Covalent Bonding: William L Masterton Cecile N. Hurley

William L Masterton
Cecile N. Hurley
Chapter 7
Covalent Bonding
Chapter Outline
• (7.1) Lewis structures; The octet rule
• (7.2) Molecular geometry
• (7.3) Polarity of molecules
• (7.4) Atomic orbitals; Hybridization
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Covalent Bonding
• Covalent bonds consist of an electron pair shared
between two atoms
• Hydrogen electrons are not fixed, but may be located
at various points about the two nuclei
H:H or H – H

Figure 7.1 - Electron Density in Hydrogen

Figure 7.2 - Energy of Two Hydrogen Atoms as a Function of
the Distance Between Their Nuclei

Lewis Structures
• Atoms may form ions that are isoelectronic with the
nearest noble gas
• Na forms Na+ 1s22s22p63s1  1s22s22p6
• F forms F- 1s22s22p5  1s22s22p6
• Some atoms share electrons rather than ionize
• Sharing results in atoms becoming isoelectronic with
the nearest noble gas, as they do in forming ions

Valence
• Outermost electrons are called valence electrons
• Consider F
• 1s22s22p5
• 1s are core electrons
• 2s and 2p are valence electrons
• Consider HF
• Hydrogen contributes a 1s electron to form a covalent
bond
• F contributes seven electrons and shares one more
• Total of eight valence electrons
• F in HF now has a total of eight valence electrons

Tools
• Lewis structures
• Distribute electron pairs in a molecule such that each
atom achieves an octet (hydrogen a duet)
• Molecular geometry
• Location of both shared and unshared electron pairs
leads to VSEPR geometry

Table 7.1 - Lewis Structures of Atoms Commonly
Forming Covalent Bonds

Electron Ownership
• Atom owns all lone electrons
• Half the number of bonding electrons
• Bond pair is shown as a line
• Multiple bonds are possible
• Double bonds are two pairs
• Triple bonds are three pairs

Examples of Lewis Structures
• OH-, H2O, NH3, NH4+, C2H4, C2H2

Octet Rule
• Main group elements seek to attain an octet of
electrons
• Recall that an s2p6 configuration is isoelectronic with a
noble gas
• Closed electron shells
• Exception - Hydrogen
• The duet rule

Writing Lewis Structures
• Draw a skeleton structure for the species, joining the
atoms by single bonds
• Count the number of valence electrons (VE)
• Determine the number of valence electrons available
for distribution (AE)
• Determine the number of valence electrons required
to complete an octet for each atom (except H) in the
structure (this is NE, needed electrons)
• If AE = NE, the skeleton is correct
• If AE < NE, place double or triple bonds as needed

Figure 7.3 - Flowchart for Writing Lewis Structures

Example 7.1
–
Draw Lewis structures of the hypochlorite ion, OCl ,
and the ethane, C2H6, molecule

Example 7.1
• Strategy:
• Follow the steps outlined in the flowchart
• For ethane, hydrogen must be a terminal atom since it
cannot form double bonds
• Carbon ordinarily forms four bonds

Example 7.1
• Solution
OCl– skeleton [O–Cl]–
VE 6 (for O) + 7 (for Cl) + 1 (–1 charge) = 14
AE AE = VE – 2 (bonds) = 14 – 2(1 bond) = 12
NE 6 (for O to have an octet) + 6 (for Cl to have
an octet) = 12
AE = NE? Yes; distribute electrons
Lewis structure
C2H6 Skeleton

Example 7.1
VE 2 × 4 (for C) + 6 × 1 (for H) = 14
AE AE = VE – 2(bonds) = 14 – 2(7 bonds) = 0
NE 0 : All the H atoms have duets and both C
atoms have octets.
AE = NE? Yes; distribute electrons
Lewis structure
• End point
• After you have written the Lewis structure, it is a good idea to add the
number of unshared electron pairs and bonding electrons. This sum
must equal the number of valence electrons (VE).
Resonance Forms
• In certain cases, Lewis structures do not represent
chemical or physical reality
• Consider SO2
• Both S-O bonds are equal in length, yet the Lewis
structure indicates one double and one single bond

Resonance in the Nitrate Ion

Figure 7.6 - Benzene Ball-and-Stick
Model, Showing Double Bonds

Resonance Structures
• Resonance forms are not different molecules, nor
are they representations of electron shifting
• Resonance structures arise when two Lewis
structures are equally plausible
• Only electrons can be shifted in resonance
structures
• Atoms cannot be moved

