Fall 2022

CHAPTER 10
Chemical Bonding II:
Molecular Shapes and
Valence Bond Theory

1
Shapes of Molecules
• Lewis structures of molecules can be used to predict the three-
dimensional structures of molecules

• Two key concepts are:

− Electrons repel each other
− Electron groups assume orientations to minimize
repulsion

• Electron groups can be chemical bonds or lone pairs

• This is the Valence Shell Electron Pair Repulsion Theory (VSEPR)
• Usually we find geometry around the central atom
2
Two Electron Groups: Linear Geometry
• Two electron groups achieve maximum separation by assuming a
180° bond angle (linear geometry)
Example: BeCl2

Example: CO2

Example: acetylene (C2H2)

3
Three Electron Groups: Trigonal Planar Geometry
• Three electron groups achieve maximum separation by assuming
120° bond angles in a single plane (trigonal planar geometry)

Example: BF3

Example: formaldehyde

4
Four Electron Groups: Tetrahedral Geometry
• Four electron groups achieve maximum separation by assuming
109.5° bond angles in 3-D space (tetrahedral geometry)

Example: CH4

5
Five Electron Groups: Trigonal Bipyramidal Geometry
• Five electron groups achieve maximum separation by assuming
the shape of a trigonal bipyramid
• Two axial groups, three equatorial groups

Example: PCl5

6
Six Electron Groups: Octahedral Geometry
• Six electron groups achieve maximum separation by assuming
the shape of an octahedron

Example: SF6

7
Let’s work a problem
Determine the geometry of the NO3- anion.

8
Effect of Lone Pairs on Geometry
• Lone pairs of electrons on central atoms count as electron groups

• Electron geometry = geometric arrangement of the electron

groups (the five examples given earlier)

• Molecular geometry = geometric arrangement of the atoms only,

may be different from electron geometry

9
Four Electron Groups, One Lone Pair
• Consider ammonia (NH3)

• Electron geometry is tetrahedral

• Molecular geometry is trigonal pyramidal

10
Four Electron Groups, Two Lone Pairs
• Consider water (H2O)

• Electron geometry is tetrahedral

• Molecular geometry is bent (or angular)

11
Effects of Lone Pairs on Bond Angles
• Bond angles in NH3 and H2O are somewhat distorted from the ideal
tetrahedral angle

• Lone pair electrons more spread out in space than bonded electron pairs,
hence they “compress” bond angles of the atoms in the molecule

Electron group repulsions:

lone pair/lone pair > lone pair/bonded pair > bonded pair/bonded pair

12
Effects of Lone Pairs on Bond Angles
• Exact bond angles in NH3 and H2O not critical but understand the
trends that are being shown:

13
Five Electron Groups, One Lone Pair
• Consider SF4

• Electron geometry is trigonal

bipyramidal, lone pair occupies
one of the five positions

• Does the lone pair occupy an

axial or equatorial position?

14
Five Electron Groups, One Lone Pair
• Lone pair occupies the equatorial position to minimize repulsive effects with
the other groups

• Molecular geometry is “seesaw”

15
Five Electron Groups, Two Lone Pairs
• Consider BrF3

• Lone pairs both occupy equatorial positions to minimize repulsions

• Molecular geometry is “T-shaped”

16
Five Electron Groups, Three Lone Pairs
• Consider XeF2

• Lone pairs occupy all equatorial positions to minimize repulsions

• Molecular geometry is linear

17
Six Electron Groups, One Lone Pairs
• Consider BrF5

• Lone pair occupies any one of the positions

• Molecular geometry is square pyramidal

18
Six Electron Groups, Two Lone Pairs
• Consider XeF4

• Lone pairs occupy positions 180°apart to minimize repulsions

• Molecular geometry is square planar

19
Summarizing VSEPR
• Table 10.1 summarizes all the geometries covered along with
ideal bond angles

• Don’t memorize – understand!

• Best way to study: practice, practice, practice

20
Polling Question
What is the molecular geometry of ICl4- ?

A) Tetrahedral
B) Octahedral
C) Square pyramidal
D) Square planar
E) Trigonal pyramidal

21
Predicting Shapes of Larger Molecules
• Larger molecules (typically organic) contain multiple interior atoms
instead of one central atom

Lewis structure of glycine:

• VSEPR can be used to determine

molecular geometries around each interior
atom

22
Polling Question
What are the molecular geometries around the indicated carbon and
nitrogen atoms?

A) C = bent, N = tetrahedral
B) C = trigonal planar, N = trigonal pyramidal
C) C = trigonal planar, N = tetrahedral
D) C = tetrahedral, N = trigonal pyramidal
23
Drawing Tetrahedral Structures
• Tetrahedral geometries arise often in organic molecules (C with
four single bonds)

• Three dimensions are shown using hashed and solid wedges

24
Molecular Shape and Polarity
• Polar covalent bonds within molecules can lead to the entire molecule
being polar if there is a net dipole moment overall

Ex: HCl

• If bond dipoles sum to zero (vector addition), they cancel out giving
zero dipole moment overall (non-polar molecule)

Ex: CO2

25
Molecular Shape and Polarity
• Understanding molecular geometries is important in determining
molecular polarities

Ex: H2O

26
Polling Question
Is CCl4 a polar or non-polar molecule?

A) Polar molecule
B) Non-polar molecule

27
Molecular Shape and Polarity
• Molecular polarity important for determining its physical properties
(melting point, boiling point, water solubility, etc.)

