CHEMISTRY

COLLEGE PHYSICS
Chapter 7 CHEMICAL BONDING AND MOLECULAR GEOMETRY
Chapter # Chapter Title
PowerPoint Image Slideshow

Slides adopted from

Hofstra University
Chemical Bonding

Things we must consider:

 What holds the atoms in a molecule or
ionic compound together?
 Why are atoms in molecules often
distributed at strange angles?
 Why are molecules three dimensional?
 Can we predict the structure of a
compound?
 How does structure relate to chemical and
physical properties?
The Chemical Bond

 The force that holds two atoms together

 Bonding occurs using valence electrons

 Electrons in an atom can be categorized as either valence or

core electrons

 Atoms try to get 8 electrons in the valence

 Lewis symbols help us to track the valence electrons and

predict bonds
Bonding
The forces that hold adjacent atoms together
 Covalent - e– sharing from the
outermost shell
 Ionic - e– transfer from the outermost
 shell Metallic - mobile valence e–

* In most chemical compounds, electrons are shared unequally

between atoms. The boundary between covalent and ionic are
somewhat objective.
 Electron Configuration of Main-
Group Cations
• For all main group elements, the number of
valence electrons is equal to the last digit of the
group number.

• Main-group metals form cations by losing all of

their valence electrons resulting in a filled shell.

• Exceptions: Tl, Sn, Pb, Bi (post-transition metals)

• Tl3+, Sn4+, Pb4+, and Bi5+ do form

• Tl+, Sn2+, Pb2+, and Bi3+ also form
 Electron Configuration of Transition
Metal and Inner Transition Metal Cations

• Transition metals and Inner Transition metals

behave differently than Main-Group metals.

• The cations formed by Transition Metals and Inner

Transition Metals are typically NOT isoelectronic with
a noble gas.
 Electron Configuration of
Anions
• Anions usually form when a non-metal atom
gains enough electrons to have a filled valence
shell.

• The charge of the anion is equal to the number

of electrons gained by the atom.
(credit a: modification of work by “Jurii”/Wikimedia Commons)
Ionic Bonding
complete transfer of 1 or more electrons
 Formation of Ionic
Compounds
• These ions then come together to form an
ionic bond.
 7.2: Covalent
Bonding
•A metal and a non-metal tend to exchange electrons
with each other and form ionic bonds.

•Nonmetals tend to share electrons with each other

forming covalent bonds.

•Covalent bonds are formed between atoms that

have similar abilities to attract electrons.
 H2: Covalent Compound
• Consider the H2 molecule
• H: 1s1
• Each hydrogen contributes a 1s electron in forming a covalent bond.

HF: Covalent Compound

• Consider HF
• Only the valence electrons are involved in the formation of a covalent bond.
• After forming a covalent bond, both H and F are each isoelectronic with a noble
gas.
 Formation of Covalent
Bonds
• To break chemical bonds, energy must be added
(endothermic process).

• The formation of chemical bonds results in the

release of energy (exothermic process).
• The bond makes each atom more stable and therefore in a
lower energy state.
Potential Energy Diagram • Formation
of H2
molecule.

• Distance
of
lowest
potential
energy is
the
bond
length.
 Types of covalent
bonds
• All covalent bonds involve the sharing of electrons. But the
electrons are not always shared equally…

• Two types of covalent bonds:

1)Pure Covalent bonds (Non-polar covalent bonds) –

Equal sharing of electrons

2) Polar Covalent Bonds – Unequal sharing of

electrons

These different types of covalent bonds arise from

electronegativitiy differences amongst the bonded
atoms.
ELECTRONEGATIVITY

The ability of an atom in a molecule to

attract electrons to itself.
 Ionization energy - measure of how hard
an atom holds onto its electrons.
 Electron affinity - measure of how strong
an atom attracts electrons to itself.

Electronegativity tells us how much a particular atom

“wants” electrons
The electronegativity values derived by Pauling follow predictable
periodic trends with the higher electronegativities toward the upper
right of the periodic table.
 Pure Covalent
Bonds
1) Pure Covalent bonds (Non-polar covalent bonds)
– Equal sharing of electrons

• Form when the atoms have the exact same or very

similar electronegativity values.

• This occurs in all bonds when the atoms are the

same (X-X)

• C-H bonds are a common pure covalent bond.

 Polar Covalent
Bonds Bonds – Unequal sharing of
2) Polar Covalent
electrons
• Form when the atoms have significantly different EN
values.

• Most covalent bonds involving different atoms (X-Y), are

polar covalent bonds.

• The polarity of a bond increases with increasing EN

difference between the bonded atoms.

