Chapter 9

Chemical Bonding I:
Basic Concepts
- Electrostatic potential map?
- Why are atoms found together in a
compound?

- What are the forces that hold atoms?

- How can we draw a simple structure?

© McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom. No reproduction or
further distribution permitted without the prior written consent of McGraw-Hill Education.
 Valence Electrons number of
Group e – configuration #of
valence e- –
valencee
1A ns1 1
Valence electrons are the outer 2A ns 2 2
shell electrons of an atom
3A ns 2np1 3
The valence electrons are the 4A ns 2np 2 4
electrons that participate in 5A ns 2np3 5
chemical bonding 6A ns 2np 4 6
7A ns 2np 5 7

• LEWIS explains a chemical bond: atoms combine to achieve

more stable electron configuration
• Maximum stability of an atom = isoelectronic with a noble gas
• For chemical bonds, only OUTERMOST regions in contact!

• Chemical bond, primarily the valence electrons

© McGraw-Hill Education. 9-2
Lewis Dot Symbols for the Representative
Elements & Noble Gases

• One dot for each valence electron

• Number of valence electrons (dots) = the group number of an
element
• Same group, similar Lewis ©dot symbols
McGraw-Hill Education. 9-3
 The Ionic Bond
Low ionization energy  Tendency to form cation
High electron affinity  Tendency to form anion
Mostly Group 1A or 2A metal + A halogen or oxygen
Ionic bond:
The electrostatic force that holds ions together in an ionic compound.

-
2 2
1s 2 2s1 1s 2s 2 p
5
1s 2 1s 2 2s 2 2 p 6
He  Ne 

© McGraw-Hill Education. 9-4

 Example 9.1
Use Lewis dot symbols to show the formation of aluminum oxide, Al2O3.

Al2O3  Lewis dot symbols: 13 Al = [Ne] 3s² 3p¹

8 O = [He] 2s² 2p⁴

Ne 3s 2 3 p1 1s 2 2s 2 2 p 4 Ne Ne 

the transfer of electrons

is from Al to O

© McGraw-Hill Education. 9-5

 Lattice Energy & The Born-Haber Cycle
Lattice energy is the energy Coulomb’s Law E: potential energy
required to separate completely Q+: charge on the cation
one mole of a solid ionic
Q++.Q
Q Q–-
E =k Q−: charge on the anion
compound into gaseous ions. r r: distance between the ions

• Formation of LiF has five separate steps:

Born-Haber Lattice energy and enthalpy

Cycle change are the same
magnitude, BUT they have
opposite sign!

ΔHoverall = ΔH1 + ΔH2 + ΔH3 + ΔH 4 + ΔH 5
(according to HESS’S LAW)

© McGraw-Hill Education. 9-6

 Lattice Energies for Some Metal Halides
and Oxides
Lattice Energies and Melting Points of Stability of an ionic compound α lattice energy
Some Alkali Metal and Alkaline Earth (the greater the lattice energy, the more stable the ionic compound)
Metal Halides and Oxides
Compound
Lattice Energy Melting Point Lattice energy always (+), solid  gas (endothermic)
(kJ/mol) (°C)
LiF 1017 845 Rough correlation between lattice energy and
LiCl 828 610 melting points:
LiBr 787 550 • smaller lattice energy  lower mp
LiL 732 450
• larger lattice energy  higher mp
NaCl 788 801
NaBr 736 750 Lattice energydoubly charged > lattice energysingly charged
Nal 686 662
KCl 699 772
LatticeEnergy
KBr 689 735 Compound
KI 632 680
kJ / mol
MgCl2 2527 714 MgF2 2957 Q :+ 2, – 1
Na2O 2570 Sub* MgO 3938 Q:+ 2,– 2
MgO 3890 2800
LiF 1036
*Na2O sublimes at 1275°C.
LiCl 853 rF –  rCl–
© McGraw-Hill Education. 9-7
 The Covalent Bond
LEWIS: chemical bond involves electron sharing by atoms
H. + .H  H : H ( H — H )
A covalent bond is a chemical bond in which two or more electrons are
shared by two atoms. ( : ) are often represented by a single line (bond)

Shared electrons are attracted to the nuclei of both atoms, this holds
atoms together, formation of covalent bond.

In many-electron atoms; only valence electrons!