Example 7.3
–
Write two resonance structures for the NO2 ion

Example 7.3
• Strategy:
–
• Lewis structure of NO2 is derived in Example 7.2
• Change the position of the multiple bond and one of

the unshared electron pairs
• Do not change the skeleton

Example 7.3
• Solution:
• The Lewis structures of the two resonance forms are

Formal Charges
• Difference between valence electrons in the free
atom and number assigned to them within a Lewis
structure
• Analogous to oxidation numbers
• Are not actual charges
• Keep track of electron ownership
formal charge = VE - number of unshared electrons - number of bonds

Rules Governing Formal Charge
• Quality of a Lewis structure can be determined by
the distribution of formal charge
• Minimize charges
• Best to have no Cf or small Cf
• Watch electronegativity
• Most electronegative atoms should have the most
negative formal charge

Calculating Formal Charge on CH3OH
• Consider CH3OH
• Formal charge on carbon is 4 – 0 – 4 = 0
• Formal charge on oxygen is 6 – 4 – 2 = 0

Exceptions to the Octet Rule
• Electron-deficient molecules
• Odd electron species (free radicals)
• Paramagnetic
• Examples: NO, NO2

Table 7.2 - Possible Structures for BeF2 and BF3

Exceptions to the Octet Rule
• Molecular oxygen, O2
• Paramagnetic
• Although it has an even number of electrons, it exists
as a diradical (two unpaired electrons)
• Lewis structure is difficult to draw

Expanded Octets
• Some elements are capable of surrounding
themselves with more than four pairs of
electrons
• Expanded octets
• PCl5, SF6

Figure 7.9 - Flowchart for Lewis Structures With
Expanded Octets

Example 7.4
Draw Lewis structures of XeF4

Example 7.4
• Strategy:
• If AE < NE, follow the process described in the Lewis
structure flowchart
• If AE = NE, your skeleton is correct; add electrons as
unshared pairs to form octets around the atoms
• If AE > NE, follow the process described in the
expanded octet flowchart

Example 7.4
Solution:
4(7 (for each F)) + 8 (for Xe) = 36

AE = VE – 2(bonds) = 36 – 2(4 bonds) = 28
4(6 (for each F to have an octet)) + 0 (Xe has an octet)
= 24
No; AE > NE. There are 4 extra electrons

Example 7.4
Lewis structure

Molecular Geometry
• Diatomic molecules are the easiest to visualize in
three dimensions
• HCl
• Cl2
• Diatomic molecules are linear

Two Electron Pairs
• Linear
• Bent
• Bond angles
• Always 180° in a linear molecule
• Always less than 180° in a bent molecule

Valence Shell Electron Pair Repulsion Theory
• Ideal geometry of a molecule is determined by the

way the electron pairs orient themselves in space
• Orientation of electron pairs arises from electron
repulsions
• Electron pairs spread out so as to minimize repulsion

Figure 7.10 - VSEPR Electron-Pair Geometries
• Fundamental geometry exists that corresponds to

the total number of electron pairs around the central
atom: 2, 3, 4, 5, and 6
linear trigonal tetrahedral trigonal octahedral

planar bipyramidal

Molecular Geometries
• Trigonal planar
• Electron pairs form an equilateral triangle around the
central atom
• Bond angles are 120°
• Tetrahedral
• Bond angles are 109.5°

• Trigonal bipyramid
• Bond angles vary
• In the trigonal plane, 120°
• Between the plane and the apexes, 90°
• Between the central atom and both apexes, 180°

• Octahedron
• Is a square bipyramid
• Bond angles vary
• 90° in and out of plane
• 180° between diametrically opposite atoms and the
central atom

Figure 7.1 - Molecular Geometry Summarized

Figure 7.8 - Molecular Geometry Summarized

Unshared Pairs and Geometry
• Electron-pair geometry
• Same as that when single bonds are involved
• Bond angles are a smaller than the ideal values
• Molecular geometry
• Quite different when one or more unshared pairs are
present
• While describing, only the positions of the bonded
atoms are referred

Figure 7.12 - Two Ways of Showing the Geometry of the
NH3 Molecule

Table 7.3 - Geometries with Two, Three, or Four
Electron Pairs Around a Central Atom