• Molecular polarities give rise to intermolecular forces between

molecules, explored in chapter 11

28
Valence Bond Theory
• Lewis bonding model represents electrons as “dot-like” particles

• Two more advanced quantum mechanical models of chemical bonding:

valence bond theory and molecular orbital theory

• Valence bond theory: covalent bonds are formed from the overlap
(constructive interference) of atomic orbitals on adjacent atoms, each usually
containing one electron

• Atomic orbitals may be “standard” (s, p, d, f) or “hybrid” (mathematical

combination of several standard orbitals)

• Orbitals involved in bonding explain the geometry of the molecule

29
Energy Diagram of H-H bond
• When two H atoms are far
apart, energy of interaction is 0

• When two H atoms get

extremely close together, nuclei
repel and energy maximizes

• In between, energy reaches

a minimum, this is the most
stable bond length/energy

30
Orbital Overlap in H2S Molecule
• Half-filled orbitals on H and S atoms overlap to form a bonded electron
pair
• Electrons spin-pair in the covalent bonds that are formed
• Experimental bond angles closely match the 90°angle between p
orbitals on S

31
Hybridization: Covalent Bonding in CH4
• Simple atomic orbital overlap approach works for H2S but fails for CH4
• Simple overlap predicts 90°bond angles about carbon, and only two
bonds can form

• CH4 known to be tetrahedral, 109.5°bond angles

32
Hybridization: Covalent Bonding in CH4
• Orbital hybridization is used to explain experimental bonding evidence
in CH4 (and many more molecules, but we will limit ourselves to the
second row elements)

• Hybridization: a mathematical combination of a certain number of

atomic orbitals to form new hybrid orbitals that are used for bonding

• Different mathematical combinations are possible to explain different

molecular geometries and bonding patterns

• # of atomic orbitals mathematically combined = # of hybrid orbitals

generated
33
sp3 Hybridization
• Mathematically combining 2s and all three 2p orbitals generates four
sp3 orbitals that are all the same energy

• Each orbital (for carbon) is occupied by 1 electron, hence four bonds

are possible (great so far for explaining CH4)

34
Polling Question
If an O atom was sp3 hybridized, what would its orbital diagram be?

A) D)

B)

C)
35
sp3 Hybridization
• The sp3 orbitals resemble both the 2s and 2p orbitals in general shape
• The four hybrid orbitals are oriented 109.5°apart (also great for explaining
CH4 geometry)

36
sp3 Hybridization
• The sp3 orbitals have two lobes (like p orbitals) but one is much smaller than
the other and pointing “inwards” and not significant for bonding purposes

• When sketching the sp3 orbitals together, we ignore

the lobes

• In carbon, each sp3 orbital is occupied with 1

electron

• Used to explain the four covalent bonds carbon

usually forms in compounds

37
sp3 Hybridization
• The full bonding picture for CH4 is the following →
• Hybridization is not utilized for H atoms

• Also used for other atoms with tetrahedral

electron geometries

• Example: NH3 , one lone pair is accommodated

in an sp3 hybrid orbital

38
sp3 Hybridization
In summary….
• If a molecule is predicted to
have tetrahedral electron
geometry by VSEPR…

• …Its bonding can be explained

by sp3 hybridization

• Remember: hybridization is a
mathematical construct used to
39 explain bonding!
sp3 Hybridization
• Second row atoms (particularly C) form reasonably strong bonds with each
other, allowing large complex molecules to exist (organic chemistry!)

• Consider ethane (C2H6): each carbon atom is tetrahedral and sp3 hybridized

40
σ Bonds
• Every covalent bond in ethane is a σ (sigma)
bond, meaning “end-to-end” or “head-on”
overlap of the orbitals involved in the bonding

• The C-C bond in ethane is capable of

rotating freely since σ bonds aren’t affected
by rotation about their axis

• In general, any covalent bond to a hybrid

orbital will be σ

• In general, all single bonds are σ bonds

41
sp2 Hybridization
• Many compounds contain trigonal planar electron geometries

• Example: formaldehyde

• The unhybridized orbital diagrams are:

• Once again, carbon needs to be hybridized to

explain the bonding scheme
42
sp2 Hybridization
• Mathematically combining 2s and two 2p orbitals generates three sp2 orbitals
that are both the same energy
• One of the 2p orbitals is “left over” , or “unhybridized”

43
sp2 Hybridization
• The sp2 orbitals resemble the sp3 orbitals in general shape
• The three hybrid orbitals are oriented 120°apart (great for trigonal planar
geometry)