F: 1s2 2s2 2p5

© McGraw-Hill Education. 9-8

 The Covalent Bond
Only valence electrons are shown in a LEWIS STRUCTURE
(bonds and lone pairs)

Single
bond

O atom achieves a noble gas configuration

OCTET RULE: An atom other than hydrogen tends to form bonds
until it is surrounded by eight valence electrons, for H it is 2 electrons

Double bond – two atoms

share two pairs of electrons

Triple bond – two atoms

share three pairs of electrons

Multiple bond – two atoms share two or more pairs of electrons 9-9
© McGraw-Hill Education.
 Lengths of Covalent Bonds
Average Bond Lengths of Some
Bond length is the distance between two nuclei Common Single, Double, and
of two covalently bonded atoms in a molecule Triple Bonds
(experimentally determined)
Bond Bond Length
Type (pm)
C−H 107
C−O 143
C=O 121
C−C 154
C=C 133
Multiple bonds are shorter than C≡C 120
single covalent bonds! C−N 143
Bond Lengths C=N 138
Triplebond < Double Bond < SingleBond C≡N 116
N−O 136
The shorter multiple bonds are also N=O 122
more stable than single bonds O−H 96
© McGraw-Hill Education. 9-10
 Comparison of the Properties of Covalent
and Ionic Compounds
Comparison of Some General
Properties of an Ionic Compound
In covalent compounds, intermolecular and a Covalent Compound
forces are present, weak and easy to Property NaCl CCl4
(ionic) (covalent)
break up, so that relatively low mp and bp
Appearance White Colorless
solid liquid
In ionic compounds, the electrostatic Melting Point (°C) 801 −23
forces are involved, strong, so that high Molar heat of fusion* 30.2 2.5
(kJ/mol)
mp
Boiling point (°C) 1413 76.5
Molar heat of 600 30
Many ionic compounds, water soluble, vaporization* (kJ/mol)
strong electrolytes, (molten) conduct Density (g/cm3) 2.17 1.59
electricity, (mobile cations and anions) Solubility in water High Very low
Electrical conductivity
Most covalent compounds, insoluble in Solid Poor Poor
water, nonelectrolytes, (molten) do not Liquid Good Poor
conduct electricity, no ions
*Molar heat of fusion and molar heat of vaporization are the amounts of heat
© McGraw-Hill
neededEducation.
to melt 1 mole of the solid and to vaporize 1 mole of the9-11
liquid,
respectively.
Comparison of the Properties of Covalent
and Ionic Compounds

© McGraw-Hill Education. 9-12

 Polar Covalent Bonds
Polar covalent bond or polar bond is a covalent bond
with greater electron density around one of the two atoms
In HF molecule, H and F atoms do not share the bonding
electrons equally! (In H2 molecule equally)

They can be thought intermediate between a nonpolar

covalent (e- sharing) and an ionic bond (e- transfer)

© McGraw-Hill Education. 9-13

 Electronegativity
Electronegativity is the ability of an atom to attract toward itself the
electrons in a chemical bond. High EN  great tendency to attract
electrons.

It is related to EA and IE; high EA, high IE, high electronegativity

It is a comparison to those of other elements, has no unit

The most EN: 5A, 6A, 7A (halogens)

Increases from bottom to top in a group
The least EN: 1A-2A and Aluminium
Beryllium  mostly covalent compounds

Electron Affinity Electronegativity

measurable, Cl is highest relative, F is highest
Xg  + e –  X – g  © McGraw-Hill Education. 9-14
The Electronegativities of Common
Elements

Increases
( → ) in a period
( ↑ ) in a group
in the PT

© McGraw-Hill Education. 9-15

Classification of Bonds by Difference in
Electronegativity
Electronegativity difference is wide  result in ionic bond
e- moves from less EN  more EN
In general, metallic and nonmetallic atom

Most covalent bonds, nonmetallic atoms

Pure covalent bond: same atoms, electronegativities
Polar covalent bond: comparable EN possessing atoms
Increasing differencein electronegativity
              


Covalent Polar Covalent Ionic

–
 –

share e partialtransfer of e transfer e –

EN Difference Bond Type

0 Covalent

≥2 lonic

0 < and < 2

© McGraw-Hill Education. Polar Covalent
9-16
 Example 9.2
Classify the following bonds as ionic, polar covalent, or covalent:
a) the bond in HCl
b) the bond in KF
c) the CC bond in H3CCH3
(Electronegativities: H = 2.1, Cl = 3.0, K = 0.8, F = 4.0, C = 2.5).

