UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

1. Give the hybridization of the central atom (atoms in the case of e and f) in each of the following molecules or
ions.

(a) CF4 The parent (and molecular) shape is tetrahedral, and thus C is sp3 hybridized.

(b) [PCl6] – The parent (and molecular) shape is octahedral, and thus P is sp3d2 hybridized.

(c) [SiCl5] – The parent (and molecular) shape is trigonal bipyramidal, and thus Si is sp3d hybridized.

(d) BBr3 The parent (and molecular) shape is trigonal planar, and thus B is sp2 hybridized.

(e) C2F4 The parent shape about each C is trigonal planar, and thus both are sp2 hybridized.
The singly occupied p orbitals on each C will overlap to form a π bond, thus completing
the double bond in the structure.

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

(f) C2Cl2 The parent shape about each C is linear, and thus both are sp hybridized.
The two singly occupied p orbitals on each C will overlap to form two π bonds, thus
completing the triple bond in the structure.

2. Consider each of the following molecules to answer parts (a) – (d). SiH4, NCCN, SF6, SeF4

(a) Which are polar molecules? SeF4

(b) Which are linear molecules? NCCN

(c) Which molecules use sp3d2 hybrid orbitals on the central atom for bonding? SF6

(d) Which molecules use sp3 hybrid orbitals on the central atom for bonding? SiH4

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

3. If z is the internuclear axis between two atoms, list all the possible combinations of atomic orbitals (s, px, py,
pz, dxy, dxz, dyz, dx2-y2, dz2) on different atoms that can overlap to produce a σ bond.

Using open and solid shading to indicate relative phases, the possible combinations to produce a σ bond
are:
s and s
pz and s
dz2 and s
pz and pz
pz and dz2
dz2 and dz2

s and s pz and s dz2 and s pz and pz pz and dz2 dz2 and dz2
x

z
y

4. If z is the internuclear axis between two atoms, list all the possible combinations of atomic orbitals (s, px, py,
pz, dxy, dxz, dyz, dx2-y2, dz2) on different atoms that can overlap to produce a π bond.

The possible combinations to produce a π bond are:

px and px
py and py
dxz and dxz
dyz and dyz
px and dxz
py and dyz

px and px dxz and dxz py and py dyz and dyz

x y

px and dxz py and dyz

z z
y x

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

5. Consider the molecule HCN.

(a) Draw a valence bond diagram and orbital overlap diagram for HCN, where z is the internuclear axis.

Valence bond diagram Orbital overlap diagram

(b) How many of the bonds are π bonds? 2

(c) How many of the bonds are σ bonds? 2

The structure of HCN is: H C N:

The H-C bond is a σ bond. The C≡N triple bond consists of one σ and two π bonds. Therefore, there are a
total of two σ bonds and two π bonds in HCN.

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

6. Consider the phosphate ion, [PO4]3—.

(a) Draw a valence bond diagram and orbital overlap diagram for phosphate.

Valence bond diagram Orbital overlap diagram

(b) How many of the bonds are π bonds? 1

(c) How many of the bonds are σ bonds? 4

(d) Which orbitals on phosphorus must be involved in the π bonding in phosphate?

The sp3 hybrid orbitals from the 3s, 3px, 3py and 3pz atomic orbitals on phosphorous form the 4 σ bonds
and a 3d orbital forms the π bond.

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

7. The Lewis structure for acetaldehyde (ethanal) is shown below. For this molecule:

(a) State the hybridization of the carbon attached to the three hydrogen atoms.

The hybridization is sp3.

(b) State the hybridization of the carbon attached to the oxygen atom.

The hybridization is sp2.

(c) Estimate the HCH bond angle.

The bond angle is ~ 109.5°.

(d) Estimate the HCO bond angle.

The bond angle is ~ 120°.

(e) State the maximum number of atoms of ethanal that can lie in the same plane.

A maximum of 5 atoms (shown in red) can be co-planar.

H C
ms are co-planar
C H

H H

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

8. The Lewis acid BF3 reacts with the Lewis base NH3 to form the adduct F3B-NH3

(a) Draw a valence bond diagram and orbital overlap diagram for i) BF 3 and ii) NH3.

i) BF3

ii) NH3

Valence bond diagrams Orbital overlap diagrams (no π bonds)

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

(b) Using the diagrams you have drawn in part (a), show how the adduct is formed.

Since B in BF3 has an empty 2p orbital, it is able to accept the pair of electrons from the sp3 orbital
of N in NH3.

B F

(c) Notice the hybridization of boron changes upon formation of the adduct. What is the hybridization of boron in
BF3 and F3B-NH3?

The hybridization on B in BF3 is sp2, and sp3 in F3B-NH3.

