CHAPTER 10

CHEMICAL BONDING II: MOLECULAR

GEOMETRY AND HYBRIDIZATION OF
ATOMIC ORBITALS
Problem Categories
Biological: 10.92, 10.109, 10.120.
Conceptual: 10.21, 10.22, 10.23, 10.24, 10.45, 10.49, 10.50, 10.53, 10.57, 10.62, 10.65, 10.66, 10.67, 10.68, 10.69,
10.70, 10.73, 10.74, 10.79, 10.81, 10.83, 10.86, 10.88, 10.89, 10.91, 10.94, 10.98, 10.102, 10.103, 10.105, 10.107,
10.111.
Descriptive: 10.19, 10.20, 10.126.
Environmental: 10.90, 10.106.
Organic: 10.23, 10.24, 10.37, 10.38, 10.42, 10.45, 10.65, 10.66, 10.67, 10.87, 10.88, 10.89, 10.96, 10.108, 10.117,
10.118.

10.7 (a) The Lewis structure of PCl3 is shown below. Since in the VSEPR method the number of bonding pairs
and lone pairs of electrons around the central atom (phosphorus, in this case) is important in
determining the structure, the lone pairs of electrons around the chlorine atoms have been omitted for
simplicity. There are three bonds and one lone electron pair around the central atom, phosphorus, which
makes this an AB3E case. The information in Table 10.2 shows that the structure is a trigonal pyramid
like ammonia.

What would be the structure of the molecule if there were no lone pairs and only three bonds?

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380 CHAPTER 10: CHEMICAL BONDING II

(b) The Lewis structure of CHCl3 is shown below. There are four bonds and no lone pairs around carbon
which makes this an AB4 case. The molecule should be tetrahedral like methane (Table 10.1).

(c) The Lewis structure of SiH4 is shown below. Like part (b), it is a tetrahedral AB4 molecule.

(d) The Lewis structure of TeCl4 is shown below. There are four bonds and one lone pair which make this
an AB4E case. Consulting Table 10.2 shows that the structure should be that of a distorted tetrahedron
like SF4.

Are TeCl4 and SF4 isoelectronic? Should isoelectronic molecules have similar VSEPR structures?

10.8 Strategy: The sequence of steps in determining molecular geometry is as follows:

draw Lewis 
 find arrangement of 
 find arrangement 
 determine geometry
structure electrons pairs of bonding pairs based on bonding pairs

Solution:

Lewis structure Electron pairs Electron Lone pairs Geometry

on central atom arrangement

(a) 3 trigonal planar 0 trigonal planar, AB3

(b) 2 linear 0 linear, AB2

(c) 4 tetrahedral 0 tetrahedral, AB4

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 CHAPTER 10: CHEMICAL BONDING II 381

10.9
Lewis Structure e pair arrangement geometry

Br
Br C Br tetrahedral tetrahedral
(a)
Br

Cl B Cl
(b) trigonal planar trigonal planar
Cl

F N F
(c) tetrahedral trigonal pyramidal
F
(d) tetrahedral Bent
H Se H

(e) − trigonal planar bent

O N O

10.10 We use the following sequence of steps to determine the geometry of the molecules.

draw Lewis 
 find arrangement of 
 find arrangement 
 determine geometry
structure electrons pairs of bonding pairs based on bonding pairs

(a) Looking at the Lewis structure we find 4 pairs of electrons around the central atom. The electron pair
arrangement is tetrahedral. Since there are no lone pairs on the central atom, the geometry is also
tetrahedral.
H
H C I
H

(b) Looking at the Lewis structure we find 5 pairs of electrons around the central atom. The electron pair
arrangement is trigonal bipyramidal. There are two lone pairs on the central atom, which occupy
positions in the trigonal plane. The geometry is t-shaped.

F Cl F
F

(c) Looking at the Lewis structure we find 4 pairs of electrons around the central atom. The electron pair
arrangement is tetrahedral. There are two lone pairs on the central atom. The geometry is bent.

H S H

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382 CHAPTER 10: CHEMICAL BONDING II

(d) Looking at the Lewis structure, there are 3 VSEPR pairs of electrons around the central atom. Recall
that a double bond counts as one VSEPR pair. The electron pair arrangement is trigonal planar. Since
there are no lone pairs on the central atom, the geometry is also trigonal planar.

O
O S O

(e) Looking at the Lewis structure, there are 4 pairs of electrons around the central atom. The electron pair
arrangement is tetrahedral. Since there are no lone pairs on the central atom, the geometry is also
tetrahedral.
2−
O
O S O
O

10.11 The lone pairs of electrons on the bromine atoms have been omitted for simplicity.

10.12 (a) AB4 tetrahedral (f) AB4 tetrahedral

(b) AB2E2 bent (g) AB5 trigonal bipyramidal

(c) AB3 trigonal planar (h) AB3E trigonal pyramidal

(d) AB2E3 linear (i) AB4 tetrahedral

(e) AB4E2 square planar

10.13 The Lewis structure is:

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 CHAPTER 10: CHEMICAL BONDING II 383

10.14 Only molecules with four bonds to the central atom and no lone pairs are tetrahedral (AB4).
2−
Cl
Cl I

Cl Cd Cl
Cl Si Cl I C I

Cl
Cl I

What are the Lewis structures and shapes for XeF4 and SeF4?