(a) electronegativity difference between H and Cl = 3.0 - 2.1 = 0.9

Since 0 < 0.9 < 2  bond is polar covalent

(b) electronegativity difference between K and F = 4.0 - 0.8 = 3.2

since 3.2 > 2  bond is ionic

(c) two C atoms are identical, bonded to each other, are bonded
to three other H atoms  C − C is purely covalent
© McGraw-Hill Education. 9-17
 Writing Lewis Structures
1. Draw skeletal structure of compound showing what atoms are bonded
to each other. Place least electronegative element in the center.
H, F; usually in the terminal positions.

2. Count total number of valence electrons;

• For each (-) add 1
• For each (+) subtract 1

3. Draw a single bond between central atom and each of the

surrounding atoms. Complete an octet for all atoms except
hydrogen.

4. If structure contains too many electrons, or if the central atom has

fewer than eight electrons, try double and triple bonds on central
atom as needed, use lone pairs to complete octet.
© McGraw-Hill Education. 9-18
 Example 9.3
Write the Lewis structure for nitrogen trifluoride (NF3) in
which all three F atoms are bonded to the N atom.
(NF3 is a colorless, odorless, unreactive gas).

Step 1. N atom: less electronegative than F, skeletal structure of NF3:

the least electronegative

‘in center’

Step 2. N: 2s2 2p3  5e-

total 26e-
F: 2s2 2p5 (7e-) x 3 = 21e-

Step 3. 2e- = 26e- - 24e- Step 4. is not required

in this case

© McGraw-Hill Education. 9-19

 Example 9.4
Write the Lewis structure for nitric acid (HNO3) in which
the three O atoms are bonded to the central N atom and
the ionizable H atom is bonded to one of the O atoms.
(HNO3 is a strong electrolyte).

© McGraw-Hill Education. 9-20

 Example 9.4
O N O H
Step 1. The skeletal structure of HNO3 (nitric acid):
O
skeletal structure
Step 2. N: 2s 2p  5e
2 3 -

O: 2s2 2p4  (6e-) x 3 = 18e- 24e- total valence electrons!

H: 1s1  1e-

Step 3. octet:  24e- already okay,

3O
BUT N has only 6e-!!
1H
1Nx

Step 4.
octet:
 24e-
3O
1H
1N

the octet rule is Education.

© McGraw-Hill also satisfied for the N atom 9-21
 Example 9.5
Write the Lewis structure for the carbonate ion (CO32-).
Step 1. CO32-  carbonate ion O skeletal
structure
O C O

Step 2. C: 2s2 2p2  4e-

22e- + 2e- = 24e- totally
O: 2s2 2p4  (6e-) x 3 = 18e-

Step 3.
octet:
 24e- 3O
1Cx

Step 4. octet:
 24e- 3O
1C

© McGraw-Hill Education. 9-22

 Formal Charge and Lewis Structure
An atom’s formal charge is the difference between the
number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis structure.

total number of bondingelectrons 

1
formalchargeon an atom totalnumber of valence total number of
  
in aLewis structure electrons in the free atom non bonding electrons
2

The sum of the formal charges of the atoms in a molecule or ion must equal the charge
on the molecule or ion.

© McGraw-Hill Education. 9-23

 Example 9.6
Write formal charges for the carbonate ion, CO32-.
Method 1:

totalnumber of bondingelectrons
1
formalcharge onatom totalnumber of valence electrons totalnumber of
=  
inaLewis structure in the free atom nonbondingelectrons
2

The C atom  (4) – (0) – (8/2) = 4 – 4 = 0

The O atom in C=O  (6) – (4) – (4/2) = 6 – 6 = 0
The O atom in C-O  (6) – (6) – (2/2) = 6 – 7 = -1

Then CO32- 

© McGraw-Hill Education. 9-24

 Example 9.6
Write formal charges for the carbonate ion, CO32-.
Method 2:

The C atom has 4 valence e-, no nonbonding e-. Breaking of double bond &
2 single bonds = transfer of 4 e- to C atom. Formal charge is 4 − 4 = 0.

