Chemical Bonding I

Kim Shih
Morphine: A Molecular Imposter
Morphine works in a body similar to endorphins
binding to the opioid receptor’s active site.

Morphine is a molecular imposter, mimicking the

action of endorphins because of similarities in
molecular shape.
 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
Kim Shih
 Lewis Bonding Theory
• The simplest bonding theories is called Lewis Theory

• A representation of an atom’s valence electrons by using

dots and indicates by the placement of dots how the
valence electrons are distributed in the molecule.

• Lewis structures allow us to predict many properties of

molecules
– such as molecular stability, shape, size, polarity

Kim Shih
 Types of Bonding

Ionic Bond:
Covalent Bond: Electrons transfer from
Atoms share electrons one atom to another.
Product: Molecule Ionic compound

Made of…. Nonmetal Nonmetal + Metal

Example: H2 , NH3, O2 NaCl, MgO, KBr

Kim Shih
 Types of Bonds
• We can classify bonds based on the kinds of
atoms that are bonded together

Bond
Types of Atoms Type of Bond
Characteristic
metals to electrons
Ionic
nonmetals transferred
nonmetals to electrons
Covalent
nonmetals shared
metals to electrons
Metallic
metals pooled
Kim Shih
 Polar Covalent Bonding
• 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

Kim Shih
 Electronegativity

• The ability of an atom to attract bonding electrons to itself

• Increases across period (left to right)
• Decreases down group (top to bottom)
– noble gas atoms are not assigned values
– opposite of atomic size trend
– Fluorine is the most electronegative element.
– Francium is the least electronegative element.
• The larger the difference are, the more polar the bond
– negative end toward more electronegative
Kim Shih
atom
 Electronegativity Difference and Bond Type
• If difference in electronegativity between bonded atoms
is 0, the bond is pure covalent
– equal sharing
• If difference in electronegativity between bonded atoms
is 0.1 to 0.4, the bond is nonpolar covalent
• If difference in electronegativity between bonded atoms
is 0.5 to 1.9, the bond is polar covalent
• If difference in electronegativity between bonded atoms
is larger than or equal to 2.0, the bond is ionic
Percent Ionic Character
4% 51% “100%”

0 0.4 2.0 4.0

Electronegativity Difference
Kim Shih
 Bond Polarity

• Most bonds have some degree of sharing and some degree of ion
formation to them
• Bonds are classified as covalent if the amount of electron transfer is
insufficient for the material to display the classic properties of ionic
compounds
• If the sharing is unequal enough to produce a dipole in the bond, the bond
Kim Shih
is classified as polar covalent
 Bond Polarity

ENCl = 3.0 ENCl = 3.0 ENCl = 3.0

3.0 − 3.0 = 0 ENH = 2.1 ENNa = 0.9
Pure Covalent 3.0 – 2.1 = 0.9 3.0 – 0.9 = 2.1
Polar Covalent Ionic

Kim Shih
 Water – A Polar Molecule

stream of stream of
water hexane not
attracted attracted to
to a a charged
charged glass rod
glass rod

Kim Shih
Polar Molecule Interactions

Polar-ion
(salt dissolved in water)

Polar-polar
(wine)
Like Dissolves Like
Kim Shih
 Bond Dipole Moments
• Dipole moment, m, 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 and directly proportional to the distance
between them
• m = (q)(r)
• measured in Debyes, 1 D = 3.34 x 10-30 C.m
• Generally, the more electrons two atoms share
and the larger the atoms are, the larger the dipole
moment.

Kim Shih
Dipole Moments

Kim Shih
 Identify the bond between each pair of
atoms is covalent, polar covalent or ionic.

1. Sr (EN= 1.0) and F (EN = 4.0) Ionic

2. N (EN = 3.0) and Cl (EN = 3.0) Covalent

3. N (EN = 3.0) and O (EN = 3.5) Polar covalent

 Percent Ionic Character
• The percent ionic character is the percentage of a bond’s
measured dipole moment compared to what it would be if the
electrons were completely transferred.

• The percent ionic character indicates the degree to which the

electron is transferred.
 The compound IF5 contains

A. nonpolar covalent bonds

55%
B. polar covalent bonds with
partial negative charges on
the I atoms. 32%

C. polar covalent bonds with

partial negative charges on 14%

the F atoms.
0%
D. ionic bonds.
polar
nonpolar
covalent
polar
covalent
bonds
covalent
with
bonds
bonds
partial
with
negative
partial
ioniccharges
negative
bonds.
on the I atoms.
on the F atoms.

