic or
paramagnetic? (d) Use average bond enthalpies (Table 8.4) to estimate the enthalpy change for the reaction
just described. Is the reaction exothermic or endothermic?
SAMPLE INTEGRATIVE EXERCISE Putting Concepts Together
Elemental sulfur is a yellow solid that consists of S
8
molecules. The structure of the S
8
molecule is a puckered
eight-membered ring (Figure 7.30). Heating elemental sulfur to high temperatures produces gaseous S
2

molecules:
Solution (a) Sulfur is a group 6A element with an [Ne]3s
2
3p
4
electron configuration. It is expected to be
most similar electronically to oxygen (electron configuration, [He]2s
2
2p
4
), which is immediately above it in the
periodic table. (Chapter 7, Introduction) (b) The Lewis structure of S
8
is
SAMPLE INTEGRATIVE EXERCISE continued
Because H
rxn
> 0, the reaction is endothermic. (Section 5.4) The very positive value of H
rxn
suggests that
high temperatures are required to cause the reaction to occur.
There is a single bond between each pair of S atoms and two nonbonding electron pairs on each S atom.
Thus, we see four electron domains around each S atom, and we would expect a tetrahedral electron-domain
geometry corresponding to sp
3
hybridization. (Sections 9.2, 9.5) Because of the nonbonding pairs, we would
expect the SSS angles to be somewhat less than 109, the tetrahedral angle. Experimentally, the
SSS angle in S
8
is 108, in good agreement with this prediction. Interestingly, if S
8
were a planar ring
(like a stop sign), it would have SSS angles of 135. Instead, the S
8
ring puckers to accommodate the
smaller angles dictated by sp
3
hybridization. (c) The MOs of S
2
are entirely analogous to those of O
2
,
although the MOs for S
2
are constructed from the 3s and 3p atomic orbitals of sulfur. Further, S
2
has the same
number of valence electrons as O
2
. Thus, by analogy to our discussion of O
2
, we would expect S
2
to have a
bond order of 2 (a double bond) and to be paramagnetic with two unpaired electrons in the molecular
orbitals of S
2
. (Section 9.8) (d) We are considering the reaction in which an S
8
molecule falls apart into four
S
2
molecules. From parts (b) and (c), we see that S
8
has SS single bonds and S
2
has double bonds.
During the course of the reaction, therefore, we are breaking eight SS single bonds and forming four
double bonds. We can estimate the enthalpy of the reaction by using Equation 8.12 and the average bond
enthalpies in Table 8.4:
Fig 7.30
BACK
Figure 7.30 Elemental sulfur. At room temperature, the most common allotropic form of sulfur is an
eight-member ring, S
8
.
Fig 9.7
BACK
Figure 9.7 Relative sizes of
bonding and nonbonding
electron domains.
Figure 9.36 Energy-level diagram for the He
2
+
ion.
Fig 9.36
BACK
Fig 9.45
BACK
Figure 9.45 The second-row diatomic molecules. Molecular orbital electron configurations and
some experimental data for several second-row diatomic molecules.
Table 8.4
BACK
Table 9.1 (part a)
Table 9.1 (go to part b) BACK
Table 9.1 (part b)
Table 9.1
(go to part a)
BACK
Table 9.2 (part a)
BACK
Table 9.2 (go to part b)
Table 9.2 (part b)
BACK
Table 9.2 (go to part a)
Table 9.2 (part a)
Table 9.2 (go to part b)
BACK
Table 9.2 (part b)
BACK
Table 9.2 (go to part a)
Table 9.3 (part a)
BACK
Table 9.3
(go to part b)
Table 9.3 (part b)
BACK
Table 9.3 (go to part a)
Table 9.4 (part a)
BACK
Table 9.4
(go to part b)
Table 9.4 (part b)
BACK
Table 9.4
(go to part a)
Table 9.4 (part a)
BACK
Table 9.4 (go
to part b)
Table 9.4 (part b)
BACK
Table 9.4
(go to part a)
Fig 8.6
BACK
Figure 8.6
Electronegativities of
the elements.
Electronegativity generally
increases from left to right
across a period and
decreases from top to
bottom down a group.
Table 2.4
BACK
Table 2.5
BACK
Table 8.1
BACK
Table 8.2
BACK