Chapter 8

Bonding and
Molecular Structure

Jeffrey Mack
California State University,
Sacramento
 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?
 Chemical Bonding

Chemical bond: attractive force holding two or more atoms

together

Covalent bond: a sharing electrons between the atoms.

non–metal / non–metal bonds.

Ionic bond: electrostatic in nature, transfer of

electrons from a metal to a nonmetal.
(cation + anion)

Metallic bond: attractive force holding pure metals

together.
Cations in a “sea” of electrons.
Two Extreme Forms of Connecting
or Bonding Atoms
Ionic Bonding: complete
transfer of 1 or more electrons
from one atom to another.
(metals and non-metals)

Covalent Bonding:
valence electrons shared
between atoms.
(non-metals and non-
metals)
Most bonds are somewhere in between.
 Ionic Bonding
Ionic Bonding results when an electron or electrons are
transferred from one atom to another.
The transfer results in each attaining an octet or Noble gas
electron configuration.

3s1 3s23p5
e–

Na + Cl  Na+ Cl

2s22p6
3s23p6
Noble gas electron Na+ Cl-
configurations  [Ne] [Ar]
 Covalent Bonding
• There are many examples of compounds
having covalent bonds, including the gases in
our atmosphere (O2, N2, H2O, and CO2),
common fuels (CH4), and most of the
compounds in your body.
• Covalent bonding is also responsible for the
atom-atom connections in polyatomic ions.
 Covalent Bond Formation
A covalent bond results from a overlap of
valence orbitals on neighboring atoms.
Valence Electrons and Lewis Symbols for Atoms:
 Covalent Bonding & Lewis
Structures
• The American chemist Gilbert Newton
Lewis (1875–1946) introduced a useful
way to represent the valence shell
electrons of an atom.
• The element’s symbol represents the
nucleus including the core electrons.
• Up to four valence electrons, indicated
by dots, are placed one at a time
around the symbol.
G. N. Lewis
• If any valence electrons remain, they
1875 - 1946
are paired with ones already there or
shared electrons up to a total of eight.
 Lewis Dot Symbols

Notice that the group numbers of the main

group elements represents the number of
valence electrons (dots) for each element.
 Valence Electrons

• Electrons are divided between

core and valence electrons
B 1s2 2s2 2p1
• Core = [He] , valence = 2s2 2p1

Br [Ar] 3d10 4s2 4p5

Core = [Ar] 3d10 , valence = 4s2 4p5
 Lewis Dot Structures & the Octet
Rule
• Covalent bonding, a bond results when one or more
electron pairs are shared between two atoms.
• 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

• The number of unpaired valence electrons gives a general

indication as to the number of bonds an atom will likely form.
• Hydrogen has only one electron and therefore can only
make one covalent bond.
• Gr 7A has only one unpaired electron, so it generally forms
one bond.
• Gr 6A had two unpaired electrons, thus the likelihood of two
bonds. ... and so on.
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

“single bond”
 The Octet Rule
• No. of valence electrons of an atom = Group number
• For Groups 1A-4A, no. of bond pairs = group number
• For Groups 5A -7A, BP’s = 8 - Grp. No.
• Hydrogen can only form one bond and never has lone
pairs.
• Boron often forms only 3 bonds.
• Elements in the 3rd period and beyond can exceed the
octet rule.
• Some stable molecules can form with an odd number of
electrons.
Example: N2
Each nitrogen atom needs 8 electrons to
complete an octet…
But each nitrogen has only 5 valence electrons!
As a result, the electrons must be shared.

There are 10
:N N: electrons
  

 N N
  

 available
   
Triple bond!   
  

There are 10 valence electrons present N2 needs 16

Therefore 6 electrons must be shared. electrons (28)
The remaining 4 electrons are the lone pairs
 Drawing Lewis Electron Dot
Structures
1. In general, for a poly atomic molecule the atom that
is the lowest and to the left on the periodic table
will be in the center. (lowest Electron Affinity)
2. Determine the total number of valence electrons in
the molecule or ion.
• In a neutral molecule, this number will be the sum
of the valence electrons for each atom.
• For an anion, add the number of electrons equal to
the negative charge.
• For a cation, subtract the number of electrons equal
to the positive charge.
 Drawing Lewis Electron Dot
Structures
3. Place one pair of electrons between each pair of
bonded atoms to form single bonds.
4. Use the remaining pairs to form more bonds or add
in as lone pairs to complete the octet of each atom.
5. If the central atom has fewer than eight electrons at
this point, change one or more of the lone pairs on
the terminal atoms into a bonding pair between the
central and terminal atom to form a multiple bond.
• Hydrogen atoms will never have lone pairs or
multiple bonds!
Building a Lewis Dot Structure
Ammonia, 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 x 1) + 5
= 8 electrons / 4 pairs
Building a Lewis Dot Structure

3. Form a single bonds between the H N H

central atom and each surrounding
atom. H

4. The remaining electrons form ••

LONE PAIRS to complete octet as H N H

needed.
H
3 BOND PAIRS and 1 LONE PAIR.