Kim Shih
Question: What is the dipole moment that result from
separating a proton and an electron by distance of
130pm?
Hint: m = (q)(r) Q= 1.6x 10-19 C R=130pm = 130 x 10-12 m
m = (1.6x 10-19 C )x(130 x 10-12 m) = 2.1 x 10-29 C.m =6.2D

Cont. previous question, the diatomic molecule with a

bond length of130pm has a dipole moment of 3.5D.
What is the percent ionic character of the bond?

Percent ionic character = 3.5D/ 6.2D x 100% = 56%

Kim Shih
 Determine whether an N―O bond is ionic,
covalent, or polar covalent

• Determine the electronegativity of each element

N = 3.0; O = 3.5
• Find the difference of electronegativities
(3.5) − (3.0) = 0.5
• If the difference is 2.0 or larger, then the bond is ionic;
otherwise it’s covalent
difference (0.5) is less than 2.0, therefore covalent
• If the difference is 0.5 to 1.9, then the bond is polar
covalent; otherwise it’s covalent
difference (0.5) is 0.5 to 1.9, therefore polar covalent
Kim Shih
 Lewis Structures of Molecules

• Understand the distribution of valence electrons

in a molecule
• Predict the bonding in many compounds
• We can study shapes, properties of molecules
and how they will interact together

Kim Shih
Octet Rule: A Guideline for Molecule Formation
• When atoms bond, they tend to gain, lose, or share
electrons to result in a “noble gas-like configuration.”
• ns2np6
• Nonmetals (2nd period elements) must obey the octet
rule (i.e., eight valence electrons around each atom in the
molecule, noble gas-like configuration).
• Exceptions to the octet rule: expanded octets
– Involve the nonmetal elements located in the 3rd
period and below
• Nonmetals (3rd period down in the periodic table) follow the octet rule when
they are not the “center” atom.
– The center atom is the atom in the molecule where the other elements
individually bond (attach).
– When they are the center atom, they can accommodate more than eight
electrons.
• Using empty valence d orbitals that are predicted by quantum theory
 Lewis Structures of Molecules
Step 1: Valence Electrons
• Count the total number of valence electrons for all
atoms in the molecule.
• Add one additional electron for each negative charge in
an anion or subtract one for each positive charge in a
cation.

Kim Shih
 Lewis Structures of Molecules
Step 2: Determine the center atom, put the others on the sides
• Usually the atom with the most available valence e-
• Hydrogen always on the side
• Halogen most of the times on the side unless involved in
higher period of atoms

Kim Shih
 Lewis Structures of Molecules
Step 3: Assign Electrons to the Terminal Atoms
• Subtract the number of electrons used for bonding on the side
atoms from the total number determined in step 1.
• Complete each terminal atom’s octet (except for hydrogen).

Step 4: Assign Electrons to the Central Atom

• If unassigned electrons remain after step 3, place them on the
central atom.

Step 5: Multiple Bonds

• If no unassigned electrons remain after step 3 but the central
atom does not yet have an octet, use one or more lone pairs of
electrons from a neighboring atom to form a multiple bond
(either a double or a triple).
Kim Shih
 Draw an electron-dot structure for H3O1+.
Step 1: 3(1) + 6 - 1 = 8 valence electrons

H
Step 2: Identify the center atom H O H
Hydrogen is always on the sides

Step 3: Step 4: 1+
H
H
H O H H O H

Kim Shih
 Draw an electron-dot structure for CH2O.

Step 1: 4 + 2(1) + 6 = 12 valence electrons

O O

Step 2: H C H Step 5: H C H

O O

Step 3: H C H H C H

Kim Shih
 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 –
we call this concept resonance
• Delocalization of charge helps to stabilize the
molecule

Kim Shih
 Resonance Structures
• 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
• Look for multiple bonds or lone pairs
.. .. ..
.. O .... S .. O .. .. .. ..
.. O .. S .... O ..
.. Kim Shih
..
 Electron-Dot Structures and Resonance
Draw an electron-dot structure for O3.

