Chemistry

The Molecular Nature of Matter and

Change Eighth Edition

Martin S. Silberberg and Patricia G. Amateis

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 The Shapes of Molecules
• 10.1 Depicting Molecules and Ions with Lewis Structures
• 10.2 Valence-Shell Electron-Pair Repulsion (VSEPR)
Theory
• 10.3 Molecular Shape and Molecular Polarity

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Steps In Converting a Molecular Formula Into a Lewis
Structure

Figure 10.1
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 Example: NF3
• Step 1: N has a lower EN than F, so N is placed in
the center.

• Step 2: N has five valence electrons, and each F

has seven:
– [1 × N(5e−)] + [3 × F(7e−)] = 5e− + 21e− = 26 valence e−

• Step 3: Draw a single bond from each

surrounding atom to the central atom:

• Step 4: Distribute the remaining electrons in pairs

so that each atom ends up with 8e− (or 2e− for H).

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 Sample Problem 10.1 - Problem
Writing Lewis Structures for Species with Single Bonds and One
Central Atom
• PROBLEM: Write a Lewis structure for the following:
a) CCl2F2
b) PCl2-

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 Sample Problem 10.1 - Solution (a)
• SOLUTION (a): CCl2F2
• Step 1: Place the atoms relative to each
other. Carbon has the lowest EN and is
the central atom. The other atoms are
placed around it.
• Step 2: [1 x C(4e–)] + [2 x F(7e–)] + [2 x
Cl(7e–)] = 32 valence e–
• Steps 3-4: Add single bonds, then give
each atom a full octet.

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 Sample Problem 10.1 - Solution (b)
• SOLUTION (b): PCl2-
• Step 1: Place atoms relative to each
other. Phosphorus has the lower EN and
is the central atom. The other atoms
are placed around it.
• Step 2: [1 x P(5e–)] + [2 x Cl(7e–)] + [1
negative charge (1e–)] = 20 valence e–
• Steps 3-4: Add single bonds, then give
each atom a full octet.
• Step 5: Since PCl2– is an ion, draw square
brackets as shown and add the negative
sign at the top (outside the brackets).

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 Sample Problem 10.2 - Problem
Writing Lewis Structures for Molecules with Single Bonds and
More Than One Central Atom
• PROBLEM: Write the Lewis structure for methanol (molecular
formula CH4O), an important industrial alcohol that can be
used as a gasoline alternative in cars.

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 Sample Problem 10.2 - Solution
• SOLUTION:
• Step 1: Place the atoms relative to
each other. H can only form one bond,
so C and O must be central and
adjacent to each other.
• Step 2: [1 x C(4e–)] + [1 x O(6e–)] + [4 x
H(1e–)] = 14 valence e–
• Step 3-4: Add single bonds, then give
each atom (other than H) a full octet.

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 Multiple Bonds
• If there are not enough electrons for the central atom to
attain an octet, a multiple bond is present.
• Step 5: If the central atom does not have a full octet, change
a lone pair on a surrounding atom into another bonding pair
to the central atom, thus forming a multiple bond.

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 Sample Problem 10.3 - Problem
Writing Lewis Structures for Molecules with Multiple Bonds
• PROBLEM: Write Lewis structures for the following:
a) Ethylene (C2H4), the most important reactant in the
manufacture of polymers
b) Nitrogen (N2), the most abundant atmospheric gas

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 Sample Problem 10.3 - Solution (a)
• SOLUTION (a):
– Step 1: Place the atoms relative to each other. In C2H4,the two
C atoms must be bonded to each other since H atoms can
have only one bond.
– Step 2: Determine the total number of valence electrons (C is
in Group 4A; H is in Group 1A):
• [2 × C(4e−)] + [4 × H(1e−) = 12 valence e−
– Step 3: Add single bonds and subtract 2e− for each bond:
5 bonds × 2e− = 10e− so 12e− − 10e−= 2e− remaining
– Step 4: Distribute the remaining valence electrons to attain
octets.
– Step 5: Change a lone pair to a bonding pair. The right C has
an octet, but the left C has only 6e−, so we change the lone
pair on the right C to another bonding pair between the two
C atoms.
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 Sample Problem 10.3 - Solution (b)
• SOLUTION (b):
– Step 1: Place the atoms relative to each other.
– Step 2: Determine the total number of valence electrons (N is
in Group 5A):
• [2 × N(5e−)] = 10 valence e−
– Step 3: Add single bonds and subtract 2e− for each bond:
1 bond × 2e− = 2e− so 10e− − 2e− = 8e− remaining
– Step 4: Distribute the remaining valence electrons to attain
octets.
– Step 5: Neither N ends up with an octet, so we change a lone
pair to a bonding pair. In this case, moving one lone pair to
make a double bond still does not give both N atoms an
octet, so we also move another lone pair from the other N to
make a triple bond.