The O atom in C=O has 6 valence e-, 4 nonbonding e-. Breaking of double
bond = transfer of 2 e- to O atom. Formal charge is 6 − 6 = 0.

The O atom in C−O has 6 nonbonding e-. Breaking of single bond =

transfers another e- to O atom. Formal charge is 6 − 7 = − 1.

Then CO32- 

© McGraw-Hill Education. 9-25

 Formal Charge and Lewis Structures
Sometimes there are more than one acceptable Lewis
structures for a given species. To choose the most
plausible Lewis structure the following guideline is used:
1. For neutral molecules, a Lewis structure in which there
are no formal charges is preferable to one in which
formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one
in which negative formal charges are placed on the
more electronegative atoms.
© McGraw-Hill Education. 9-26
 Example 9.7
Formaldehyde (CH2O) a liquid with a disagreeable odor,
traditionally has been used to preserve laboratory specimens.
Draw the most likely Lewis structure for the compound.

© McGraw-Hill Education. 9-27

 Example 9.7
• Formaldehyde (CH2O)
H
 The two plausible skeletal structures:
C O
H C O H H
a  b 
a) C (least electronegative, center): 4e-, O: 6e-, H: (1e-) x 2 = 2e-  12e-
octet:
2H
H C  O  H 1Cx
1O

octet:
2H
1C
1O
© McGraw-Hill Education. 9-28
 Example 9.7
b)
octet: octet:
2H 2H
1O 1O
1Cx 1C

a)

Both structures satisfy the OCTET rule;

BUT (b) is the most plausible structure,

b) because it carries NO formal charges!!!

© McGraw-Hill Education. 9-29

 Resonance Structures
For ozone (O3) there are two equivalent Lewis structures:

Neither one of these two Lewis structures accounts for the known bond lengths in O 3

Expection: O – O (147.5 pm in H2O2) > O = O (120.74 pm in O2)

BUT experimentally measured; both bonds are in equal length (128
pm), resolved this problem by using both Lewis structures

A resonance structure is one of two or more Lewis structures for a single

molecule that cannot be represented accurately by only one Lewis
structure.

© McGraw-Hill Education. 9-30

 Example 9.8
Draw three resonance structures for the molecule nitrous oxide, N2O (the
atomic arrangement is NNO). Indicate formal charges. Rank the structures
in their relative importance to the overall properties of the molecule.

 skeletal structure N N O N: 2s2 2p3  (5e-) x 2 = 10e- 16e-

O: 2s2 2p4  6e- total

x x 

All three structures have formal charges!

b  the most important; (-) charge on the more electronegative atom
c  the least important; larger formal charges and the (+) charge is on the
more electronegative atom
 a, b, and c do not contribute© equally
McGraw-Hill Education. 9-31
 Exceptions to the Octet Rule
Octet rule is applied mainly to the 2nd period elements.
3 categories of exceptions:

• 1) The Incomplete Octet: In some compounds, number of

surrounding electrons are fewer than eight. e.g. Be (2A): 1s 2 2s2

BeH2 Be – 2e –
2H – 2 1e –
4e –

The structure does not satisfy the octet rule!

© McGraw-Hill Education. 9-32

 Exceptions to the Octet Rule
Octet rule is applied mainly to the 2nd period elements.
3 categories of exceptions:

1) The Incomplete Octet: In some compounds, number of

surrounding electrons are fewer than eight. e.g. B (3A): 1s 2 2s2 2p1

Β – 3e –
BF3 3F – 3 7e –
24e –

Rezonance structures satisfy the octet rule for Boron! :

© McGraw-Hill Education. 9-33

 Exceptions to the Octet Rule
• 2) Odd-Electron Molecules: Some molecules contain an odd
number of electrons. e.g. Nitric oxide (NO), nitrogen dioxide (NO 2)
N – 5e –
NO 0 – 6e
–

11e –
 We need even number of electrons but here octet rule cannot be satisfied…

Odd-electron molecules are called sometimes as radicals.

Highly reactive. Great tendency to pair the unpaired electron!