Step 1:

3(6) = 18 valence electrons Step 5: O O O

Step 2: O O O
O O O
Step 3: O O O
Resonance
Move a lone pair from this oxygen?
Step 6: O O O
Step 4: O O O
Kim Shih
Or, move a lone pair from this oxygen?
Resonance

Kim Shih
 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
• Formal charges must total same

Kim Shih
 Practice: Resonance Structures
Write the Lewis structure for the NO3– ion. Include resonance
structures.

Write the Lewis structure for the NO2– ion. Include resonance
structures.
 Evaluating Resonance Structures

• Better structures have fewer formal charges

• Better structures have smaller formal charges
• Better structures have the negative formal
charge on the more electronegative atom

Kim Shih
 Formal Charges
# of # of # of
Formal - 1
= valence e - bonding - nonbonding
Charge in free atom 2 e- e-

Calculate the formal charge on each atom in O3.

O O O

1 1 1
6 - 2(4) - 4 = 0 6 - 2(6) - 2 = +1 6 - 2(2) - 6 = -1

• Better structures have smaller formal charges

• Better structures have the negative formal
charge on the more electronegative atom
Kim Shih
 What are the formal charges for the following structure?
Which structure is the most stable structure?
.. ..
[:O
.. C N ] : [ O:.. C
..:
N ] :
[ O C N:]
..
# of valence e- 6 4 5 6 4 5 6 4 5

# of nonbonding e- 6 0 2 4 0 4 2 0 6

½ bonding e- 1 4 3 2 4 2 3 4 1

Formal Charge -1 0 0 0 0 -1 1 0 -2

O has stronger electronegativity then C and N

The first structure is more stable.

Kim Shih
Which is the best Lewis Structure of
HCN?
Structure A Structure B

H : C ::: N: H : N ::: C:
 Practice - Assign formal charges
CO2 H3PO4
all 0 P = +1
rest 0

SeOF2 SO32−
S = +1
Se = +1

NO2− P2H4
all 0
Kim Shih
Exercise

Kim Shih
What are the formal charges for the following structure?
Which structure is the most stable structure?
a. .. .. b. .. c. ..
:N N O : :N N O :
.. : ..
N N O :

Kim Shih
 Drawing Lewis Structures
1. Draw first Lewis structure that
maximizes octets −1
2. Assign formal charges
3. Move electron pairs from atoms
with (−) formal charge toward −1
atoms with (+) formal charge
4. If (+) fc atom 2nd row, only move +1
in electrons if you can move out
electron pairs from multiple
−1
bond
5. If (+) fc atom 3rd row or below,
keep bringing in electron pairs to −1
reduce the formal charge, even
if get expanded octet +1
Kim Shih
 Drawing Lewis Structures
Expanded Octets
1. Draw first Lewis structure that −1
maximizes octets
2. Assign formal charges +2
3. Move electron pairs from atoms
with (−) formal charge toward
atoms with (+) formal charge
−1
4. If (+) fc atom 2nd row, only move
in electrons if you can move out
electron pairs from multiple bond
5. If (+) fc atom 3rd row or below,
keep bringing in electron pairs to
reduce the formal charge, even if
get expanded octet

Kim Shih
 Exceptions to the Octet Rule
• Expanded octets
– elements with empty d orbitals can have more
than eight electrons
• Odd number electron species e.g., NO
– will have one unpaired electron
– free-radical
– very reactive
• Incomplete octets
– B, Al
Kim Shih
 Exceptions to the Octet Rule:
Incomplete Octets
Exceptions to the octet rule fall into three categories:

1) The central atom has fewer than eight electrons due to a

shortage of electrons.

H Be H only 4 total valence electrons in

the system

 Elements in group 3A also tend to form compounds surrounded

by fewer than eight electrons.

 Boron, for example, reacts with halogens to form compounds

of the general formula BX3 having six electrons around the
boron atom.
Kim Shih
 Exceptions to the Octet Rule:
Odd Numbers of Electrons

2) The central atom has fewer than eight electrons due to an

odd number of electrons.
•• •
17 valence electrons in the
O=N−O •• •• system

Molecules with an odd number of electrons are sometimes referred

to as free radicals.

Kim Shih
 Exceptions to the Octet Rule:
Expanded Octets
3) The central atom has more than eight electrons.

Sulfur has 6 bonds corresponding to 12

electrons

 Atoms in and beyond the third period can have more than eight
valence electrons.