Bond Angles and Lone Pairs
• Ammonia and water show smaller bond angles than
predicted from the ideal geometry
• Lone pair is larger in volume than a bond pair
• Nucleus exists at only one end of the bond, so the
electrons are free to spread out over a larger area of
space

Example 7.5
+
Predict the geometry of NH4 , BF3, and PCl3

Example 7.5
• Strategy:
• Start by writing Lewis structures for each species
• Focus on the central atom, then decide what species
type (AX2, AX3, . . . ) the molecule or ion is
• A represents the central atom
• X represents the terminal atoms
• E represents the unshared electron pairs
• Match the species type with the molecular geometry
and ideal bond angles for the species

Example 7.5
Solution:
• Lewis structure for NH4+
Species type A = N, X = H(4), no E→

AX4
Geometry tetrahedral, 109.5° bond
angles

Example 7.5
Lewis structure for BF3
Species type A = B, X = F(3), no E→

AX3
Geometry trigonal planar, 120° bond
angles

Example 7.5
Lewis structure for PCl3
Species type A = P, X = Cl(3), no E =

1→ AX3E
Geometry trigonal pyramid (The ideal
bond angles are 109.5° but
actually are 104°)

The A-X-E Notation
• A denotes a central atom
• X denotes a terminal atom
• E denotes a lone pair
• Example
• Water
• H2O
• O is central
• Two lone pairs
• Two hydrogens
• AX2E2

Lone Pairs and Expanded Octets
• Where expanded octets are possible, place the extra
lone pairs on the central atom
• Example: XeF4

Multiple Bonds
• For molecular geometry purposes, multiple bonds
behave the same as single bonds
• Electron pairs are located in the same place (between
the nuclei)
• Geometry of the molecule is determined by the
number of terminal atoms
• Not affected by the presence of a double or triple bond

Figure 7.15 - Molecular Geometries for Molecules with
Expanded Octets

Figure 7.15 - Molecular Geometries for Molecules with
Expanded Octets

Example 7.6
– –
Predict the geometries of the ClO3 ion, the NO3 ion,
and the N2O molecule, which have the following Lewis
structures, respectively

Example 7.6
• Strategy
• Classify each species as AXmEn
• Multiple bonds count as single bonds. It is the number
of terminal atoms (X) that are counted, not the number
of bonds

Example 7.6
• Solution
–
For ClO3 :
Species type A = Cl, X = O =3, E = 1 →
AX3E
Geometry trigonal pyramid, ideal
bond angles are 109.5°
–
For NO3 :
Species type A = N, X = O = 3, E = 0 →
AX3
Geometry trigonal planar, ideal bond
angles are 120°
Example 7.6
For N2O:
Species type A = N, X = N and O = 2, E
= 0 → AX2
Geometry linear, ideal bond angles
are 180°

Polarity - Bonds
• Polar bond has an asymmetric distribution of
electrons
• X-X is nonpolar
• X-Y is polar
• Polarity of a bond increases with increasing
difference in electronegativity between the two
atoms
• Bond is a dipole
• One end is (δ+), while the other is (δ-)

Polarity - Molecules
• Molecules may also possess polarity
• Positive and negative poles
• Molecule is called a dipole
• Consider HF
• H is δ+, while F is δ–
• Consider BeF2
• Be-F bond is polar
• BeF2 is nonpolar

Figure 7.18 - Polarity of Molecules

Example 7.7
• Determine which of the following is polar: SO2, CO2,
and CHCl3

Example 7.7
• Strategy:
• Write the Lewis structure
• Classify the molecule or ion as AXmEn
• Decide on the geometry
• Consider A — X bonds and answer the following
questions:
(a) Are the terminal atoms identical?
Yes; possibly nonpolar (depends on symmetry)
No; polar

Example 7.7
(b) Are the A — X bonds arranged symmetrically around
the central atom?
No; polar,
Yes; nonpolar if the answer to (a) is also yes

Example 7.7
Solution:
Lewis structure for SO2
Species type AX2E
Geometry bent
Identical terminal atoms? yes - polar
Symmetric A — X bonds no - polar
Lewis structure for CO2
Species type AX2
Geometry linear
Identical terminal atoms? yes - nonpolar
Symmetric A — X bonds yes - nonpolar
Example 7.7
Lewis structure for SO2
Species type AX4

