Chapter 5

Chemical
Bonding I

Drawing Lewis Structures and

Determining Molecular Shapes
 Chapter 5

Chemical
Bonding I

Drawing Lewis Structures and Determining Molecular Shapes

Key Points:
5.1 Morphine
5.2 Electronegativity and Bond Polarity
5.3 Writing Lewis Structures For Molecular Compounds and Polyatomic Ions
5.4 Resonance and Formal Charge
5.5 Exceptions to the Octet Rule
5.6 Bond Energies and Bond Length
5.7 VSEPR Theory: The Five basic shapes
5.8 VSEPR Theory: The Effect of Lone Pairs
5.9 VSEPR Theory: Predicting Molecular Geometries
5.10 Molecular Shape and Polarity
 5.1 Morphine
Why do we care about molecular shape?
• Biological example in the news: Morphine and other opioids are natural
products from the sap of the opium poppy that has pain relieving attributes.
• Morphine binds to nerve (opioid) receptors by altering the transmitted
nerve signals similar to endorphins binding to the opioid receptor’s active
site.
– Like a key in a lock or lock-in-key
• Morphine is a molecular imposter, mimicking the action of endorphins
because of similarities in molecular shape.
• To understand drug interactions, researchers use bonding theories to
simulate the shape of potential drug molecules and how they would
interact.
 Bonding Theories
• Explain how and why atoms attach to form molecules.

• Explain why some combinations of atoms are stable and others are not.
– Why is water H2O, not HO or H3O?

• Can be used to predict the chemical and physical properties of compounds

• Structure determines properties!

• One of the simplest bonding theories is called Lewis theory.

• Lewis theory:
– Emphasizes valence electrons to explain bonding
– Predicts many properties of molecules such as molecular stability, shape, size,
and polarity
 Why Do Atoms Bond?
• Chemical bonds form because they lower the potential energy
between the charged particles that compose atoms.

• A chemical bond forms when the potential energy of the bonded

atoms is less than the potential energy of the separate atoms.

• To calculate this potential energy, you need to consider

the following interactions:
– Nucleus-to-nucleus repulsions
– Electron-to-electron repulsions
– Nucleus-to-electron attractions
 Types of Bonds
• Bonds between atoms are classified based on the types
of atoms that are bonded together.
 5.2 Bond Polarity
• Most bonds have some degree of sharing and some
degree of ion formation to them.

• Covalent bonding between unlike atoms results in unequal

sharing of the electrons.
– One atom pulls the electrons in the bond closer to its side.
– One end of the bond has larger electron density than the other.

• The result is a polar covalent bond.

– Bond polarity
– The end with the larger electron density gets a partial negative charge.
– The end that is electron-deficient gets a partial positive charge.
 5.2 Electronegativity
• The ability of an atom to attract bonding electrons to itself
is called electronegativity.

• The larger the difference in electronegativity, the more

polar the bond.
– Negative end toward more electronegative atom




EN 2.1 H F EN 4.0



 Electronegativity (EN)
• Increases across a period (left to right) and decreases
down a group (top to bottom)
– Fluorine is the most electronegative element.
– Francium is the least electronegative element.
– Noble gas atoms are not assigned EN values.
– Opposite of atomic size trend
 Electronegativity Difference and Bond Type
• If the difference in electronegativity between bonded atoms is 0, the
bond is pure covalent.
– Equal sharing of the atoms in the bond
– If the difference in electronegativity between bonded atoms is 0.1 to
0.4, the bond is nonpolar covalent.
• If the difference in electronegativity between bonded atoms is 0.5 to
1.9, the bond is polar covalent.
– Unequal sharing of electrons between the atoms in
the bond
• If the difference in electronegativity between bonded atoms is larger
than or equal to 2.0, the bond is ionic.
 Bond Dipole Moments
• Dipole moment, μ, is a measure of bond polarity.
– A dipole is a material with a + and − end.
– It is directly proportional to the size of the partial charges (q) and
directly proportional to the distance (r) between them.

