Chapter 7 Chemical Bonding and Molecular Geometry

Chapter 7
Outline
1. : Ionic Bonding
2. : Covalent Bonding: Electronegativity, Polarity
3. : Lewis Symbols and Structures: Electron Dot
Formulas, Octet Rule, Multiple bonds, exceptions
4. Formal Charge and Resonance
5. Strengths of Ionic and Covalent Bonds: Born-
Haber cycle, Enthalpies of Reaction
6. Molecular Structure and Polarity: VSEPR, bond-
order, polarity, angle, distance, strength, Molecular
Polarity, Dipole moment
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.
FIGURE 7.2

(a) Sodium is a soft metal that must be stored in mineral oil to prevent reaction with air or water.
(b) Chlorine is a pale yellow-green gas.
(c) When combined, they form white crystals of sodium chloride (table salt). (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.
FIGURE 7.3

The atoms in sodium chloride (common table salt) are arranged to (a) maximize
opposite charges interacting. The smaller spheres represent sodium ions, the larger
ones represent chloride ions. In the expanded view (b), the geometry can be seen more
clearly. Note that each ion is “bonded” to all of the surrounding ions—six in this case.
 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 H molecule
2

• 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.
FIGURE 7.6

The electronegativity values derived by Pauling follow predictable periodic trends with
the higher electronegativities toward the upper right of the periodic table.
 Bond Polarity & Electronegativity

ty Trend
i
r
gativ
one
ect
El

Recall that electronegativity () measures the relative

tendency for an atom to polarize a bond. It follows Zeff on the
periodic
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
 Electronegativity tells us how much a particular atom
“wants” electrons
 Electronegativity increases (left to right) across a period
 Electronegativity decreases down the periodic table
 A molecule with no polar bonds is nonpolar molecule
 A molecule with 1 polar bond is a polar molecule
 If the individual bond dipoles do not cancel, the molecule
is polar
 If the individual bonds dipoles cancel, the molecule is
nonpolar
 If there are lone pairs on the central atom, the molecule is
polar
Bond Polarity & Electronegativity
 A difference in electronegativity of 0 indicates that the
bond is purely covalent. There is equal sharing of
electrons.
 A difference of electronegativity between 0.1 to 0.3
indicates that the bond is non-polar covalent.
 A difference of electronegativity between 0.4 to 1.7
indicates that the bond is polar covalent.
 A difference of electronegativity that is greater than 1.8
indicates that the bond is ionic.
 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-).
FIGURE 7.5

(a) The distribution of electron density in the HCl molecule is uneven. The electron
density is greater around the chlorine nucleus. The small, black dots indicate the
location of the hydrogen and chlorine nuclei in the molecule.
(b) Symbols δ+ and δ– indicate the polarity of the H–Cl bond.
FIGURE 7.8 Electronegativity and Bond
Type

As the electronegativity difference increases between two atoms, the bond becomes more
ionic.
The absolute value of the difference in electronegativity (DEN) 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
 Electronegativity Difference

EN ()
0 0.5 1.7 3.3

nonpolar polar covalent ionic

H—H + –
Na+ Cl–
Cl—Cl H—Cl
 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 elements.

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.
Concept Check
How many valence electrons are in?
 Phosphorous

 Chlorine

 Carbon
Lewis Symbols
 Valence e–

e–
from shell of highest n value
 Octet rule
 noble gas e– configuration is stable
 ns2 np6
 Useful only for “A” group elements
Concept Check
 What is the electron configuration of
Carbon?

 What is the Lewis structure?

Lewis Structures
 :&—
 Cl:Cl or Cl — Cl
 lp & bp (lone pair & bonding pair)
 octet rule (duet rule for H)
 Examples
H
2

 HF
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 in honor of G. N. Lewis.
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)
hydrogen fluoride: HF
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–
 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 Place one pair of e– between bonded atoms.
4 Complete the octets of the atoms attached to the central atom by
adding electron pairs.
5 Count the total number of e– ; 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

Multiple Bonds
 Acetylene, C2H2
 Nitrogen, N2

 Atoms that have a tendency to form

multiple bonds:
 C, O, N, S, P
Concept Check
What is the Lewis symbol for NH3?
1.Decide on the central atom; Central atom is generally
the atom of lowest affinity for electrons & never
hydrogen.
Therefore, N is the central atom.
2. Count valence electrons
H = 1
and N = 5
Total =
(3 × 1) + 5
= 8 electrons /
4 pairs
 Concept Check
3. Form a single bonds between the central H N H
atom and each surrounding atom.
H

4. The remaining electrons form LONE ••

PAIRS to complete octet as
needed.
H N H

3. BOND PAIRS and 1 LONE PAIR.

H

Note that N has a share in 4 pairs (8 electrons), while H

shares 1 pair.
 Concept Check
Carbon Dioxide, CO2

1. Central atom = C
2. Valence electrons = 16 valence
electrons
3. Form bonds.

4. Place lone pairs on outer atoms.

Carbon Dioxide, CO2
4. Place lone pairs on outer atoms.