10.19 All four molecules have two bonds and two lone pairs (AB2E2) and therefore the bond angles are not linear.
Since electronegativity decreases going down a column (group) in the periodic table, the electronegativity
differences between hydrogen and the other Group 16 element will increase in the order Te  Se  S  O.
The dipole moments will increase in the same order. Would this conclusion be as easy if the elements were in
different groups?

10.20 The electronegativity of the halogens decreases from F to I. Thus, the polarity of the HX bond (where X
denotes a halogen atom) also decreases from HF to HI. This difference in electronegativity accounts for the
decrease in dipole moment.

10.21 CO2  CBr4 (  0 for both)  H2S  NH3  H2O  HF

10.22 Draw the Lewis structures. Both molecules are linear (AB2). In CS2, the two CS bond moments are equal in
magnitude and opposite in direction. The sum or resultant dipole moment will be zero. Hence, CS2 is a
nonpolar molecule. Even though OCS is linear, the CO and CS bond moments are not exactly equal, and
there will be a small net dipole moment. Hence, OCS has a larger dipole moment than CS2 (zero).

10.23 Molecule (b) will have a higher dipole moment. In molecule (a), the trans arrangement cancels the bond
dipoles and the molecule is nonpolar.

10.24 Strategy: Keep in mind that the dipole moment of a molecule depends on both the difference in
electronegativities of the elements present and its geometry. A molecule can have polar bonds (if the bonded
atoms have different electronegativities), but it may not possess a dipole moment if it has a highly
symmetrical geometry.

Solution: Each vertex of the hexagonal structure of benzene represents the location of a C atom. Around
the ring, there is no difference in electronegativity between C atoms, so the only bonds we need to consider
are the polar CCl bonds.

The molecules shown in (b) and (d) are nonpolar. Due to the high symmetry of the molecules and the equal
magnitude of the bond moments, the bond moments in each molecule cancel one another. The resultant

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384 CHAPTER 10: CHEMICAL BONDING II

dipole moment will be zero. For the molecules shown in (a) and (c), the bond moments do not cancel and
there will be net dipole moments. The dipole moment of the molecule in (a) is larger than that in (c), because
in (a) all the bond moments point in the same relative direction, reinforcing each other (see Lewis structure
below). Therefore, the order of increasing dipole moments is:

(b) = (d) < (c) < (a).

10.31 AsH3 has the Lewis structure shown below. There are three bond pairs and one lone pair. The four electron
pairs have a tetrahedral arrangement, and the molecular geometry is trigonal pyramidal (AB3E) like ammonia
3
(See Table 10.2). The As (arsenic) atom is in an sp hybridization state.

3
Three of the sp hybrid orbitals form bonds to the hydrogen atoms by overlapping with the hydrogen 1s
3
orbitals. The fourth sp hybrid orbital holds the lone pair.

10.32 Strategy: The steps for determining the hybridization of the central atom in a molecule are:

draw Lewis Structure use VSEPR to determine the use Table 10.4 of
of the molecule electron pair arrangement the text to determine
surrounding the central the hybridization state
atom (Table 10.1 of the text) of the central atom

Solution:
(a) Write the Lewis structure of the molecule.

Count the number of electron pairs around the central atom. Since there are four electron pairs around
Si, the electron arrangement that minimizes electron-pair repulsion is tetrahedral.
3 3
We conclude that Si is sp hybridized because it has the electron arrangement of four sp hybrid orbitals.

(b) Write the Lewis structure of the molecule.

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 CHAPTER 10: CHEMICAL BONDING II 385

Count the number of electron pairs around the “central atoms”. Since there are four electron pairs
around each Si, the electron arrangement that minimizes electron-pair repulsion for each Si is
tetrahedral.
3 3
We conclude that each Si is sp hybridized because it has the electron arrangement of four sp hybrid
orbitals.

10.33 The Lewis structures of AlCl3 and AlCl

4 are shown below. By the reasoning of the two problems above, the
2 3
hybridization changes from sp to sp .

What are the geometries of these molecules?

2
10.34 Draw the Lewis structures. Before the reaction, boron is sp hybridized (trigonal planar electron arrangement)
3
in BF3 and nitrogen is sp hybridized (tetrahedral electron arrangement) in NH3. After the reaction, boron and
3
nitrogen are both sp hybridized (tetrahedral electron arrangement).

10.35 (a) NH3 is an AB3E type molecule just as AsH3 in Problem 10.31. Referring to Table 10.4 of the text, the
3
nitrogen is sp hybridized.