μ (dipole moment) = (q)(r)

– Measured in Debyes, D

• Generally, the more electrons two

atoms share and the larger the atoms
are, the larger the dipole moment.
 Practice
Is the bond between each pair of atoms covalent, polar covalent, or ionic?
a. C and F b. N and Cl c. N and O

d. I and I e. Cs and Br f. P and O

 5.3. Writing Lewis Structures for Molecular
Compounds
Steps to write the correct skeletal structure for the molecule.
1. Determine the total number of valence electrons each atom is
bringing in to form the molecule.
2. The less electronegative atom in the molecule is usually the
center atom.
• Simple molecules have a “center” atom to which all of the other atoms in the
molecules are attached (bonded).
3. Attach the other atoms to the center atom through a single bond.
4. Distribute the electrons among the atoms in the molecule giving
octets (or duets in the case of hydrogen) to as many atoms as
possible.
• Place two electrons around an atom at a time as lone pairs.
• The total number of electrons brought in must be accounted for in the
Lewis structure and must not violate any criteria (i.e., octet rule and H
atoms can only have single bonds).
5. If any atoms lack an octet, form double or triple bonds as
necessary to give them octets
 Lewis Structures Symbols

Bonding pairs
bonding pair and
Covalent bonds are pairs (2) of shared valence electrons
a single bond
H
Single bond (2 electrons)
Cl C Cl
Double bond (4 electrons)
Cl
Triple bond (6 electrons) lone pair aka
nonbonding pair
Lone pairs
Electron pairs that are not involved in bonds
 Lewis Structures Practice
Draw Lewis structure for H2O

Draw Lewis structure for CO2

 Lewis Structures Practice
Draw Lewis structure for NH3

Draw Lewis structure for CH2O

 Lewis Structures Practice
Draw Lewis structure for NH4+

Draw Lewis structure for NO3-

 5.4 Resonance and Formal Charges
• Two additional concepts to write the best possible
Lewis structures for a large number
of compounds
• The concepts are:
– Resonance, used when two or more valid Lewis structures
can be drawn for the same compound
– Formal charge, an electron bookkeeping system that
allows us to discriminate between alternative Lewis
structures
 Resonance
• Lewis theory localizes the electrons between the atoms that are
bonding together.
• Extensions of Lewis theory suggest that there is some degree of
delocalization of the electrons; the concept is called resonance.
– Delocalization of charge helps to stabilize the molecule.
• When there is more than one Lewis structure for a molecule that differ
only in the position of the electrons, they are called resonance
structures.
– The actual molecule is a combination of the resonance forms—a
resonance hybrid.
– The molecule does not resonate between the two forms, though we
often draw it that way.
• Example: O3 molecule
 Resonance

Resonance hybrid: Just as the offspring of two different dog breeds is a hybrid
that is intermediate between the two breeds (a), the structure of a resonance
hybrid is intermediate between that of the contributing
resonance structures (b).
 Rules of Resonance Structures
• Resonance structures must have the same connectivity.
– Only electron positions can change.
• Resonance structures must have the same number of electrons.
• Second row elements have a maximum of eight electrons.
– Bonding and nonbonding
– Third row can have expanded octet
 Practice
Write the Lewis structure for the NO2– ion. Include resonance structures.
 Formal Charge
The concept of formal charge is useful because it helps distinguish between competing
skeletal structures or competing resonance structures. In general, these four rules apply:
1. The sum of all formal charges in a neutral molecule must be zero.
2. The sum of all formal charges in an ion must equal the charge of the ion.
3. Small (or zero) formal charges on individual atoms are better than large ones.
4. When formal charge cannot be avoided, negative formal charge should reside on the
most electronegative atom.

Formal charge:
(# of valence electrons) – (# of nonbonding electrons) - (1/2 × # of bonding electrons)

• Example: The molecule HF has 0 (zero) formal charge.

• The formal charge on H atom: Formal charge = 1 − [0 + ½ (2)] = 0

The formal charge on F atom: Formal charge = 7 − [6 + ½ (2)] = 0
 Question
Which of the following is the most correct Lewis structure for N2O?

A. B. C.

D. Need more information

Formal charge:
(# of valence electrons) – (# of nonbonding electrons) - (1/2 × # of bonding electrons)
Formal charges must total the same.
Better structures have fewer formal charges.
Better structures have smaller formal charges.
Better structures have the negative formal charge on the more
electronegative atom.
 Example: Formal Charge, SO2
• During bonding, atoms may end up with more or fewer electrons than
the valence electrons they brought in order to fulfill octets.
– This results in atoms having a formal charge.