5. So that C has an octet, we shall form DOUBLE

BONDS between C and O.

The second bonding pair forms a double bond.

Formaldehyde, CH2O
C H O
4 + (2 × 1) + 6 = 12 electrons available

C
Carbon is the least electronegative,
hydrogen can form only one bond.
Formaldehyde, CH2O
C H O

4 + (2 × 1) + 6 = 12 electrons available

H C H
Carbon is the least electronegative,
hydrogen can form only one bond.

O
Formaldehyde, CH2O
C H
O
4+2×6 = 12 electrons available

H C H
Carbon is the least electronegative,
hydrogen can form only one bond.
O
Formaldehyde, CH2O

H C H
Carbon is the least electronegative,
hydrogen can form only one bond.
O
Formaldehyde, CH2O

H O H
:C :
 Formaldehyde, CH2O
Additional

Stuctures:

:
:
H O H H C O H
:C :
 Formaldehyde, CH2O
Additional correct structure

Stuctures:

Not this one…

:
:
H O H H C O H
or this one…
:C :
 Formaldehyde, CH2O
Additional correct structure

Stuctures: nature likes symmetry!

Not this one…

:
:
H O H H C O H
or this one…
:C :
 Formaldehyde, CH2O
Additional correct structure

Stuctures: nature likes symmetry!

Not this one…

:
:
H O H H C O H
or this one…
:C :
You will see why the first structure is favored by formal
charges later.
Concept Check
 Write the Lewis structures for:

 SiO2

 CH4
 IBr2
+

 What is the shape of these species?

 More on this later.
 Examples of Lewis
• H2O, OH-, NH4
Structures +
 Examples of Lewis
•Structures
CH,CH
2 4 2 2
Multiple Bonds

What are the Lewis structures

Do on paper, then with the models
 C2H3Cl


 CH2O2
 C 2 H 3N
 CH5N
 C3H 6
HCN
 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)

a BF3

3 Molecules with more than an octet (Hypervalent molecules)

a only possible when valence shell is n  3 (d orbitals available
to accommodate extra e–)
b PCl5

c SF6
 Electron Deficient
Molecules
• 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

 Electron Deficient
Molecules

•Structure II is confirmed by experiment for both

molecules.
• More on C (formal charge) shortly…
f
 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
Compounds in Which an Atom Has
More Than Eight Valence Electrons
FIGURE 7.12 EXAMPLES OF HYPERVALENT MOLECULES

In PCl5, the central atom phosphorus shares five pairs of electrons. In

SF6, sulfur shares six pairs of electrons.
EXAMPLE 7.5.1
EXAMPLE 7.5.4
Draw the Lewis structure of
phosphorous pentachloride
Draw PCl4 ion
+
Draw the Lewis Structure of PCl6-
Draw the Lewis structure of xenon
tetrafluoride
EXAMPLE 7.4.4
EXAMPLE 7.4.5
EXAMPLE 7.6.2
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
What is the formal charge of CH4?

F.C. = number of valence e– – [lone pair e– + ½ bonding e–]

 Formal charge of C: 4 – [0 + ½ (8)] = 0
 Formal charge of H: 1− [0 + ½ (2)] = 0
Formal Charge
F.C. = number of valence e– – [lone pair e– + ½ bonding e–]

:C O:
Formal charge of C: 4 – [2 + ½ (6)]
= –1

Formal charge of O: 6 – [2 + ½
(6)]
= +1
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
Write Lewis Structure and Determine
the Formal Charge of
 HCN
 HN
 C
Which is the best way to represent
 hydrocyanic acid?
Why?
More on Formal Charges
 The sum of the formal charges on all the atoms in a molecule
will be zero while for an ion it will be equal to the charge on the
ion. In using the concept of formal charge we should keep the
following rules in mind.
 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.
 Adjacent atoms in a structure should not carry formal charges of
the same sign.
 Formal charges on the atoms in a Lewis structure must total to
zero for a molecule and to the net charge for a polyatomic
ion.
Oxidation Numbers
 Charges on bonded atoms are
assigned by giving the more EN atom
all the shared e–
 Such charge assignments are called
oxidation numbers… we have seen this
before
Charge Assignment Summary
 Ion charge: e– transferred