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

H shares 1 pair.
 Sulfite Ion, SO32−
Step 1. Central atom = S
Step 2. Count valence electrons:
S= 6
3 x O = 3 x 6 = 18
Negative charge = 2
TOTAL = 26 e- or 13 pairs
Step 3. Form bonds

10 pairs of electrons are

now left.
 Sulfite Ion, SO32−
4. The remaining pairs become lone pairs, first
on outside atoms and then on central atom.

••
•
• O •
•

•• ••
•
• O
••
S••
O
••
•
•

Each atom is surrounded by an octet

of electrons.
 Carbon Dioxide, CO2
1. Central atom = _______
2. Valence electrons = __ or __ pairs
3. Form bonds.
This leaves 6 pairs.

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×+
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×+
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×+
1 6 = 12 electrons available

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

Additional H
Stuctures:
C H
O

H O H
:C :
 Formaldehyde, CH2O

Additional H
Stuctures:
C H
O

:
:
H O H H C O H
:C :
 Formaldehyde, CH2O

Additional H
Stuctures:
C H correct structure

O
Not this one…

:
:
H O H H C O H
:C : or this one…
 Formaldehyde, CH2O

Additional H
Stuctures:
C H correct structure

O nature likes symmetry!

Not this one…

:
:
H O H H C O H
:C : or this one…
 Formaldehyde, CH2O

Additional H
Stuctures:
C H correct structure

O nature likes symmetry!

Not this one…

:
:
H O H H C O H
:C : or this one…

You will see why the first structure is favored by formal

chargers later.
 Double & Triple Bonds
H2CO
Double and even
triple bonds are
commonly observed
for C, N, P, O, and S

SO3

C2F4
Lewis Structures of Common
Oxoacids & Their Anions
Common Isoelectric Molecules &
Ions

Molecules and ions having the same number of valence

electrons and the same Lewis structures are said to be
isoelectronic
Atom Formal Charges in Covalent
Molecules & Ions
• The formal charge is the charge that would reside on an
atom in a molecule or polyatomic ion if we assume that all
bonding electrons are shared equally.
• The formal charge for an atom in a molecule or ion is
calculated based on the Lewis structure of the molecule or
ion, using:

FC = NVE  [LPE + ½ BE]

• NVE = the number of valence electrons in the uncombined

atom (and equal to its group number in the periodic table).
• LPE = number of lone pair electrons on an atom.
• BE = number of bonding electrons around an atom.
Calculating the Formal Charge on
Each Atom in a Covalent Molecule
Hydrogen Fluoride: HF FC = NVE  [LPE + ½ BE]

H F
Number of valence
electrons: 1 7
Number of bonding 2 2
electrons:
Number of lone pair 0 6
electrons:
Formal charge: 0 0

 2
FC(H)  1  0  
 2
HF  2
FC(F)  7  6  
 2
0 0
Calculating the Formal Charge on
Each Atom in a Covalent Molecule
When the sum of the formal charges on the atoms in
a molecule equals the expected overall charge on the
molecule, the Lewis structure is valid.

HF
0+0 =0

HF is expected to be a neutral compound, and the

formal charges validate this Lewis dot structure.
Carbon Dioxide, CO2

O-atom: FC = 6 – [4 + ½  4] = 0

•• ••
• •
• O C O •

0 + 0 + 0 = 0

C-atom: FC = 4 – [0 + ½  8] = 0
 Use Formal Charges to Predict Which
Atom Carries the Negative Charge on CN−

[ :C  N: ] –
–1 0

 6  6
FC(C)  4  2   FC(N) 5  2  
 2  2

The negative charge resides on the carbon atom.

As expected the overall charge is 1
 CH2O Formal Charges
Generally, the structure with 0 0 0
the lowest formal charges on
each atom or negative H C H
charges on the atoms with
the highest EA’s are often This one is
most favored. O most
favorable!
0
0 +2 0
H O H 0 0

:
:
:C : not favorable!
H C O H
-2 -1 +1
not favorable!
 Resonance
Consider the nitrate anion: The double bond does not
have to be on the vertical O-atom. There are three
equivalent structures that can be drawn.
– – –
: :

: :

: :
: :
: :

: :
:O N O: :O N O O N O:

:O : :O : :O :

We see that the double bond moves around or

“resonates” between the structures indicating that
the molecule exhibits what is called “Resonance” .
 Resonance
All three of the Lewis structures are equivalent
Resonance Structures.