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 Resonance Structures: Lewis Structures
• O3 can be drawn in 2 ways:

• These are two different reasonable Lewis structures for the

same molecule.
• Neither structure depicts O3 accurately, because in reality the
O-O bonds are identical in length and energy.

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 Resonance Structures: Arrows
• The structure of O3 is shown more correctly using both Lewis
structures, called resonance structures.
– A two-headed resonance arrow is placed between them.

• Resonance structures have the same relative placement of

atoms but different locations of bonding and lone electron
pairs.

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 The Resonance Hybrid
• A species like O3, which can be depicted by more than one
valid Lewis structure, is best represented as a resonance
hybrid.
• Resonance forms are not real bonding depictions.
– O3 does not change back and forth between its two resonance forms.

• The real structure of the resonance hybrid for O3 is an

average of its contributing resonance forms.

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 A Purple Mule

• A mule is a genetic mix, a hybrid,

of a horse and a donkey. It is not a
horse one instant and a donkey
the next. Likewise, a resonance
hybrid has a single structure
although it retains characteristics
of its resonance forms.

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 Electron Delocalization
• Lewis structures depict electrons as localized either on an
individual atom (lone pairs) or in a bond between two atoms
(shared pair).
• In a resonance hybrid, electrons are delocalized: their density
is “spread” over a few adjacent atoms.

• Dotted lines are used to show delocalized electrons.

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 Fractional Bond Orders
• Resonance structures often have fractional bond orders due
to partial bonding.
• For O3, bond order =
3 electron pairs / 2 bonded-atom pairs = 1 ½

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 Sample Problem 10.4 - Problem and Plan
Writing Resonance Structures and Assigning Formal Charges
• PROBLEM: Write resonance structures for the nitrate
ion, NO3-​, assign formal charges to the atoms in each
resonance structure, and find the bond order.
• PLAN: We write a Lewis structure, remembering to add 1e− to
the total number of valence electrons because of the 1− ionic
charge. Then we move lone and bonding pairs to write other
resonance structures and connect them with resonance
arrows. We assign formal charges. The bond order is the
number of shared electron pairs divided by the number of
atom pairs.

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 Sample Problem 10.4 - Solution
• SOLUTION:
• Steps 1 and 2. Nitrogen has the lower group number and is placed in the
center. There are [1 × N(5e−)] + [3 × O(6e−)] + [charge (1e−)] = 24 valence e−.
• Steps 3 and 4 give us:

• Step 5: Since N does not have a full octet, we change a lone pair from O to
a bonding pair to form a double bond.

• Bond order = 4 shared electron pairs / 3 bonded-atom pairs = 1 ⅓

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 Formal Charge
• Formal charge is the charge an atom would have if all
electrons were shared equally.
• Formal charge of atom =
– # of valence e– - (# of unshared valence e– + ½ # of shared valence e–)

• For OA in resonance form I, the formal charge is given by

• 6 valence e– - (4 unshared e– + ½(4 shared e–) = 6 – 4 – 2 = 0

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 Formal Charge: All Resonance Forms
• Formal charges must sum to the actual charge on the species
for all resonance forms.

Resonance Structure I Resonance Structure II

OA [6 – 4 – ½(4)] = 0 OA [6 – 6 – ½(2)] = –1
OB [6 – 2 – ½(6)] = +1 OB [6 – 2 – ½(6)] = +1
OC [6 – 6 – ½(2)] = –1 OC [6 – 4 – ½(4)] = 0

• For both these resonance forms the formal charges sum to

zero, since O3 is a neutral molecule.

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 Choosing the More Important Resonance Form
• Smaller formal charges (positive or negative) are preferable to
larger ones.
• The same nonzero formal charges on adjacent atoms are not
preferred.
• Avoid like charges on adjacent atoms.

• A more negative formal charge should reside on a more

electronegative atom.

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 Preferred Resonance Form of NCO-

• Resonance forms with smaller formal charges are preferred.