 Oxidation number: e– belongs to more EN

atom

 Formal charge: e– equally shared

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
 only one bond length exists
 bond length is shorter than a single bond but not as short as a
double or triple bond
 Resonance structures have the same arrangements of
atoms, but different arrangements of electrons
 The actual structure of the molecule is a composite, or
hybrid of the equivalent resonance structures
Resonance

O O
O O
O O
What is the Lewis Structure of
(oxygen will have single bonds) check the formal
 PO43-

 charge
 Draw Three Lewis structures for the thiocyanate ion NCS-1
Determine the FORMAL charge and pick the correct one, put in
lone pairs
 [N-C≡S]- [N=C=S]- [N≡C-
S]-
EXAMPLE 7.8.1
EXAMPLE 7.8.2
EXAMPLE 7.8.3
EXAMPLE 7.8.4
EXAMPLE 7.9.1
EXAMPLE 7.9.2
FIGURE 7.13

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.
Molecular Shape
 Why is it important?
 PtCl2(NH3)2
 cis-platin — a potent anti-tumor agent
 trans-platin — toxic
 Only difference is in the molecular shape
 affects physical properties
 affects chemical properties
cis- and trans-retinal

cis-retinal  trans-retinal
Different shape due to light triggering a signal that is
ultimately interpreted by the brain as “I see the
light”
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 & H CH
that 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 +
H 109.5 =

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

This process is known as:

Valence Shell Electron Pair Repulsion (VSEPR)
theory.
Molecular Shapes
Valence Shell Electron Pair Repulsion
A molecule can be described in terms of the
distribution of the bonding atoms about the
central atom:
Molecular Geometry (MG)
A molecule can be described in terms of the
distribution of the bonding pair electrons (bp)
and lone pair electrons (lp) about the central
atom:
Electron Pair Geometry (EPG)
 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 Only by Single-Bond Pairs

Electron Domains
 Regions where it is most probable to find
pairs of electrons
 Bonding pairs – electron domain
 Single, double and triple bonds all represent
just
one domain
 Nonbonding pairs – electron domain
Geometry
 Electron-Domain geometry
 Arrangement of electron-pairs in
space
 Molecular geometry
 Arrangement of atoms in
space
Balloon Demo
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
Example: PCl5
P has 5 valence electrons

Each Cl-atom needs one electron to complete the octet

Cl
: Cl Cl
P
P. : Cl Cl

Molecular Geometry : Trigonal Bipyramidal

Electron Pair Geometry: Trigonal Bipyramidal
Example: SF4
S has 6 valence electrons

Each F-atom needs one electron to complete the octet

F
F :
:S : S :
:

F
F
Molecular Geometry : See-Saw
Electron Pair Geometry: Trigonal Bipyramidal
Molecular Geometries for 6 Electron Pairs

All are based on the 8-

sided octahedron
Compounds with 5 or 6 Pairs Around
the Central Atom

Octahedron

90 F
° F
F S 90
F F °
F
6 electron
pairs
Predicting Molecular (or Ion) Shape
1. Write the Lewis structure
2. Count the number of electron-domains
around the central atom to determine the
arrangement minimizing repulsion
3. Describe the molecular geometry in terms
of the arrangement of the bonding
domains.
4. Double and triple bonds are counted as
one domain for determining molecular
shape
Remember that when predicting shapes of
molecules with double or triple bonds
 For the VSEPR model, multiple bonds
count as one effective electron pair.
Influence of Lone Pairs around an
Atom
 Lone pairs require more room than bonding
pairs and tend to compress the angles
between the bonding pairs.
Influence of Lone Pairs on the Molecular
Geometry

Bond angles:
CH4 109.5 0 LP Tetrahedral
NH3 107.5 1 LP Trigonal pyramidal
H2O 104.5 2 LP Bent
Overall Polarity in Molecules
The polarity of the individual bonds in a molecule will determine the overall
polarity of a molecule.

All homonuclear diatomic molecules

a non-polar.

Noti
ce
• When divided, the top and bottom as well
the as the left and right are mirror images of
I : I sym
met
one another.
• One also knows the molecule is non polar
ry
of because the bond is non polar.
iodine (I2) the
mol
 = 2.7  2.7 = ecul
0 e:
Example: HF
• 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.

This polarizes the molecule

H F
more positive end more negative end
(+) ()
 Electronegativity: H vs. F
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
Molecular Polarity
 Must have polar bonds
 Depends on molecular shape
 polar if centers of + and –
charge ARE NOT
the same
Bond Polarity & Molecular Polarity
When a molecule possesses a net dipole moment, it is
polar.