– – –
: :

: :

: :
: :

: :
: :
:O N O: :O N O O N O:

:O : :O : :O :

Resonance stabilizes the energy (lowers) by

distributing electron density over the entire molecule.
The measured fHo is more exothermic than the
predicted value.
 Resonance
Identifying Resonance: Compounds that exhibit
resonance will have fractional bond orders.
# of A-B bonds
Bond Order =
# of A-B links
–

: :
: :
:O N O

:O :

4 N  O bonds
BO   1.333
3 N  O links
 Exceptions to the Octet Rule
Certain elements can violate the octet rule. Boron
may form stable compounds with only 6 valence
electrons.

BF3 SF4

Compounds in the 3rd period and beyond can have

more than 8 electrons.
 Exceptions to the Octet Rule
There are three classes of exceptions to the
octet rule:
1. Molecules with an odd number of electrons.
2. Molecules in which one atom has less than
an octet
3. Molecules in which one atom has more than
an octet.
 Odd Numbers of Electrons
Examples: Generally molecules such as ClO2, NO,
and NO2 have an odd number of electrons.

NO (nitrogen monoxide) Available electrons = 11

11
 5.5...?
2

N O or N O
There must be an odd electron!
Molecular Orbital Theory will explain why NO is
stable later.
 Incomplete Octet
• Relatively rare.
• Molecules with less than an octet are typical for
compounds of Groups 1A, 2A, and 3A
Most typical example is BH3.
H
Available Electrons = 3 + 3(1) = 6 H B H

There are only 6 electrons on the central atom.

Hydrogen may only form one bond.
The formal charges (all zero) support the drawn
structure.
 Central Atoms that Exceed the
Octet Rule
• Atoms from the 3rd period onwards can
accommodate more than an octet.
• Beyond the third period, the d-orbitals are low
enough in energy to participate in bonding and
accept the extra electron density.

Example: BrF3

Available Electrons = 7 + 3(7) = 28

Each fluorine atom can only share one electron.

What does this mean??

BrF3 Bromine has 7 valence electrons (4s24p5)
Fluorine also has 7 (2s22p5)
Br has the lowest electronegativity so it will be the
central atom in the molecule.

Each F shares
There are 10
one electron to
complete an Br F total electrons in
the Br valence
octet.
F
 SF6
Available Electrons = 48
Sulfur has 6 valence electrons, fluorine has seven.

If each F shares one electron with one of the six

from S, F completes its octet.

This will yield a compound with

F
F F
S in the center having 6 F’s
bonded. S
F F
12 valence electrons around
the S
F
Compounds in Which an Atom Has
More Than Eight Valence Electrons
 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 C H
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° = 360°
90° 90°
H C H
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 C H 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

No. of e- Pairs
Around Central
Atom Example Geometry
No. of e- Pairs
Around Central
Atom Example Geometry

2 F—Be—F linear
180°
No. of e- Pairs
Around Central
Atom Example Geometry

2 F—Be—F linear
180°
F
planar
3 trigonal
B
F F
120°
No. of e- Pairs
Around Central
Atom Example Geometry

2 F—Be—F linear
180°
F
planar
3 trigonal
B
F F
120°

H 109°
4 tetrahedral
C
H
H
H
Electron Pair Geometries
 Central Atoms with Single-Bond
Pairs & Lone Pairs
4 bonding pairs of electrons about the central atom, no lone
pairs on the central atom:
4 groups of electrons (all bonding)

Electron Pair Geometry (EPG) :

Tetrahedral
Molecular Geometry (MG):
Tetrahedral

When there are no lone pairs of

electrons in a molecule, the molecular
and electronic geometries are the same!
 Central Atoms with Single-Bond
Pairs & Lone Pairs
4 total pairs of electrons about the central atom, three bonding,
one lone pair on the central atom:

Electron Pair Geometry (EPG) :

Tetrahedral
Molecular Geometry (MG):
Trigonal Pyramidal

The lone pair forces the bonds to

reduce below the normal 109.5°.
 Central Atoms with Single-Bond
Pairs & Lone Pairs
Four groups of electrons, 2 bonding, 2 lone pairs on the central
atom:

Electron Pair Geometry (EPG) :

Tetrahedral
Molecular Geometry (MG):
Bent

The lone pairs force the bonds to

reduce below the normal 109.5°.
 Compounds with Less Than an
Octet
BF3 •
••
•
• F •

12 pairs of electrons available, F

forms only 1 bond B
The B atom is surrounded by only
3 electron pairs.
Bond angles are 120°

Molecular and Electron Pair geometries are

described as trigonal planar.
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
:P : Cl Cl
. 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
Three groups of electrons, all bonding,
no lone pairs on the central atom:
 Example: SO2
The lone pair of electrons forces the molecule into a
bent molecular geometry.