Resonance form I is therefore not an important contributor.
• A negative formal charge should be placed on a more
electronegative atom, so resonance form III is preferred to
resonance form II.
• The overall structure of the NCO– ion is a weighted average of
all three forms; resonance forms II and III contribute more
than I, and III contributes more than II.

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 Formal Charge Versus Oxidation Number
• For a formal charge, bonding electrons are shared equally by
the atoms.
– The formal charge of an atom may change between resonance forms.
• For an oxidation number, bonding electrons are transferred
to the more electronegative atom.
– The oxidation number of an atom is the same in all resonance forms.

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 Exceptions to the Octet Rule
• Molecules with Electron-Deficient Atoms
– B and Be are commonly electron-deficient.

• Odd-Electron Species
– A molecule with an odd number of electrons is called a free radical.

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 Exceptions to the Octet Rule: Expanded
Valence Shells
• Expanded Valence Shells
• An expanded valence shell is only possible for nonmetals
from Period 3 or higher because these elements have
available d orbitals.

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 Sample Problem 10.5 - Problem and Plan
Writing Lewis Structures for Octet-Rule Exceptions
• PROBLEM: Write a Lewis structure and identify the octet-rule exception
for
a) XeF4
b) H3PO4
c) BFCl2
• PLAN: We write each Lewis structure and examine it for exceptions to the
octet rule.
a) The central atoms are in Periods 5 and 3, respectively, so they can
have more than an octet.
b) The central atoms are in Periods 5 and 3, respectively, so they can
have more than an octet.
c) The central atom is B, which can have fewer than an octet of
electrons.
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 Sample Problem 10.5 - Solution (a)
• SOLUTION (a):
a) XeF4 has a total of 36 valence electrons: 8 form the bonds
and 24 complete the octets of the F atoms. The remaining 4
valence electrons are placed on the central atom, resulting in
an expanded valence shell:

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 Sample Problem 10.5 - Solution (b)
• SOLUTION (b):
b) H3PO4 has 32 valence electrons: 14 form bonds and 18 complete the
octets of the O and P atoms (structure I, shown with formal charges).
Another resonance structure (structure II) can be drawn in which a lone
pair from the O atom with nonzero formal charge is changed to a
bonding pair.

Structure I obeys the octet rule but has nonzero formal charges. Structure
II has an expanded valence shell with zero formal charges. According to
formal charge rules, structure II is the more important structure.

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 Sample Problem 10.5 - Solution (c)
• SOLUTION (c):
c) BFCl2 has 24 valence electrons: 6 form bonds and 18
complete the octets of the F and Cl atoms. This molecule has
an electron-deficient atom (incomplete octet); B has only six
electrons surrounding it:

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 Valence-Shell Electron-Pair Repulsion Theory
(VSEPR)
• Each group of valence electrons around a central atom is
located as far as possible from the others, to minimize
repulsions.
• A “group” of electrons is any number of electrons that
occupies a localized region around an atom.
– A single bond, double bond, triple bond, lone pair, or single electron
all count as a single group.

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 Electron-group Repulsions and Molecular Shapes

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 Electron-group Arrangement vs Molecular Shape
• The electron-group arrangement is defined by both bonding
and nonbonding electron groups.
• The molecular shape is the three-dimensional arrangement of
nuclei joined by the bonding groups. This is defined only by
the relative positions of the nuclei.
• Molecular shape is classified using the following designation:
AXmEn
A = central atom
X = surrounding atom
E = nonbonding valence electron group
m and n are integers
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 Bond Angle
• The bond angle is the angle formed by the nuclei of two
surrounding atoms with the nucleus of the central atom.

• The angles shown in Figure 10.2 are ideal bond angles,

determined by basic geometry alone. Real bond angles
deviate from the ideal value in many cases.

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 The Single Molecular Shape of the Linear Electron-
group Arrangement

Figure 10.3
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 The Two Molecular Shapes of the Trigonal Planar
Electron-group Arrangement

Figure 10.4
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 Factors Affecting Bond Angles
• Nonbonding (Lone) Pairs
– A lone pair repels bonding pairs more strongly than bonding pairs
repel each other. This decreases the angle between the bonding pairs.

• Double Bonds
– A double bond has greater electron density than a single bond, and
repels the single bond electrons more than they repel each other.