• The polar bond is a dipole

• Less EN atom is partially positive (δ+), while the more
EN atom is partially negative (δ-).
 Electronegativity and Bond
ype

As the electronegativity difference increases between two atoms, the bond becomes more
ionic.
The absolute value of the difference in electronegativity (∆EN) provides a rough measure of
bond type.
BOND POLARITY & ELECTRONEGATIVITY

As the difference in Electronegativity

increases, so does the ionic character of
the bond.
Increasing covalent character
 7.3: Lewis Symbols and
• Structures
All bonds involve the sharing or transfer of valence
electrons between atoms.

• Lewis Symbol – Consists of an elemental symbol

surrounded by one dot for each of its valence electrons.

Boron Carbon Nitrogen

1s2 2s22p1 1s22s22p2 1s22s22p3

LEWIS SYMBOLS OF ELEMENTS

Basic rules

Draw the atomic symbol. This

represents the atomic nucleus along
with the core electrons.

X Treat each side as a box that can

hold up to two electrons.

Count the electrons in the valence

shell.

Start filling boxes - don’t make pairs

unless you need to.
Core and Valence Electrons
For group A elements, valence electrons can easily be predicted
from the periodic table. Core electrons are not involved in bonding.
Lewis Dot Structures & the Octet Rule
The electron pair bond between the two atoms of an
H2 molecule is represented by a pair of dots or a line.

H-atom: H2 molecule:

H HH
H–H
The representation of a molecule in this fashion is
called a Lewis electron dot structure or just a
Lewis structure
Lewis Dot Structures & the Octet Rule
When other covalent species form, there are
additional electron pairs that do not participate in
bonding.
These are called “lone pairs” (lp)
+ 
H F →HF
one bonding pair & three lone pairs
(octet)

H–F
 The Octet
Rule
• Noble gases, except for He, have 8 valence electrons.

• The Octet Rule – Nonmetals, except for hydrogen, form

molecules whereby sharing electrons allows them to be
surrounded by eight valence electrons and therefore
isoelectronic with a noble gas.

• Hydrogen is an octet rule exception, because it only

needs two electrons (duet of electrons) to have a filled
valence shell.
COVALENCY

The number of bonds an atom normally forms

How many e– from other atoms are needed to form
an octet?
WRITING LEWIS STRUCTURES

1 Calculate the total number of valence e from all atoms

 anions - add one e– for each negative charge.
 cations - subtract one e– for each positive charge.
2 Write the skeleton structure. (In general, the least electronegative
atom occupies the central position; hydrogen and fluorine occupy
terminal positions.)
3 Draw single bonds between the central and the outer atoms
4 Complete the octet/duet of the outer atoms by adding electron lone
pairs.
5 Count the total number of e used ; subtract from Step 1
 Place any remaining e– on the central atom in pairs.
 If the central atom has fewer e– than an octet, form double
or triple bonds as necessary.
** Hydrogen atoms will never have lone pairs or multiple bonds
What is the Lewis symbol for NH3?
1. Valence electrons

2. Skeleton

3. Form single bonds

4. Place lone pairs on outer atoms

5. Complete octet for the central atoms

 Carbon Dioxide, CO2

1. Valence electrons

2. Skeleton

3. Form single bonds

4. Place lone pairs on outer atoms

5. Complete octet for the central atoms

 Formaldehyde, CH2O
1. Valence electrons

2. Skeleton

3. Form single bonds

4. Place lone pairs on outer atoms

5. Complete octet for the central atoms

 Examples of Lewis
Structures
OH-

NH4+
Multiple Bonds

Atoms that have a tendency to form

multiple bonds: C, O, N, S, P
EXCEPTIONS TO THE OCTET RULE

• Most molecules and polyatomic ions do follow the octet rule.

• There are some notable exceptions
1 Molecules with an odd number of electrons (free radicals)

NO
2 Molecules with less than an octet (electron deficient)

BF3
3 Molecules with more than an octet (Hypervalent molecules)
a only possible for the 3rd row element and below (d orbitals
available to accommodate extra e–)
b PCl5

c SF6
FREE RADICALS
• Occasionally a molecule or ion contains an odd number of
valence electrons.
• These species are known as free radicals.
• Impossible to write a Lewis structure with all atoms
obeying the octet rule.
• Get each atom as close as possible to 8 electrons.
• Example: NO
 Electron Deficient
Molecules
• Sometimes a central atom will violate the octet rule by only being
surrounded by 4 or 6 electrons.

• This sometimes occurs in molecules where the central atom is from

group 2 or 13, such as Be or B.

• Examples: BeF2, BeH2, BH3, BF3

 Hypervalent
Molecules
• Elements in the second period (n = 2) can only
accommodate 8 electrons in their valence shell.

• Beginning with the third period (n = 3), the presence of empty d

orbitals may allow central atoms to have 10 or 12 electrons.

• Hypervalent Molecules – Molecules with a central atom surrounded by

more than 8 electrons.

• Most common violation of the octet rule.