 In addition to the 3s and 3p orbitals, elements in the third

period also have 3d orbitals that can be used in bonding.
Kim Shih
Worked Example 5.1
Draw the Lewis structure of chlorine dioxide (ClO2).
Strategy The skeletal structure is

This puts the unique atom, Cl, in the center and puts the more electronegative O
atoms in terminal positions.

There are a total of 19 valence electrons (7 from the Cl and 6 from each of the
two O atoms). We subtract 4 electrons to account for the two bonds in the
skeleton, leaving us with 15 electrons to distribute as follows: three lone pairs on
each O atom, one lone pair on the Cl atom, and the last remaining electron also on
the Cl atom.
Solution

Kim Shih
Worked Example 5.2
Draw the Lewis structure of boron triiodide (BI3).
Strategy The skeletal structure is

There are a total of 24 valence electrons (3 from the B and 7 from each of the
three I atoms). We subtract 6 electrons to account for the three bonds in the
skeleton, leaving 18 electrons to distribute in lone pairs on each I atom.

Solution

Kim Shih
Worked Example 5.2 (cont.)
Think About It Boron is one of the elements that does not always follow the octet
rule. Like BF3, however, BI3 can be drawn with a double bond in order to satisfy
the octet of boron. This gives rise to a total of four resonance structures.

Kim Shih
Worked Example 5.3 (cont.)
Draw the Lewis structure of arsenic pentafluoride (AsF5).
Strategy The skeletal structure already has more than an octet around the As
atom.

There are 40 total valence electrons [5 from As (Group 5A) and 7 from each of
the five F atoms (Group 7A)]. We subtract 10 electrons to account for the five
bonds in the skeleton, leaving 30 to be distributed. Next, we place three lone pairs
on each F atom, thereby completing all their octets and using up all the electrons.
Solution

Kim Shih
Worked Example 5.4 (cont.)
Draw the Lewis structure of xenon tetrafluoride (XeF4).
Strategy Follow the steps for drawing Lewis structures. The skeletal structure is

There are 36 total valence electrons (8 from Xe and 7 from each of the four F
Think About It Atoms beyond the second period can accommodate
atoms). We subtract 8 electrons to account for the bonds in the skeleton, leaving
more than an octet of electrons, whether those electrons are used in
28 to distribute. We first complete the octets of all four F atoms. When this is
bonds or reside on the atoms as lone pairs.
done, 4 electrons remain, so we place two lone pairs on the Xe atom.
Solution

Kim Shih
 Which of the following Compound
follow octet rule?
A. NH3 83%

B. XeF4
C. BF3
D. H2

13%
5%
0%

NH3 XeF4 BF3 H2

Kim Shih
 Bond Lengths
• The distance between the nuclei of
bonded atoms is called the bond
length
• Because the actual bond length
depends on the other atoms
around the bond we often use the
average bond length
– averaged for similar bonds from
many compounds

Kim Shih
 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 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
Kim Shih
 Place the following in order of
increasing bond length.
C-F, C-S, C-Cl
7% A. C-S < C-Cl < C-F
15% B. C-S < C-F < C-Cl
41% C. C-F < C-Cl < C-S
29% D. C-F < C-S < C-Cl
7% E. C-Cl < C-F < C-S

Kim Shih
 Bond Energies
• 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.
Average Bond Energies
Covalent Bonding: Model versus Reality for Bond Strength

• Lewis theory predicts that the more electrons two atoms share,
the stronger the bond.

– Single bond < Double bond < Triple bond

– Lewis theory would predict that double bonds are twice

as strong as single bonds, but the reality is they are less than
twice as strong.

• Bond strength is measured by how much energy must be added

into the bond to break it in half.
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.

 Calories
• C12 H22 O11 + 12 O2 ---------- 12CO2 + 11H2 O
ΔHrxn = -5644kJ
How do we reduce calories intake in our life?
Enzymes only recognize certain structures from our food.