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 The Three Molecular Shapes of the Tetrahedral Electron-
group Arrangement

Figure 10.5
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 Lewis Structures Do Not Indicate Molecular Shape

Figure 10.6
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 The Four Molecular Shapes of the Trigonal Bipyramidal
Electron-group Arrangement

Figure 10.7
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 Axial and Equatorial Positions
• A five electron-group system has two different positions for
electron groups, and two ideal bond angles.
• Where possible, lone pairs in a five electron-group system
occupy equatorial positions.
• Equatorial-equatorial repulsions are weaker than axial-
equatorial repulsions.

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 The Three Molecular Shapes of the Octahedral
Electron-group Arrangement

Figure 10.8
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 Molecular Shapes for Central Atoms in Period 2 and
in Higher Periods

Figure 10.9
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 A Summary of Common Molecular Shapes with Two
to Four Electron Groups

Figure 10.10
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 A Summary of Common Molecular Shapes with Five
or Six Electron Groups

Figure 10.10
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 The Four Steps in Converting a Molecular Formula to
a Molecular Shape

Figure 10.11
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 Sample Problem 10.6 - Problem
Examining Shapes with Two, Three, or Four Electron Groups
• PROBLEM: Draw the molecular shapes and predict the bond
angles (relative to the ideal angles) of:
a) PF3 and
b) COCl2

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 Sample Problem 10.6 - Solution (a)
• SOLUTION (a): For PF3:
• Step 1. Write the Lewis structure from the formula.
• Step 2. Assign the electron-group arrangement: Three bonding groups and
one lone pair give four electron groups around P and the tetrahedral
arrangement.
• Step 3. Predict the bond angle: The ideal bond angle in a tetrahedron
is 109.5°. There is one lone pair, so the actual bond angle will be less
than 109.5°.
• Step 4. Draw and name the molecular shape: With one lone pair, PF 3has
a trigonal pyramidal shape (AX3E):

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 Sample Problem 10.6 - Solution (b)
• SOLUTION (b): For COCl2.
• Step 1. Write the Lewis structure from the formula (see below).
• Step 2. Assign the electron-group arrangement: Two single bonds and one
double bond give three electron groups around C and the trigonal planar
arrangement.
• Step 3. Predict the bond angles: The ideal bond angle in the trigonal
planar arrangement is 120°, but the double bond between C and O will
compress the Cl─C─Cl angle to less than 120°.
• Step 4. Draw and name the molecular shape: With three electron groups
and no lone pairs, COCl2 has a trigonal planar shape(AX3)

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 Sample Problem 10.7 - Problem and Plan
Examining Shapes with Five or Six Electron Groups
• PROBLEM: Draw the molecular shapes and predict the bond
angles (relative to the ideal angles) of
a) SbF5 and
b) BrF5
• PLAN: We proceed as in Sample Problem 10.6, being sure to
minimize the number of axial-equatorial repulsions.

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 Sample Problem 10.7 - Solution (a)
• SOLUTION (a): For SbF5.
• Step 1. Lewis structure (see below).
• Step 2. Electron-group arrangement: With five electron
groups (five bonding pairs), this molecule has the trigonal
bipyramidal arrangement.
• Step 3. Bond angles: All the groups and surrounding atoms are
identical, so the bond angles are ideal: 120° between
equatorial groups and 90° between axial and equatorial
groups.
• Step 4. Molecular shape: Five electron groups and no lone
pairs give the trigonal bipyramidal shape (AX5).

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 Sample Problem 10.7 - Solution (b)
• SOLUTION (b): For BrF5.
• Step 1. Lewis structure (see below).
• Step 2. Electron-group arrangement: Six electron groups (five
bonding pairs and one lone pair) give
the octahedral arrangement.
• Step 3. Bond angles: The lone pair will make all bond angles
less than the ideal 90°.
• Step 4. Molecular shape: With one lone pair, BrF5 has
the square pyramidal shape (AX5E).

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 The Tetrahedral Shapes Around the Central Atoms and the
Overall Shapes of Ethane and Ethanol

Figure 10.12
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 Sample Problem 10.8 - Problem and Plan
Predicting Molecular Shapes with More Than One Central Atom
• PROBLEM: Determine the shape around each central atom in
acetone, (CH3)2CO.
• PLAN: There are three central C atoms, two of which are in
CH3─ groups. We determine the shape around one central
atom at a time.