The individual O-H

bond dipoles The molecule
result in a “net” or is therefore
overall dipole
moment for the
polar.
molecule.

H 2O
Molecular Shape & Molecular Polarity
Notice also that the molecule’s symmetry can be broken
along either O-H bond axis:

This side…

does not look like this

side!
Whenever there exists a line or plane of
asymmetry, the molecule is Polar!
Molecular Shape & Molecular Polarity

CO2

Symmetry across all

bond axes.

non–polar
Bond and Molecular Polarity
Bond and Molecular Polarity
Dipole Moments & Molecular Polarity
Examples
 H2 - nonpolar bond

 nonpolar bonds only; nonpolar molecule

 HCl - polar H Cl

 polar bond; polar molecule

– + 
 CO2 - nonpolar O=C=
–
 polar bonds; nonpolar molecule O
Relationship between Molecular
Geometry and Dipole Moment
Formula Mole.Geom Dipole moment
AX Linear Can be 0
AX2 Linear Zero
Bent Can be 0
AX3 Trig Planar Zero
Trig pyram Can be 0
T-shaped Can be 0
AX4 Tetrahedral Zero
Square pla Zero
See saw Can be 0
AX5 Trig plan Zero
Square pla Can be 0
AX6 Octahedral Zero
Remember what we said about
polarity?
 If lone pairs are around the central atom,
they will be considered POLAR
 In the case of Xenon tetrafluoride the
dipoles do cancel
Most Important Example
 H2O
 polar bonds
 bent molecular shape
 polar molecule
 Demonstration
 rod(charged with static electricity) and
 water
 cyclohexane, C6H12

Microwave oven
 polar water in food
 nonpolar N2 and O2 in air
Examples:
Do at desk and share with neighbor

 Predict shape and polarity

 A. polar (  0) B. nonpolar ( =
0)
 PCl3 vs BCl3
 PCl5 vs SbCl52–

SF4 vs ICl4–

ClF3 vs XeF2

CCl4 vs SF6
More Examples
 Predict molecular polarity of
 XeF4
 XeF3Cl
 XeF2Cl2
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.
 Bond strength increases with bond order.
 Bond length is inversely proportional to bond order.
 Bond strength also increases with the difference in
electronegativity between two covalently bonded atoms.
Bond Properties: Order, Length, Energy
Covalent bond strength increases with increasing 
example: HCl bond is stronger than the HBr bond

Covalent bond strength increases with increasing bond order.

example: O=O bond in stronger than O–O bond
triple > double > single
Bond Order: 3 2 1

Bond length decreases with increasing bond order (Strength)

example: O=O bond is shorter than O–O bond
Bond Order: Number of Bonds Between
a Pair of Atoms

Double bond
Single bond

Acrylonitrile
Tripl
e
bond
 Fractional Bond Order
Fractional bond orders occur in molecules with
resonance structures.

:
O=N :
[ O ]-

:
Consider NO2−
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 Length & Bond Strength
Bond order is proportional to two important
bond properties:
(a) bond strength
414 kJ
(b) bond length
123 pm

110 pm 745 kJ
Bond strength
 Bond enthalpy is the energy required to break a
bond in a mole of gaseous substance.
Cl–Cl(g)  2Cl(g) H = D(Cl–Cl) =
242enthalpies
 Bond kJ are always +
 energy is always required to break a bond
 H is always
+ always released when a bond forms
 energy
 H is always
–
 Tabulated bond enthapies are averages
Strengths of Covalent Bonds
The energy required to break a covalent bond is called the bond dissociation
enthalpy, D.
For the Cl2 molecule, D(Cl–Cl) is given by H for the reaction:

Cl2(g)  2Cl(g)
When more than one bond is broken:

CH4(g)  C(g) + 4H(g) H = 1660 kJ

the bond enthalpy is a fraction of H for the atomization reaction:

D(C–H) = ¼H = ¼(1660 kJ) = 415 kJ

Example of Formation of a Covalent Bond
 H2(g) + Cl2(g)  2HCl(g)
 Calculate Hrfor the reaction
 Table 8.8 data
 Calculate Emin
 Cl—Cl bond
 H—H bond
Bond Dissociation Enthalpies
Using Bond Enthalpy to Calculate
rH
 rH= (bonds broken) – (bonds
formed)
 See example 8.16 in Kotz
Bond Strength
BOND Bond dissociation enthalpy (kJ/mol)
H—H 436
C—C 346
C=C 602
CC 835
NN 945