Kim Shih
 Using Lewis Theory to Predict
Molecular Shapes
• Lewis theory says that these regions of electron
groups should repel each other
– because they are regions of negative charge
• This idea can then be extended to predict the
shapes of molecules
– the position of atoms surrounding a central atom will be
determined by where the bonding electron groups are
– the positions of the electron groups will be determined by
trying to minimize repulsions between them

Kim Shih
 VSEPR Theory
• Electron groups around the central atom will be
most stable when they are as far apart as
possible – we call this 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
Kim Shih
Kim Shih
 Electron Group Geometry
• There are five basic arrangements of electron groups
around a central atom
– based on a maximum of six bonding electron groups
• 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 – the electron
geometry will be the same

Kim Shih
Molecular Shapes: The VSEPR Model
Two Charge Clouds (CO2 and HCN)

Kim Shih
 Two Clouds:e -

Linear Electron Geometry

• This results in the electron groups taking a linear
geometry
• The bond angle is 180°

Kim Shih
 Three Clouds: e-

Trigonal Planar Electron Geometry

• This results in the electron groups taking a trigonal
planar geometry
• The bond angle is 120° such as BF3

Kim Shih
 Four Clouds: e -

Tetrahedral Electron Geometry

• This results in the electron groups taking a
tetrahedral geometry
• The bond angle is 109.5°

Kim Shih
 Five e- Clouds:
Trigonal Bipyramidal Electron Geometry
• This results in the electron groups taking a trigonal bipyramidal
geometry
• The bond angle between equatorial positions is 120°
• The bond angle between axial and equatorial positions is 90°

Kim Shih
 Six Clouds: e -

Octahedral Electron Geometry

• 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°

Kim Shih
 What geometric arrangement of charge clouds is
expected for an atom that has four charge clouds?

9% A. Square planar
0% B. Trigonal bipyramidal
88% C. Tetrahedral
0% D. Octahedral
3% E. Linear

Kim Shih
What geometric arrangement of charge clouds is
expected for PCl3 ?
A. Square planar 56%
B. Trigonal bipyramidal
C. Tetrahedral 36%
D. Octahedral
E. Linear
8%

0% 0%

1 2 3 4 5

Kim Shih
 Predict the electron geometry of PCl3

1. Draw the Lewis

structure
26 valence electrons
2. Determine the
Number of electron
groups around central
atom
four electron groups
around P
Tetrahedral Structure

Kim Shih
 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.
 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
– they occupy space on the central atom, but are not
“seen” as points on the molecular geometry
Kim Shih
 Not Quite Perfect Geometry
Effect of Double Bonds

Because the bonds and atom

sizes are not identical in
formaldehyde, the observed
angles are slightly different
from ideal

Kim Shih
 Not Quite Perfect Geometry
The Effect of Lone Pairs
• Lone pair groups “occupy more space” on the
central atom
– because their electron density is exclusively on the
central atom rather than shared like bonding electron
groups
• Relative sizes of repulsive force interactions is
Lone Pair – Lone Pair > Lone Pair – Bonding Pair > Bonding Pair – Bonding Pair

• This affects the bond angles, making the bonding

pair – bonding pair angles smaller than expected
Kim Shih
 Effect of Lone Pairs

bonding electrons
The nonbonding are shared
electrons by twoonatoms,
are localized the
so someatom,
central of thesonegative charge is charge
area of negative removed from
takes
the central
more spaceatom

Kim Shih
Bond Angle Distortion
from Lone Pairs (NH3 )

Kim Shih
Bond Angle Distortion
from Lone Pairs (H2O)

Kim Shih
Molecular Shapes: The VSEPR Model
Three Charge Clouds(CH2O, SO2)

Kim Shih
 Bent Molecular Geometry:
Derivative of Trigonal Planar Electron Geometry
• When there are three electron groups around the
central atom, and one of them is a lone pair, the
resulting shape of the molecule is called a trigonal
planar — bent shape
• The bond angle is less than 120°
– because the lone pair takes up more space

Kim Shih
 Derivatives of Tetrahedral Electron Geometry
Pyramidal & Bent Molecular Geometries
• When there are four electron groups around the
central atom, and one is a lone pair, the result is
called a trigonal 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 tetrahedral—bent shape
– it is planar
– it looks similar to the trigonal planar—bent shape, except
the angles are smaller
• For both shapes, the bond angle is less than 109.5°
Kim Shih
Methane (CH4)

Kim Shih
Trigonal Pyramidal Shape
(NH3)

Kim Shih
Tetrahedral–Bent Shape (ClO2-1 )

Kim Shih
Molecular Shapes: The VSEPR Model
Four Charge Clouds(CH4 , NH3, H2O)

Kim Shih
Molecular Shapes: The VSEPR Model
Five Charge Clouds

Kim Shih
 Replacing Atoms with Lone Pairs
in the Trigonal Bipyramid System (SF4)

Shape: Seesaw

Kim Shih
T–Shape (BrF3)