Structure F

B F

hybridization on B sp2 sp3

hybridization on N sp3 sp3

9. For each of the following, draw the BEST Lewis structure (show lone pairs as pairs of dots, show bonds as
lines and label all non-zero formal charges). Use valence bond theory to describe the bonding in each molecule.
Draw a 3-dimensional perspective drawing showing the overall shape of each molecule (Hint: orient each
molecule such that the maximum number of atoms are in the same plane).

(a) CN2H2 (the atom connectivity is HNCNH).

The best Lewis structure is: H N C N H

Consider the hybridization on the two nitrogen atoms and the carbon atom. The nitrogen atoms are sp2
hybridized, the carbon is sp hybridized. The σ bond between the nitrogen and carbon consists of overlap
of a sp2 orbital on N and a sp orbital on C. The π bonds are formed by overlap of a p orbital on N and a p
orbital on C. The carbon has two p orbitals available to form these bonds, one to the nitrogen on the left,
one to the nitrogen on the right. The two p orbitals are oriented 90º with respect to one another, thus the
trigonal planar arrangement of electron groups bonded to the nitrogen atoms are twisted by 90º with
respect to each other:

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

H
N C N
H

p bonds
The 3-dimensional perspective drawing is:

H
N C N
H

(b) C4H4 (the atom connectivity is H2CCCCH2).

The best Lewis structure is: H H

C C C C

H H
Consider the hybridization at the four carbon atoms. The terminal carbon atoms (CA) are sp2 hybridized,
whereas the two central carbons (CB) are sp hybridized. The σ bond between each CA and CB consists of
overlap of a sp2 orbital on CA and a sp orbital on CB. The 2 CA carbons each have one p orbital available
for formation of π bonds, and the 2 CB carbons have 2 p orbitals each available for π bonding. The π
bonds are formed as shown below, resulting in the trigonal planes of the two C A carbon atoms being
coplanar:

H H
CA CB CB CA
H H

p bonds

The 3-dimensional perspective drawing is:

H H
C C C C
H H

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

10. Compounds containing the ion [SiF6]2– exist; however, compounds containing [CF6]2– do not. Briefly explain
this experimental observation using arguments based on valence bond theory and electron configurations.

Hybrid orbitals must be combined from atomic orbitals with similar energies. In [SiF 6]2–, sp3d2 hybrid
orbitals can form, as there are s, p, and d orbitals available in the n = 3 shell (the shell in which all the
valence electrons of silicon are found). [CF6]2- would require sp3d2 hybrid orbitals to form, but there are no
d orbitals available in the n = 2 shell (the shell in which all the valence electrons of carbon are found).
Therefore, these hybrid orbitals will not form and [CF6]2– cannot be prepared.

11. The molecular structure of acetylsalicylic acid, commonly known as Aspirin, is shown below (lone pairs are
not shown).

(a) Give the hybridization of the indicated atoms:

sp2

sp3
2
sp

(b) What is the maximum number of atoms that may be located in the same plane in Aspirin?

The answer is 19. All atoms, except two of the methyl hydrogens, can be co-planar. The one methyl carbon
is sp3 hybridized and tetrahedral; thus two of the three hydrogens are outside the plane of the molecule. The
remaining carbons and all of the oxygens are sp2 hybridized and can be co-planar.

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

12. Esomeprazole is a proton pump inhibitor used in the treatment gastric ulcers. Sold under the trade name
Nexium, sales of this drug exceed $5 billion per year. The chemical structure of this drug is shown below (lone
pairs are not shown):

(a) Give the hybridization of the atoms labeled (a-d).

(a) sp2

(b) sp3

(c) sp2

(d) sp3

(b) The structure of esomeprazole contains a S=O bond.

i) With the aid of an orbital overlap diagram, describe the orbitals involved in forming the S-O double bond in
this molecule.

With a lone pair of electrons, sulfur is sp3 hybridized. Thus a 3d orbital must be used to form the π bond
with a 2p orbital from the sp2 hybridized oxygen. A possible combination is shown below.

ii) What is the predicted C-S-C bond angle?

With sp3 hybridization of the S, the C-S-C bond angle will be approximately 109.5°.

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 UBC Chem 120/121 ChIRP: Chapter 9 – Additional Problem Answers (2022)

13. Both NOF3 and POF3 are known. NOF3 is highly reactive, whereas POF3 is less reactive.

(a) Draw all possible resonance Lewis structures for each molecule.

(b) Compare and contrast the bonding in each of the Lewis structures that you have drawn.

Elements such as N with n = 2 valence shells cannot form expanded octets because the 3d orbitals are
too high in energy to be hybridized with 2s and 2p orbitals. However, elements such as P with n = 3 or
higher valence shells, are capable of hypervalency.

(c) What is the key difference in the bonding in POF 3 vs. NOF3? In other words, why is NOF3 more reactive (or a
more powerful oxidizing agent)?

The bond order for the N-O bond in NOF3 is less than the bond order of the P-O bond in POF3. Thus, the
N-O bond is weaker, leading to NOF3 being more reactive than POF3.

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