Central Atoms Capable of forming Hypervalent Molecules

Period Grp 14 Grp 15 Grp 16 Grp 17 Grp 18
3 Si P S Cl

4 As Se Br Kr

5 Sb Te I Xe
PCl5

-
ICl4
USING FORMAL CHARGE TO PREDICT
STABILITY

When several Lewis structures are

possible, the most stable structure will
be when
- the atoms have the smallest amount of
formal charge
- any negative charge resides on the more
electronegative atom

F.C. = # valence e – # lone pair e - # bond line

FORMAL CHARGE

F.C. = # valence e – # lone pair e - # bond line

:C O-H
MORE ON FORMAL CHARGE

The sum of the formal charges on the atoms in a molecule must = 0

The sum for the atoms in an ion equals the charge on the ion

- Usually the most plausible Lewis structure is one with no formal

charges (formal charges of zero on all atoms).

- Where formal charges are required, they should be as small as

possible, and negative formal charges should appear on the most
electronegative atoms.
Write 3 Lewis Structures and Determine the Formal Charge of
all atoms in SCN-
Which is the best structure and why?
RESONANCE STRUCTURES

Equivalent Lewis structures that are the same except for

the placement of e
- more than one Lewis structure
- structure contains double or triple bonds

The actual structure of the molecule is a

composite, or hybrid of the equivalent
resonance structures
Draw resonance structures for SO32-
Bond Strength: Covalent Bonds

The average C–H bond energy, DC–H, is 1660/4 = 415 kJ/mol

Lattice Energy

Lattice energy (∆H°lattice): the energy associated with the formation

of a crystalline lattice of alternating cations and anions from the
gaseous ions.
Higher lattice energy = stronger interaction = higher melting point
Lattice Energy Trend
The Born-Haber cycle shows the relative energies of each step involved in the
formation of an ionic solid from the necessary elements in their reference states.
Example: Born-Haber Cycle for NaCl
Molecular Shape
Why is it important?

Photochemical events in vision involve 2 similar chemical structures: cis and

trans retinal.
Upon absorption of a photon of light in the visible range, cis-retinal can
isomerize to all-trans-retinal, triggers the signal to brain.
 Molecular Shapes
Lewis structures tell us how atoms are connected in a molecule:
bonds (bp) & lone pairs (lp) etc…
The 3–D shape of a molecule is however, determined by its bond
angles.

The Lewis structure

H
90o
suggests that the H–C– H
bond angles are 90o & that H CH
the molecule is flat.
H
Molecular Shapes
Experimentally however, the H–C–H bond angles are found to be 109.5°.
If this is the case, the molecule cannot be planar…

H 90° + 90° + 90° +90° =

90°
90° 360°
H CH
90° 90° 109.5 + 109.5 + 109.5 + 109.5 =
H 438.0°

The methane molecule must be 3-D since the sum of the angles is greater than
360 degrees!
Molecular Shapes
To accommodate the 109.5o bond angles, the atoms adopt a new 3-D geometry
to minimize the repulsion between the atoms:

H H
109.5o
H CH becomes… H C H
H H
• The molecular geometry of CH4 is said to be “tetrahedral”
• The H-atoms fit at the corners of a regular tetrahedron shape with the carbon
at the center.
 Molecular Shapes
• In order to predict molecular shape, we assume the valence electrons of each
atom in the molecule repel one another.
• When this occurs, the molecule adopts a 3D geometry that minimizes this
repulsion where:

lp-lp > lp-bp > bp-bp

Valence Shell Electron Pair Repulsion (VSEPR

theory.
Electron Pair Geometries

2 pairs 3 pairs 4 pairs 5 pairs 6 pairs

of of of of of
electrons electrons electrons electrons electrons

Central Atoms Surrounded by Single-Bond Pairs

Geometry
Electron domain geometry
Arrangement of electron-pairs in space

Molecular geometry
Arrangement of atoms in space
Valence Shell Electron-Pair
Repulsion Theory
(VESPR)
Electron domains repel each other

space between electron domains is maximized

Electron-domain geometries
6 balloons - octahedral
5 balloons - trigonal bipyramidal
4 balloons - tetrahedral
3 balloons - trigonal planar
2 balloons - linear
Molecular Geometries for 5 Electron Pairs

All based on trigonal

bipyramidal shape
Molecular Geometries for 6 Electron Pairs
All are based on the
8- sided octahedron
Influence of Lone Pairs on the Molecular Geometry
Lone pairs require more room than bonding pairs and tend to compress the
angles between the bonding pairs.