Kim Shih
Linear Shape (XeF2)

Kim Shih
 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 first
because there is more room
• When there are five electron groups around the central atom, and
one is a lone pair, the result is called the seesaw shape
• When there are five electron groups around the central atom, and
two are lone pairs, the result is called the T-shaped
• When there are five electron groups around the central atom, and
three are lone pairs, the result is a linear shape
• 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

Kim Shih
Molecular Shapes: The VSEPR Model

Six Charge Clouds

Kim Shih
Square Pyramidal Shape (SbCl5 2-)

Sb(Antimony, 5A group)

Kim Shih
Square Planar Shape (XeF4)

Kim Shih
 Derivatives of the
Octahedral Geometry
• 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
pyramid shape
– the bond angles between axial and equatorial positions is less
than 90°
• 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 is 90°
Kim Shih
Kim Shih
Kim Shih
Illustrations of Molecular Geometries of Molecules
Using 3-D Notations
 Predicting the Shapes
Around Central Atoms
1. Draw the Lewis structure(count valence e- first)
2. Determine the number of electron groups
around the central atom
3. Classify each electron group as bonding or lone
pair, and count each type
– remember, multiple bonds count as one group

Kim Shih
Brain Exercise

Kim Shih
 Predict the molecular geometry in
SiF5─
A. Trigonal bipyramid 59%

B. Square Pyramidal
C. Square planar
34%
D. T Shape
E. Bent
7%
0% 0%

1 2 3 4 5

Kim Shih
Predict the molecular geometry and bond angles in SiF5─

Si least electronegative
5 electron groups on Si
Si is central atom

Si = 4e─ 5 bonding groups

F5 = 5(7e─) = 35e─ 0 lone pairs
(─) = 1e─
total = 40e─
Shape = trigonal bipyramid
Bond angles
Feq–Si–Feq = 120°
Feq–Si–Fax = 90°

Kim Shih
Predict the molecular geometry and
bond angles in ClO2F
2% A. Tetrahedral
56% B. Trigonal pyramidal
5% C. Linear
34% D. Trigonal planar
2% E. Octahedral

Kim Shih
 Predict the molecular geometry and bond angles
in ClO2F

Cl least electronegative
4 electron groups on Cl
Cl is central atom

Cl = 7e─ 3 bonding groups

O2 = 2(6e─) = 12e─ 1 lone pair
F = 7e─
Total = 26e─
Shape = trigonal pyramidal

Bond angles
O–Cl–O < 109.5°
O–Cl–F < 109.5°

Kim Shih
Determine the electron geometry (eg) and
molecular geometry (mg) of XeF2.
A. eg=linear, mg=linear
63%
B. eg=trigonal bipyramidal,
mg=linear
C. eg=trigonal bipyramidal,
mg=bent
17%
D. eg=tetrahedral, mg=bent
7% 7% 5%
E. eg=tetrahedral, mg=linear
1 2 3 4 5

Kim Shih
eg=trigonal bipyramidal, mg=linear
Kim Shih
Determine the electron geometry (eg) and
molecular geometry (mg) of XeF4

A. eg=linear, mg=linear 93%

B. eg=trigonal bipyramidal,
mg=linear
C. eg=octahedral, mg=
Square Planar
D. eg=tetrahedral, mg=bent
5% 3%
E. eg=tetrahedral, mg=linear
0% 0%

1 2 3 4 5

Kim Shih
Electron – octahedral
Molecular – square planar
Kim Shih
Determine the electron geometry, molecular
geometry and idealized bond angle of
the following………
1. PF3 Electron- tetrahedral, molecular- trigonal pyramidal,
Bond angle< 109.5°
2. SBr2 Electron – tetrahedral, molecular – bent
Bond angle <109.5 °
3. CHCl3 Electron – tetrahedral, molecular – tetrahedral
Bond angle =109.5 °
Electron – linear, molecular – linear
4. CS2
Bond angle =180 °
Electron- tetrahedral, molecular- trigonal pyramidal,
5. NF3
Bond angle< 109.5°

6. OF2 Electron – tetrahedral, molecular – bent

Bond angle <109.5Kim°Shih
 Determine the electron geometry, molecular
geometry and idealized bond angle of
the following………

SF4 Electron – trigonal bipyramidal,

molecular – seesaw

ClF3 Electron – trigonal bipyramidal,

molecular – T shape
IF2- Electron – trigonal bipyramidal,
molecular – linear
IBr4- Electron – octahedral,
molecular – square planar