:
SO2 S

3 groups of electrons (2 bonds, 1 lp)

Electron Pair Geometry (EPG) Trigonal Planar
Molecular Geometry (MG): bent
Bond Polarity & Electronegativity

Recall that electronegativity () measures the relative

tendency for an atom to polarize a bond. It follows Zeff on
the periodic table.
Bond Polarity & Electronegativity

As the difference in Electronegativity increases

(), so does the ionic character of the bond.

Increasing covalent character

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.
 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 Notice the symmetry of the
a non-polar. molecule:
• When divided, the top and
bottom as well as the left and
I : I right are mirror images of one
another.
iodine (I2) • One also knows the molecule
 = 2.5  2.5 = 0
is non polar because the
bond is non polar.
 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 > C-F > O-F
Bond Polarity & Molecular Polarity
When a molecule possesses a net dipole moment, it
is polar.

The individual O-H

bond dipoles result The molecule
in a “net” or is therefore
overall polar.
dipole moment for
the molecule.
H2O
 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
Dipole Moments & Molecular
Polarity
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
Therefore shorter!
Bond length decreases with increasing bond order
(Strength)
example: O=O bond is shorter than O–O bond
Bond Order: # of Bonds Between a
Pair of Atoms

Double bond
Single bond

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

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

110 pm 745 kJ
 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.
 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
Using Bond Dissociation Enthalpies

Estimate the energy of the reaction

H—H(g) + Cl—Cl(g)  2 H—Cl(g)
Net energy = ∆rH =
= energy required to break bonds
 energy evolved when bonds are made

H—H = 436 kJ/mol

Cl—Cl = 242 kJ/mol
H—Cl = 432 kJ/mol
It takes energy to break bonds. (endothermic)
Energy is releases when bonds are made.
(exothermic)
Energy Supplied (H>0)

Molecule (g)  Molecular fragments (g)
Energy Released (H<0)

rH =  (bonds broken)   (bonds formed)

If more energy is released than is required to break

the reactant bonds, then the over all reaction is
exothermic.
If more energy is required to break bonds than is
released when the product bonds form, then the over
all reaction is endothermic.
Estimate the rH for the following reaction using
average bond dissociation enthalpies.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
Estimate the rH for the following reaction using
average bond dissociation enthalpies.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

First draw out the Lewis structures to determine

the number and types of bonds
Estimate the rH for the following reaction using
average bond dissociation enthalpies.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

First draw out the Lewis structures to determine

the number and types of bonds
H
H
H C H + 2 O=O  O=C=O +2
O H
H
Estimate the rH for the following reaction using
average bond dissociation enthalpies.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

First draw out the Lewis structures to determine

the number and types of bonds
H
H
H C H + 2 O=O  O=C=O +2
O H
H

Second, count up the bonds of each type:

Estimate the rH for the following reaction using
average bond dissociation enthalpies.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

First draw out the Lewis structures to determine

the number and types of bonds
H
H
H C H + 2 O=O  O=C=O +2
O H
H

Second, count up the bonds of each type:

4  (C–H) + 2  (O=O)  2 (C=O) + 4  (O–H)
Now sum up the bonds broken and subtract the
bonds formed.
rH = 4 (C–H) + 2 (O=O) – [2  (C=O) + 4  (O–H) ]
Now sum up the bonds broken and subtract the
bonds formed.
rH = 4 (C–H) + 2 (O=O) – [2  (C=O) + 4  (O–H) ]

rH = {4 (413 kJ/mol) + 2 (495 kJ/mol)}

– { 2 (745 kJ/mol + 4 (463 kJ/mol) }
Now sum up the bonds broken and subtract the
bonds formed.
rH = 4 (C–H) + 2 (O=O) – [2  (C=O) + 4  (O–H) ]

rH = {4 (413 kJ/mol) + 2 (495 kJ/mol)}

– { 2 (745 kJ/mol + 4 (463 kJ/mol) }

= –718 kJ/mol
Now sum up the bonds broken and subtract the
bonds formed.
rH = 4 (C–H) + 2 (O=O) – [2  (C=O) + 4  (O–H) ]

rH = {4 (413 kJ/mol) + 2 (495 kJ/mol)}

– { 2 (745 kJ/mol + 4 (463 kJ/mol) }

= –718 kJ/mol

By way of comparison, rH from fHo = –890 kJ/mol

890  (718)
% error =  100  19.3%
890