(b) N2H4 has two equivalent nitrogen atoms. Centering attention on just one nitrogen atom shows that it is
3
an AB3E molecule, so the nitrogen atoms are sp hybridized. From structural considerations, how can
N2H4 be considered to be a derivative of NH3?

 2
(c) The nitrate anion NO3 is isoelectronic and isostructural with the carbonate anion CO3 that is
discussed in Example 9.5 of the text. There are three resonance structures, and the ion is of type AB3;
2
thus, the nitrogen is sp hybridized.

10.36 Strategy: The steps for determining the hybridization of the central atom in a molecule are:

draw Lewis Structure use VSEPR to determine the use Table 10.4 of
of the molecule electron pair arrangement the text to determine
surrounding the central the hybridization state
atom (Table 10.1 of the text) of the central atom

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386 CHAPTER 10: CHEMICAL BONDING II

Solution:
Write the Lewis structure of the molecule.

Count the number of electron pairs around the central atom. Since there are five electron pairs around P, the
electron arrangement that minimizes electron-pair repulsion is trigonal bipyramidal (AB5).

3 3
We conclude that P is sp d hybridized because it has the electron arrangement of five sp d hybrid orbitals.

3
10.37 An sp d hybridization indicates that the electron-pair arrangement about iodine is trigonal bipyramidal. If four
fluorines are placed around iodine, the total number of valence electrons is 35. Only 34 electrons are required
to complete a trigonal bipyramidal electron-pair arrangement with four bonds and one lone pair of electrons.
Taking one valence electron away gives the cation, IF4 .

3 2
10.38 An sp d hybridization indicates that the electron-pair arrangement about iodine is octahedral. If four
fluorines are placed around iodine, the total number of valence electrons is 35. Thirty-six electrons are
required to complete an octahedral electron-pair arrangement with four bonds and two lone pairs of electrons.
Adding one valence electron gives the anion, IF4 .

10.40 (a) Each carbon has four bond pairs and no lone pairs and therefore has a tetrahedral electron pair
3
arrangement. This implies sp hybrid orbitals.
H H

H C C H

H H

3
(b) The left-most carbon is tetrahedral and therefore has sp hybrid orbitals. The two carbon atoms
2
connected by the double bond are trigonal planar with sp hybrid orbitals.

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 CHAPTER 10: CHEMICAL BONDING II 387

H H H

H C C C H

3
(c) Carbons 1 and 4 have sp hybrid orbitals. Carbons 2 and 3 have sp hybrid orbitals.
H H

H C1 C2 C3 C4 OH

H H

3
(d) The left-most carbon is tetrahedral (sp hybrid orbitals). The carbon connected to oxygen is trigonal
2
planar (why?) and has sp hybrid orbitals.
H H

H C C O

H
3 2
(e) The left-most carbon is tetrahedral (sp hybrid orbitals). The other carbon is trigonal planar with sp
hybridized orbitals.
H O

H C C O H

10.41 (a) sp (b) sp (c) sp

10.42 Strategy: The steps for determining the hybridization of the central atom in a molecule are:

draw Lewis Structure use VSEPR to determine the use Table 10.4 of
of the molecule electron pair arrangement the text to determine
surrounding the central the hybridization state
atom (Table 10.1 of the text) of the central atom

Solution:
Write the Lewis structure of the molecule. Several resonance forms with formal charges are shown.
− + − − + 2− − 2− + −
N N N N N N N N N

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388 CHAPTER 10: CHEMICAL BONDING II

Count the number of electron pairs around the central atom. Since there are two electron pairs around N, the
electron arrangement that minimizes electron-pair repulsion is linear (AB2). Remember, for VSEPR purposes
a multiple bond counts the same as a single bond.

We conclude that N is sp hybridized because it has the electron arrangement of two sp hybrid orbitals.

2
10.43 The Lewis structure is shown below. The two end carbons are trigonal planar and therefore use sp hybrid
orbitals. The central carbon is linear and must use sp hybrid orbitals.

A Lewis drawing does not necessarily show actual molecular geometry. Notice that the two CH2 groups at the
ends of the molecule must be perpendicular. This is because the two double bonds must use different 2p
orbitals on the middle carbon, and these two 2p orbitals are perpendicular. The overlap of the 2p orbitals on
each carbon is shown below.

C C C

Is the allene molecule polar?

10.44 A single bond is usually a sigma bond, a double bond is usually a sigma bond and a pi bond, and a triple bond
is always a sigma bond and two pi bonds. Therefore, there are nine pi bonds and nine sigma bonds in the
molecule.

10.45 It is almost always true that a single bond is a sigma bond, that a double bond is a sigma bond and a pi bond,
and that a triple bond is always a sigma bond and two pi bonds.

(a) sigma bonds: 4; pi bonds: 0 (b) sigma bonds: 5; pi bonds: 1

(c) sigma bonds: 10; pi bonds: 3

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