Kim Shih
 Multiple Central Atoms
• Many molecules have larger structures with many
interior atoms
• We can think of them as having multiple central atoms
• When this occurs, we describe the shape around each
central atom in sequence
 


shape around left C is tetrahedral H O


| ||  
shape around center C is trigonal planar H  C  C  O  H
|  
shape around right O is tetrahedral-bent
H

Kim Shih
Describing the Geometry
of Methanol

Kim Shih
Describing the Geometry
of Glycine

Kim Shih
 Predict the molecular geometries in H3BO3

oxyacid, so H attached to O
B least electronegative 34 electron
electron groups
groups on
on BO

B Is Central Atom O has

B has
3 bonding groups
2
B = 3e─ 0 lone
2 ponepairs
pairs
O3 = 3(6e─) = 18e─
H3 = 3(1e─) = 3e─
Shape on B = trigonal planar
Total = 24e─
Shape on O = tetrahedral bent

Kim Shih
 Polarity of Molecules
• For a molecule to be polar it must
1. have polar bonds
 electronegativity difference - theory
 bond dipole moments - measured
2. have an unsymmetrical shape
 vector addition
• Polarity affects the intermolecular forces of attraction
 therefore boiling points and solubility
 like dissolves like
• Nonbonding pairs affect molecular polarity, strong pull
in its direction
Kim Shih
 Molecule Polarity

The H─Cl bond is polar. The bonding

electrons are pulled toward the Cl end
of the molecule. The net result is a
polar molecule.
Kim Shih
 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.
 Molecule Polarity

The H─O bond is polar. Both sets of

bonding electrons are pulled toward the O
end of the molecule. The net result is a
polar molecule.

Kim Shih
Vector Addition
 Vector Addition: One Dimension

One Dimension:
• To add two vectors that lie on
the same line, assign one
direction as positive.

• Vectors pointing in that

direction have positive
magnitudes.

• Consider vectors pointing in the

opposite direction to have
negative magnitudes.
 Vector Addition: Two or More Dimensions
Two or More Dimensions:
• To add two vectors, draw a
parallelogram in which the two
vectors form two adjacent sides.

• Draw the other two sides of the

parallelogram parallel to and the
same length as the two original
vectors.

• Draw the resultant vector beginning

at the origin and extending to the far
corner of the parallelogram as shown
in Examples 4 and 5.

• To add three or more vectors, add

two of them together first, and then
add the third vector to the result
(Examples 6 and 7).
Molecular Polarity Affects
Solubility in Water
• Polar molecules are attracted to
other polar molecules
• Because water is a polar
molecule, other polar
molecules dissolve well in water
– and ionic compounds as well
– like dissolves like
• Some molecules have both
polar and nonpolar parts
Kim Shih
 Predicting Polarity of Molecules

1. Draw the Lewis structure and determine the

molecular geometry
2. Determine whether the bonds in the molecule
are polar
a) if there are not polar bonds, the molecule is
nonpolar
3. Determine whether the polar bonds add
together to give a net dipole moment

Kim Shih
Predict whether NH3 is a polar molecule

1. Draw the Lewis

structure and
determine the
molecular geometry

ENN = 3.0
2. Determine if the bonds ENH = 2.1
are polar 3.0 − 2.1 = 0.9
therefore the
bonds are polar
covalent
Kim Shih
 Predict whether NH3 is a polar molecule

3) Determine whether
the polar bonds add
together to give a
net dipole moment
a) vector addition
b) generally, asymmetric The H─N bond is polar. All the sets of
shapes result in bonding electrons are pulled toward the
N end of the molecule. The net result is
uncompensated a polar molecule.
polarities and a net
dipole moment

Kim Shih
Brain Exercise

Kim Shih
Decide whether the following molecules Are polar

Trigonal
Bent Trigonal
Planar
2.5

1. polar bonds, N-O

2. asymmetrical shape 1. polar bonds, all S-O
2. symmetrical shape
polar
nonpolar
Kim Shih
How many of the following molecules are polar?
CBrCl3, CS2, SiF4, SO3
A. 0 58%

B. 1
C. 2
D. 3
22%
E. 4
14%

4%
2%

1 2 3 4 5

Kim Shih
Where does Decaf coffee come from?

caffeine
Kim Shih