The GREATER the number of bonds (bond order) the HIGHER the
bond strength and the SHORTER the bond.
Calculate the Energy of this Reaction
 H2 + Cl2 → 2HCl
 1046-1172 = −126kJ/mol
FIGURE 7.14

Bond distances (lengths) and angles are shown for the formaldehyde molecule, H2CO.
FIGURE 7.15

The BeF2 molecule adopts a linear structure in which the two bonds are as far apart as
possible, on opposite sides of the Be atom.
FIGURE 7.16

The basic electron-pair geometries predicted by VSEPR theory maximize the space
around any region of electron density (bonds or lone pairs).
FIGURE 7.17

The molecular structure of the methane molecule, CH4, is shown with a tetrahedral arrangement
of the hydrogen atoms. VSEPR structures like this one are often drawn using the wedge and dash
notation, in which solid lines represent bonds in the plane of the page, solid wedges represent
bonds coming up out of the plane, and dashed lines represent bonds going down into the plane.
FIGURE 7.18

(a) The electron-pair geometry for the ammonia molecule is tetrahedral with one lone pair and three single
bonds.
(b) The trigonal pyramidal molecular structure is determined from the electron-pair geometry.
(c) The actual bond angles deviate slightly from the idealized angles because the lone pair takes up a
larger region of space than do the single bonds, causing the HNH angle to be slightly smaller than
109.5°.
FIGURE 7.19

The molecular structures are identical to the electron-pair geometries when there are
no lone pairs present (first column). For a particular number of electron pairs (row), the
molecular structures for one or more lone pairs are determined based on modifications
of the corresponding electron-pair geometry.
FIGURE 7.20

(a)In a trigonal bipyramid, the two axial positions are located directly across from one another,
whereas the three equatorial positions are located in a triangular arrangement. (b–d) The two lone
pairs (red lines) in ClF3 have several possible arrangements, but the T-shaped molecular structure
(b)is the one actually observed, consistent with the larger lone pairs both occupying equatorial
positions.
EXAMPLE 7.11.1
EXAMPLE 7.11.2
FIGURE 7.21
EXAMPLE 7.12
FIGURE 7.22

The ammonium ion displays a tetrahedral electron-pair geometry as well as a

tetrahedral molecular structure.
EXAMPLE 7.13
FIGURE 7.23

(a) H2O has four regions of electron density around the central atom, so it has a
tetrahedral electron-pair geometry.
(b) Two of the electron regions are lone pairs, so the molecular structure is
bent.
EXAMPLE 7.14
FIGURE 7.24

(a) SF4 has a trigonal bipyramidal arrangement of the five regions of electron density.
(b) One of the regions is a lone pair, which results in a seesaw-shaped molecular
structure.
EXAMPLE 7.15
FIGURE 7.25

(a) XeF4 adopts an octahedral arrangement with two lone pairs (red lines) and four bonds
in the electron-pair geometry.
(b) The molecular structure is square planar with the lone pairs directly across from one
another.
EXAMPLE 7.16.1
EXAMPLE 7.16.2
EXAMPLE 7.16.3
FIGURE 7.26

(a) There is a small difference in electronegativity between C and H, represented as a

short vector.
(b) The electronegativity difference between B and F is much larger, so the vector
representing the bond moment is much longer.
FIGURE 7.27

The overall dipole moment of a molecule depends on the individual bond dipole moments and how they are
arranged.
(a) Each CO bond has a bond dipole moment, but they point in opposite directions so that the net CO2 molecule is
nonpolar.
(b) In contrast, water is polar because the OH bond moments do not cancel out.
FIGURE 7.28

(a) Molecules are always randomly distributed in the liquid state in the absence of an
electric field.
(b) When an electric field is applied, polar molecules like HF will align to the dipoles with
the field direction.
EXERCISE 26A
EXERCISE 26B
EXERCISE 26C
EXERCISE 26D
EXERCISE 39A
EXERCISE 39B
EXERCISE 39C
EXERCISE 39D
EXERCISE 39E
EXERCISE 44D
EXERCISE 44E
EXERCISE 45D
EXERCISE 48
EXERCISE 62
EXERCISE 67
EXERCISE 74
Chapter Outline
 Chemical Bond Formation
 Covalent Bonding and Lewis Structures
 Atom Formal Charges in Covalent Molecules and Ions
 Resonance
 Exceptions to the Octet Rule
 Molecular Shapes
 Bond Polarity and Electronegativity
 Bond and Molecular Polarity
 Bond Properties: Order, Length,
and Energy