Bond angles deviated from ideal bond angle

CH4 109.5 0 LP Tetrahedral
NH3 107.5 1 LP Trigonal pyramidal
H2O 104.5 2 LP Bent
Representing Molecular Geometries on Paper
Predicting Molecular Shape
Step 1: Predict electron geometry
- Complete the Lewis structure
- Focus on the central atom: count the total number of arms
around the central atom. 1 single bond = 1 arm,
1 double bond = 1 arm, 1 triple bond = 1 arm, 1 lone pair = 1 arm
- Draw the electron geometry: 2 arms = linear, 3 arms = trigonal
planar, 4 arms = tetrahedral, 5 arms = trigonal bipyramidal,
6 arms = octahedral
Step 2: Predict real molecular shape from electron geometry
- Erase the lone pair. What left over is the real molecular shape.
The structure with the central atom and surrounding atoms only
Example: KrCl4
Step 1: Predict electron geometry
- Complete the Lewis structure
- Focus on the central atom: count the total number of arms around the central atom. 1
single bond = 1 arm, 1 double bond = 1 arm, 1 triple bond = 1 arm, 1 lone pair = 1 arm
- Draw the electron geometry: 2 arms = linear, 3 arms = trigonal planar, 4 arms =
tetrahedral, 5 arms = trigonal bipyramidal, 6 arms = octahedral
Step 2: Predict real molecular shape from electron geometry
- Erase the lone pair. What left over is the real molecular shape. The structure with the
central atom and surrounding atoms only
Example: SOCl2
Step 1: Predict electron geometry
- Complete the Lewis structure
- Focus on the central atom: count the total number of arms around the central atom. 1
single bond = 1 arm, 1 double bond = 1 arm, 1 triple bond = 1 arm, 1 lone pair = 1 arm
- Draw the electron geometry: 2 arms = linear, 3 arms = trigonal planar, 4 arms = tetrahedral,
5 arms = trigonal bipyramidal, 6 arms = octahedral
Step 2: Predict real molecular shape from electron geometry
- Erase the lone pair. What left over is the real molecular shape. The structure with the
central atom and surrounding atoms only
 Molecular Polarity

Fluorine has a larger

electroegativity value than
hydrogen.

This means that the electrons in

the bond are skewed toward the F
atom. The electrons shift toward
the F-atom.
Polarity vs. Electronegative Difference
The greater the difference in electronegativity, the more polar the covalent bond.

H vs. F
4.0 – 2.2 = 1.8
C vs. F
4.0 – 2.5 = 1.5
O vs. F
4.0 – 3.5 = 0.5

So in terms of polarity,
H-F
Bond Polarity & Molecular Polarity
When a molecule has more than 1 bond, the polarity of the individual bonds in
a molecule will determine the overall polarity of a molecule.
Bond Polarity & Molecular Polarity

Each O-H bond is polar

The “net” or overall dipole

moment for the molecule is the
sum of each bond dipole

When net dipole moment is non-

zero, the molecular is polar.
H 2O
Molecular Shape & Molecular Polarity

If the molecule is symmetrical,

all dipoles are canceled out.

Net dipole = 0.

The molecule is non-poplar

Dipole Moments & Molecular Polarity
Predicting polarity for a molecule
Step 1: complete the molecular geometry
Step 2: determine each bond is polar or not polar. Draw
a dipole for the polar bonds
Step 3: The net dipole of a molecule is the sum of all
dipoles from each polar bond.
- If the net dipole is non zero, the molecule is polar.
- If all dipoles from the polar bonds are cancelled out
(symmetrical), the molecule is non-polar.
Example: Determine the polarity of NF3
Step 1: complete the molecular geometry
Step 2: determine each bond is polar or not polar. Draw a dipole for the polar
bonds
Step 3: The net dipole of a molecule is the sum of all dipoles from each polar
bond. If the net dipole is non zero, the molecule is polar. If all dipoles from the
polar bonds are cancelled out (symmetrical), the molecule is non-polar.
Example: Determine the polarity of SCO
Step 1: complete the molecular geometry
Step 2: determine each bond is polar or not polar. Draw a dipole for the polar
bonds
Step 3: The net dipole of a molecule is the sum of all dipoles from each polar
bond. If the net dipole is non-zero, the molecule is polar. If all dipoles from
the polar bonds are cancelled out (symmetrical), the molecule is non-polar.
Bond Properties: Order, Length, Energy
The order of a bond is the number of bonding electron pairs
shared by two atoms in a molecule
Bond orders may be 1, 2, and 3, as well as fractional values.
 Fractional Bond Order
Fractional bond orders occur in molecules with
resonance structures.
[ O=N ]

: :
: -

:
Consider NO2− O
The N—O bond order = 1.5
Bond Length
Bond length is the distance between the nuclei of two
bonded atoms.
Bond Length
Bond length depends on
size of bonded atoms.

H—F

H—Cl
Bond distances measured in
Angstrom units where
1Å = 10−10 m.
H—I
Bond Length

Bond length depends on bond

order.

Bond distances measured in Angstrom

units where
1Å = 10−10 m.
Bond Properties: Order, Length, Energy