Formal Charge (FC) = (valence e–) – (nonbonding e–) – ( ½ bonding e–)

The Lewis structure for SO2:

left O FC = 6 − 4 − ½ (4) = 0
S FC = 6 − 2 − ½ (6) = +1
right O FC = 6 − 6 − ½ (2) = −1

• Sum of all the formal charges in a molecule = 0

– In an ion, total equals the charge.
 5.5 Expanded Octet (Hypervalency)
• Octet rule states that electron sharing continues
until eight electron fill the outer shell.
• Expanded valence shell- when the central atom is
able to accommodate 10, 12, or even more
electrons in the d orbitals
• It can arise several ways:
• More atoms attach to a central atom
• More double bonds
• Adding lone pairs to central atom
• Only p-block atoms in period 3 or later can
expand valence shells
 Practice:
Draw the Lewis Structure for XeF2 and PCl5.
 5.5 Incomplete Octet (Hypovalency)
• Incomplete octets:
• Elements (specifically metalloids and H atom) whose tendency
is not to have a complete octet
• H can only accommodate two electrons (duet).
• Boron (metalloid)
• Prefers six electrons over eight electrons
 5.6 Bond Energies
H H H + H

• Chemical reactions involve breaking bonds in reactant

molecules and making new bonds to create the products.

• The ΔH°reaction can be estimated by comparing the cost of

breaking old bonds to the income from making new bonds.

• The amount of energy, in the gaseous state, that it takes to

break one mole of a bond in a compound is called the bond
energy.
 Trends in Bond Energies
• In general, the more electrons two atoms share, the stronger the covalent bond.
– Must be comparing bonds between like atoms
– C≡C (837 kJ) > C═C (611 kJ) > C—C (347 kJ)
– C≡N (891 kJ) > C ═ N (615 kJ) > C—N (305 kJ)
• In general, the shorter the covalent bond, the stronger the bond.
– Must be comparing similar types of bonds
– Br—F (237 kJ) > Br—Cl (218 kJ) > Br—Br (193 kJ)
– Bonds get weaker down the column.
– Bonds get stronger across the period.
 Covalent Bonding: Model versus Reality for
Bond Length
• Lewis theory predicts that the more electrons two
atoms share, the shorter the bond should be.
– When comparing bonds to
like atoms

• Bond length is determined by measuring the

distance between the nuclei of bonded atoms.
• Bond strength is measured by how much energy
must be added into the bond to break it in half.

• In general, triple bonds are shorter than double

bonds, and double bonds are shorter than single
bonds.
 Trends in Bond Lengths
• In general, the more electrons two atoms share, the shorter the
covalent bond.
– Must be comparing bonds between like atoms
– C≡C (120 pm) < C═C (134 pm) < C—C (154 pm)
– C≡N (116 pm) < C═N (128 pm) < C—N (147 pm)

• Generally, bond length decreases from left to right across

a period.
– C—C (154 pm) > C—N (147 pm) > C—O (143 pm)

• Generally, bond length increases down the column.

– F—F (144 pm) > Cl—Cl (198 pm) > Br—Br (228 pm)

• In general, as bonds get longer, they also get weaker.

 5.7 VSEPR Theory and Molecular Geometries
Structure Determine Properties!
Structure of Compounds Determines Their Properties!

• Properties of molecular substances depend on the structure

of the molecule.

• The structure includes many factors:

– The skeletal arrangement of the atoms
– The kind of bonding between the atoms
• Ionic, polar covalent, or covalent
– The shape of the molecule

• Bonding theory predicts the shapes of molecules.

 VSEPR (Valence Shell Electron Pair Repulsion)
Theory
• Extension of Lewis Theory
• Electron groups around the central atom will be
most stable when they are as far apart as
possible.
– This is the basis for VSEPR (valence shell
electron pair repulsion) theory.
– Because electrons are negatively charged, they
should be most stable when they are separated
as much as possible.

• The resulting geometric arrangement will allow

us to predict the shapes and bond angles in the
molecule.
 Electron Groups
• The Lewis structure predicts the number of valence
electron pairs around the central atoms.

• Each lone pair of electrons constitutes one electron group

on a central atom.

• Each bond constitutes one electron group on a central

atom, regardless of whether it is single, double, or triple.