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 Sample Problem 10.8 - Solution
• SOLUTION:
• Step 1. Lewis structure (see below).
• Step 2. Electron-group arrangement: Each CH3─ group has four electron
groups around its central C, so its electron-group arrangement
is tetrahedral. The third C atom has three electron groups around it, so it
has the trigonal planar arrangement.
• Step 3. Bond angles: The H─C─H angle in CH3─ should be near the
ideal 109.5°. The C═O double bond will compress the C─C─C angle to less
than the ideal 120°.
• Step 4. Shapes around central atoms: With four electron groups and no
lone pairs, the shape around C in each CH3─ is tetrahedral(AX4). With three
electron groups and no lone pairs, the shape around the middle C
is trigonal planar (AX3):

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 Molecular Shape and Molecular Polarity
• Overall molecular polarity depends on both shape and bond
polarity.
• The polarity of a molecule is measured by its dipole moment
(μ), which is given in the unit debye (D).
• A molecule is polar if:
– it contains one or more polar bonds and
– the individual bond dipoles do not cancel.

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 The Orientation of Polar Molecules in an Electric
Field

Figure 10.13
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 Bond Polarity, Bond Angle, and Dipole Moment: CO2
• Example: CO2
• The DEN between C (EN = 2.5) and O (EN = 3.5) makes each
C=O bond polar.
• CO2 is linear, the bond angle is 180°, and the individual bond
polarities therefore cancel. The molecule has no net dipole
moment (μ = 0 D).

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 Bond Polarity, Bond Angle, and Dipole Moment: H2O
• Example: H2O
• The DEN between H (EN = 2.1) and O (EN = 3.5) makes each H-
O bond polar.
• H2O has a V shaped (bent) geometry and the individual bond
polarities do not cancel. This molecule has an overall
molecular polarity. The O is partially negative while the H
atoms are partially positive.

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 Bond Polarity, Bond Angle, and Dipole Moment:
Same Shapes, Different Polarities
• Molecules with the same shape may have
different polarities.

• Bonds are polar, but individual bond

polarities cancel.

• Bond polarities do not cancel. This

molecule is polar (μ = 1.01 D).

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 Sample Problem 10.9 - Problem and Plan
Predicting the Polarity of Molecules
• PROBLEM: For each of the following, use the molecular shape
and EN values and trends to predict the direction of bond and
molecular polarity, if present:
a) ammonia, NH3
b) boron trifluoride, BF3
c) carbonyl sulfide, COS (atom sequence SCO).
• PLAN: We draw and name the molecular shape and point a
polar arrow toward the atom with higher EN in each bond. If
the bond polarities balance one another, the molecule is
nonpolar; if they reinforce each other, we show the direction
of the molecular polarity.
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 Sample Problem 10.9 - Solution (a)
• SOLUTION (a): For NH3. The molecular shape is trigonal
pyramidal. N (EN = 3.0) is more electronegative than H (EN =
2.1), so the bond polarities point toward N and partially
reinforce each other; thus the molecular polarity points
toward N.

• Therefore, ammonia is polar.

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 Sample Problem 10.9 - Solution (b)
• SOLUTION (b): For BF3. The molecular shape is trigonal planar.
F (EN = 4.0) is farther to the right in Period 2 than B (EN =
2.0), so it is more electronegative; thus, each bond polarity
points toward F. However, the bond angle is 120°, so the three
bond polarities balance each other, and BF3 has no molecular
polarity.

• Therefore, boron trifluoride is nonpolar.

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 Sample Problem 10.9 - Solution (c)
• SOLUTION (c): For COS. The molecular shape is linear. With C
and S having the same EN, the C═S bond is nonpolar, but
the C═O bond is quite polar (ΔEN = 1.0), so there is a net
molecular polarity toward the O.

• Therefore, carbonyl sulfide is polar.

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 The Effect of Molecular Polarity on Behavior
• Example: The cis and trans isomers of C2H2Cl2

• The cis isomer is polar while the trans isomer is not. The
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 The Influence of Atomic Properties on Macroscopic
Behavior

Figure 10.4
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 Chemical Connections: Shapes of Some Olfactory
Receptor Sites

Figure B10.1
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 Different Molecules With the Same Odor

Figure B10.2
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 Molecular Shape and Enzyme Action

A. A small sugar molecule (bottom) is B. When the sugar lands in that

shown near a specific region region, the reaction begins.
of an enzyme molecule.

Figure B10.3
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