Geometry tetrahedral
Identical terminal atoms? no - polar

Atomic Orbitals and Hybridization
• Valence bond model
• Linus Pauling
• Nobel Prize, 1954
• Orbital diagrams
• Isolated F atom (↑↓) (↑↓) (↑↓)(↑↓)(↑ )
1s 2s 2p
• F atom in HF (↑↓) (↑↓) (↑↓)(↑↓)(↑↓)
1s 2s 2p

Valence Bond Theory
• Unpaired electrons from one atom pair with unpaired
electrons from another atom and give rise to
chemical bonds
• Simple extension of orbital diagrams

Limitations of the Valence Bond Model
• Molecules that form from electron-deficient central
atoms such as Be and B are not explained by the
valence bond model
• Some discrepancies cannot be explained and hence
the model needs to be modified

Figure 7.19 - Formation of sp Hybrid Orbitals
• Number of hybrid orbitals formed always equals the
number of atomic orbitals that are combined
• Two atomic orbitals produce two hybrid orbitals
• One s + one p  two sp

Table 7.4 - Hybrid Orbitals and Geometry

Hybrid Orbitals and Electron
Occupancy
• Same rules observed before
• In an atom, an orbital holds two electrons
• In a molecule, an orbital also holds two electrons
• Electrons in hybrid orbitals
• Lone pairs
• One pair per bond
• Even for a double bond, only one pair goes into the
hybrid orbital

Example 7.10
–
State the hybridization of nitrogen in NH3, NO2 , and N2

Example 7.10
• Strategy:
• Start by writing a Lewis structure for each species
• Determine the species type
• The extra electron pairs in a multiple bond are not
located in a hybrid orbital. Thus the number of
terminal atoms (m) equals the number of bonds in
hybrid orbitals
• Add m + n
• Hybridization type will be based on the (m + n) count

Example 7.10
• Solution
Lewis structure for NH3
Species type AX3E

m+n 3+1=4
hybridization m + n = 4 = sp3
–
Lewis structure for NO2
Species type AX2E

m+n 2+1=3
hybridization m + n = 3 = sp2
Example 7.10
Lewis structure for N2
Species type AXE
m+n 1+1=2
hybridization m + n = 2 = sp

Multiple Bonds
• Sigma (σ) bonds
• Electron density is located between the nuclei
• One pair of each bond is called a sigma pair
• Pi bonds (π)
• Electron density is located above and below or in front
of and at the back of the nuclei
• One pair of a double bond is called pi (π)
• Two pairs of a triple bond are called pi (π)

Figure 7.20 - Bonding Orbitals in Ethylene and
Acetylene

Example 7.11
–
Give the number of pi and sigma bonds in NH3, NO2 ,
and N2

Example 7.11
• Strategy:
• The Lewis structures for these species are given in
Example 7.10.
• Determine the species type. The number of sigma
bonds is m
• Count total bonds in the Lewis structure
• pi bonds = total bonds – m

Example 7.11
• Solution:
• For NH3
Species type AX3; m = 3 → 3 sigma (σ)
bonds
Number of bonds 3
Number of pi bonds 3 – m = 3 – 3 = 0 → no pi
(π) bonds
–
• For NO2
Species type AX2E; m = 2 → 2 sigma (σ)
bonds
Number of bonds 3
Example 7.11
Number of pi bonds 3 – m = 3 – 2 = 0 → 1 pi
(π) bond
• For N2
Species type AXE; m = 1 → 1 sigma (σ)
bond
Number of bonds 3
Number of pi bonds 3 – m = 3 – 1 = 2 → 2 pi
(π) bonds

Key Concepts
• Draw Lewis structures for molecules and polyatomic
ions
• Write resonance forms
• Use the VSEPR theory to predict molecular
geometry
• From the geometry of a species, predict whether it
will be polar or not
• State the hybridization of an atom in a bonded
species
• State the number of sigma and pi bonds in a species

Covalent Bonding: William L Masterton Cecile N. Hurley

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• Change the position of the multiple bond and one of

• Do not change the skeleton

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formal charge = VE - number of unshared electrons - number of bonds

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4(7 (for each F)) + 8 (for Xe) = 36

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• Ideal geometry of a molecule is determined by the

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• Fundamental geometry exists that corresponds to

linear trigonal tetrahedral trigonal octahedral

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Species type A = N, X = H(4), no E→

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Species type A = B, X = F(3), no E→

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Species type A = P, X = Cl(3), no E =