44
sp2 Hybridization
• The three hybrid orbitals are all in the same plane, and all are oriented
perpendicular to the unhybridized 2p orbital

• The sp2 hybrid orbitals will form σ bonds

(1 each) with three adjacent atoms

• The unhybridized p orbital is used to

explain the double bond in formaldehyde

45
sp2 Hybridization
• Valence bond model (bonding scheme) of formaldehyde

• One C-O bond is a σ bond from sp2 orbital on C with p orbital on O

46
Terminal Atoms
• Tro textbook does not hybridize non-H terminal atoms since it’s not needed to
explain the geometry of the molecule

• Terminal N, O and halogens use their atomic p orbitals to form σ bonds to the
central hybridized atoms as shown earlier

• Example: NF3

• Other sources do hybridize non-H terminal atoms so be mindful

47
π Bonds
• Two unhybridized p orbitals can form π bonds caused by “side-to-side”
overlap
• The two mathematical phases of the orbital must overlap with the same sign
• Half the bond above the atoms, half the bond below

• 48 Don’t worry about whether the p orbital is px, py or pz

π Bonds
• p orbitals can also form σ bonds with hybrid orbitals (sp3, sp2, etc.)
• Hence, the C=O double bond is actually one σ bond: C(sp2) – O(p) and
one π bond: C(p) – O(p)
• Double bonds always consist of 1 σ bond and 1 π bond

49
π Bonds
• π bonds are weaker than corresponding σ bonds due to less efficient orbital
overlap, increases chemical reactivity

• π bonds do not rotate freely as rotation would break the bond

50
sp2 Hybridization: Structure of C2H2Cl2
• Dichloroethylene (C2H2Cl2) has
a C=C double bond consisting
of 1 σ and 1 π bond

• Since π bonds don’t rotate,

the molecule is flat and rigid

51
sp2 Hybridization: Structure of C2H2Cl2
• Since the double bond can’t rotate, there are two structures that can be
drawn that represent entirely different molecules!

• These two compounds are called

“cis/trans” isomers

• Isomers = molecules with the same

molecular formula but different
structures

• cis and trans refer to the arrangement

of groups relative to the double bond axis
52
Structure of C2H4Cl2
• In contrast, C2H4Cl2 has only σ bonds (sp3 hybridization about the
carbons) and hence rotates freely

• There are no cis/trans isomers

53
sp2 Hybridization
In summary….
• If a molecule is predicted to
have trigonal planar electron
geometry by VSEPR…

• …Its bonding can be explained

by sp2 hybridization

• Not all sp2 hybridized atoms

have double bonds

54
Polling Question
Consider the BH3 trigonal planar molecule. What statement is true
regarding the electron configuration of the B atom itself?

H H
A) D)

B) H

C)
55
sp Hybridization
• Some compounds contain linear electron geometries

• Example: acetylene (C2H2)

• The unhybridized orbital diagrams are:

• Once again, carbon needs to be hybridized to

explain the bonding scheme
57
sp Hybridization
• Mathematically combining 2s and one 2p orbital generates two sp orbitals
that are the same energy
• Two of the 2p orbitals are “left over” , or “unhybridized”

58
sp Hybridization
• The sp orbitals are a “50:50” mix of s and p in terms of shape
• The two hybrid orbitals are oriented 180°apart (great for linear geometry)

59
sp Hybridization
• The two hybrid orbitals are all in the same plane, and both are oriented
perpendicular to both unhybridized 2p orbitals

• The unhybridized 2p orbitals are perpendicular

to each other

• The sp hybrid orbitals will form σ bonds

(1 each) with two adjacent atoms

• The unhybridized p orbitals can form

two π bonds

60
sp Hybridization
• The full valence bonding picture in acetylene
• C≡C triple bond is formed from 1 σ bond and 2 π bonds
• The π bonds are oriented 90°apart from each other

61
Polling Question
Are cis/trans isomers possible for molecules containing C≡C?

A) Yes

B) No

62
sp Hybridization
In summary….
• If a molecule is predicted to have linear electron geometry by VSEPR…

• …Its bonding can be explained by sp hybridization

• Not all sp hybridized atoms have triple bonds (ex: BeCl2)

63
Polling Question
What is the hybridization of the oxygen atom in H3O+ ?

A) sp
B) sp2
C) sp3
D) It is not hybridized
64
Polling Question
What is the hybridization of the carbon atom in CO2?

A) sp
B) sp2
C) sp3
D) It is not hybridized

65
Overall Summary

66 * Some 4 electron group atoms have sp2 hybridization: CHEM 2020!

Let’s work a problem
Consider NF3. Draw a figure depicting the geometry of the molecule, the
hybridization of the nitrogen atom, the valence orbitals of each atom and label
each bond as σ or π using the notation in Tro.

67
Let’s work a problem
Draw a figure showing the geometry of the molecule, the hybridization of the
carbon atoms, the valence orbitals of each atom and label each bond as σ or π
using the notation in Tro.

68