• Example: NO2–
 Practice
Determine the number of electron groups for the following:
 Electron Group Geometry
• There are five basic arrangements of electron groups around a
central atom.
– Arrangements are as follows:
• Linear, trigonal planar, tetrahedral, bipyramidal, and octahedral
• Based on a maximum of six bonding electron groups
– Though there may be more than six on very large atoms, it is
very rare.

• Each of these five basic arrangements results in five different

basic electron geometries.
– In order for the molecular shape and bond angles to be a “perfect”
geometric figure, all the electron groups must be bonds and all the
bonds must be equivalent.

• For molecules that exhibit resonance, it doesn’t matter which

resonance form you use as the electron geometry will be the
same.
 Electron Groups
• When there are two electron groups around the central atom, they will occupy positions on
opposite sides of the central atom.
• This results in the electron groups taking a linear geometry.
– The bond angle is 180°.

• When there are three electron groups around the central atom, they will occupy positions
in the shape of a triangle around the central atom.
• This results in the electron groups taking a trigonal
planar geometry.
The bond angle is 120°.
 Four Electron Groups: Tetrahedral Electron
Geometry
• When there are four electron groups around the central atom,
they will occupy positions in the shape of a tetrahedron
around the central atom.

• This results in the electron groups taking a tetrahedral

geometry.
– The bond angle is 109.5°.
 Five Electron Groups: Trigonal Bipyramidal
Electron Geometry
• When there are five electron groups around the central atom, they
will occupy positions in the shape of two tetrahedra that are base-
to-base with the central atom in the center of the shared bases.
– This results in the electron groups taking a trigonal bipyramidal
geometry.
• The positions above and below the central atom are called the
axial positions.
– The bond angle between axial and
equatorial positions is 90°.
• The positions in the same base
plane as the central atom are
called the equatorial positions.
– The bond angle between
equatorial positions is 120°.
 Octahedral Electron Geometry
• When there are six electron groups
around the central atom, they will
occupy positions in the shape of two
square-base pyramids that are base-to-
base with the central atom in the
center of the shared bases.

• This results in the electron groups

taking an octahedral geometry.
– It is called octahedral because the
geometric figure has eight sides.

• All positions are equivalent.

– The bond angle is 90°.
 Practice
What is the electron geometry of CH2O?

(a)Linear
(b)Trigonal Planar
(c)Tetrahedral
(d)Octahedral
 5.8 Electron Pair Geometry versus Molecular
Geometry
• The actual geometry of the molecule may be different from the electron
geometry.
– When the electron groups are attached to atoms of different size,
or when the bonding to one atom is different than the bonding to another,
this will affect the molecular geometry around the
central atom.

• Lone pairs also affect the molecular geometry.

– Lone pair groups:
• Occupy space on the central atom but are not “seen” as points on the
molecular geometry
• “Take up more space” on the central atom because their electron density is
exclusively on the central atom, rather than shared like bonding electron
groups
– This affects the bond angles, making the bonding-pair angles smaller than
expected.
 Effect of Lone Pairs on Molecular
Structure

The bonding electrons are shared by two atoms, so some of the

negative charge is removed from the central atom.

Relative sizes of repulsive force interactions are as follows:

Lone pair to Lone pair > Lone pair to Bonding pair > Bonding pair to Bonding pair
 Derivatives of tetrahedral
• When there are four electron groups around the central atom, and one is a lone
pair, the result is called a pyramidal shape because it is a triangular-base
pyramid with the central atom at the apex.

When there are four electron groups around the central atom, and two are lone pairs,
the result is called a bent shape.
Bond Angle Distortion from Lone Pairs
 Derivatives of the Trigonal Bipyramidal
Electron Geometry
• When there are five electron groups around the central atom, and some are
lone pairs, they will occupy the equatorial positions because there is more
room.
– The bond angles between equatorial positions are less than 120°.
– The bond angles between axial and equatorial positions are less than 90°.
– Linear = 180° axial to axial.

• When there are five

electron groups around
the central atom, and
one is a lone pair, the
result is called the
seesaw shape or
sawhorse (aka
distorted tetrahedron).
 Derivatives of the Trigonal Bipyramidal
Electron Geometry
• When there are five electron groups around the central atom, and
some are lone pairs, they will occupy the equatorial positions because
there is more room.
• When there are five electron groups around the central atom,
and two are lone pairs, the result is T-shaped.
 Derivatives of the Trigonal Bipyramidal
Electron Geometry
• When there are five electron groups around the central atom, and
some are lone pairs, they will occupy the equatorial positions because
there is more room.
• When there are five electron groups around the central atom, and
three are lone pairs, the result is Linear.
 Derivatives of the Octahedral Geometry
• When there are six electron groups around the central atom, and some
are lone pairs, each even number lone pair will take a position opposite
the previous lone pair.
• When there are six electron groups around the central atom, and one is
a lone pair, the result is called a square pyramidal shape.
– The bond angles between axial and equatorial positions are less
than 90°.
 Derivatives of the Octahedral Geometry
• When there are six electron groups around the central atom, and some
are lone pairs, each even number lone pair will take a position opposite
the previous lone pair.
• When there are six electron groups around the central atom, and two
are lone pairs, the result is called a square planar shape.
– The bond angles between equatorial positions are 90°.
 5.9 Using VSEPR to Predict Molecular
Geometries
The steps:
1. Draw the Lewis structure.

2. Determine the number of electron groups around the central

atom.

3. Classify each electron group as a bonding or lone pair, and

count each type.
– Remember, multiple bonds count as one group.

4. Use Table 5.5 to determine the shape and bond angles.

 Practice
Determine the molecular and electronic geometry:
• CO2

• PH3

• ClF5
Representing Three-Dimensional Shapes on
Paper
• Drawing molecules to show their dimensionality on paper (2-D)
is difficult.
• How to draw a 3-D representation of a molecule on paper:
– By convention, the central atom is put in the plane of the paper.
– Put as many other atoms as possible in the same plane and indicate
with a straight line.
– For atoms in front of the plane, use a solid wedge.
– For atoms behind the plane, use a hatched wedge.
Illustrations of Molecular Geometries of
Molecules Using 3-D Notations
 Multiple Central Atoms and Their Geometries
• Many molecules have larger structures with many interior
atoms.
– Think of them as having multiple central atoms.

• For multiple-center molecules:

– Each center atom has a designated shape.

• Example: Glycine

• The shape around the:

• N atom is trigonal pyramidal
• Left C is tetrahedral
• Right C is trigonal planar
• O is bent
 Molecular Polarity

• The bond between the H atom and Cl atom in HCl molecule

is polar.
• The bonding electrons are pulled toward the Cl end of the molecule
because Cl is more electronegative (EN) than the
H atom.
– The net result is a polar molecule.
 Molecular Polarity

• The bond between the C atom and O atoms in CO2 molecule

is polar.

• The bonding electrons are pulled toward the O ends of the molecule
equally because O is more electronegative (EN) than the C atom.
– The net result is a nonpolar molecule.
 Molecular Polarity
• The bond between the O atom and H atoms in H2O molecule
is polar.
• Both sets of bonding electrons are pulled toward the O end of the
molecule equally because O is more electronegative (EN) than the H
atom.
• Because of its geometry, the lone pairs do not negate the dipole
moments that result from the two O–H bonds.
• The net result is a polar molecule.
 Molecular Polarity Flow Chart
Formula-
Draw Lewis
Structure

Is there a polar yes Are the polar bonds yes

bond in the arranged so that Not polar
molecule? they cancel out?
no no

Not polar Polar

 PRACTICE
• Determine if the following molecules are polar:

Formula-
Draw Lewis Structure

yes
Is there a polar bond in Are the polar bonds arranged yes
the molecule? so that they cancel out? Not polar

no no

Not polar Polar

 Summarizing Determining Molecular Shape
and Polarity
• Draw the Lewis structure for the molecule and determine its
molecular geometry.
• Determine if the molecule contains polar bonds.
– A bond is polar if the two bonding atoms have sufficiently different
electronegativities.
– If the molecule contains polar bonds, superimpose a vector, pointing
toward the more electronegative atom, on each bond.
– Make the length of the vector proportional to the electronegativity
difference between the bonding atoms.

• Determine if the polar bonds add together to form a net dipole

moment.
– Sum the vectors corresponding to the polar bonds together. If the
vectors sum to zero, the molecule is nonpolar.
– If the vectors sum to a net vector, the molecule is polar.