 Dinitrogen tetroxide satisfies the octet rule of N and O

© McGraw-Hill Education. 9-34
 Exceptions to the Octet Rule
3) The Expanded Octet: 3rd and beyond the 3rd period elements
form compounds in which the central atom has more than eight
electrons surrounding
(2nd period elements cannot have more than eight valence electrons around the central atom!)

 3d orbitals enable an atom to form an expanded octet.

e.g. SF6, very stable compound.

S: [Ne] 3s2 3p4 S – 6e – 6 Single bonds 6 2  = 12

18 lone pairs 18 2  = 36
6F – 42e –
Total = 48
48e –

 There are 12 electrons around the central SULFUR atom!

BUT in this compound, S obeys the octet rule 

© McGraw-Hill Education. 9-35
 Example 9.9
Draw the Lewis structure for aluminum triiodide (AlI3).

Al  3s2 3p1  3e-

24e- total
I  5s2 5p5  (7e-) x 3 = 21e-

less electronegative, central

 No formal charge for Al, I

 Do not obey the octet rule
 6 valence e- around the Al, therefore this is an example of
the Incomplete Octet
© McGraw-Hill Education. 9-36
 Example 9.10
Draw the Lewis structure for phosphorus pentafluoride (PF5),
in which all five F atoms are bonded to the central P atom.

P  3s2 3p3  5e-

40e- total
F  2s2 2p5  (7e-) x 5 = 35e-
less electronegative, central

 No formal charge on the P and F

 Do not obey the octet rule
 10 valence e- around the P, therefore this is an example of
the Expanded Octet
© McGraw-Hill Education. 9-37
 Example 9.11
Draw a Lewis structure for the sulfate ion (SO42-) in
which all four O atoms are bonded to the central S atom.
O
SO42-  sulfate ion O S O skeletal structure
O

S  3s2 3p4  6e-

30e- + 2e- = 32e- total
O  2s2 2p4  (6e-) x 4 = 24e-

formal charges:
for O: 6 – 6 – 1 = – 1
for S: 6 – 0 – 4 = +2

© McGraw-Hill Education. 9-38

 Example 9.11
Draw a Lewis structure for the sulfate ion (SO42-) in
which all four O atoms are bonded to the central S atom.

too large formal charges!

Both of
them
eliminate some of them!
are
valid
The expanded octet for S atom!

S(-2), O(0) are inconsistent with the electronegativity of these elements!

© McGraw-Hill Education. 9-39
 Example 9.12
Draw a Lewis structure of the noble gas compound xenon tetrafluoride
(XeF4) in which all F atoms are bonded to the central Xe atom.

F F
Xe  5s2 5p6  8e- 36e-
skeletal structure Xe total
F 2s2 2p5  (7e-) x 4 = 28e-
F F

32e- BUT there are 36e- in total as

octet: valence electrons…
4F 36 - 32 = 4e-, namely 2 Lone Pairs
1 Xe 
are shown on the Xe central atom!

 No formal charges on the Xe and F

 Xe atom has an Expanded Octet!

© McGraw-Hill Education. 9-40

 End of Presentation

© McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom. No
reproduction or further distribution permitted without the prior written consent of McGraw-Hill Education. 9-41
Appendix of Image Long Descriptions

© 2019 McGraw-Hill Education. 9-42

Lewis Dot Symbols for the Representative
Elements & Noble Gases Long Description

The symbol is the elemental symbol surrounded by up to eight dots,

each dot representing a valence electron. By convention, the dots
appear on the left, right, top, and bottom of the elemental symbol.
For elements in Groups 1A through 8A, the number of valence
electrons for the atom is the same as the group number. For
example, sodium is a Group 1A element and has one valence
electron. Sulfur is a Group 6A element and has six valence
electrons.

© McGraw-Hill Education. 9-43

Born-Haber Cycle for Determining Lattice
Energy Long Description
To produce one mole of LiF from its elements, first lithium must be
sublimed and fluorine must dissociate from its molecular to elemental
form. Once both Li and F atoms are in the gaseous state, an electron
is transferred from Li to F, forming lithium and fluoride ions. The
formation of solid LiF from its gaseous ions is the lattice energy of the
compound.
The heat of formation of LiF is considered the overall heat of the
reaction. The overall heat of reaction is equal to the enthalpy of
sublimation of Li, the bond dissociation energy of fluorine, the
ionization of Li, the electron affinity of F, and the lattice energy of LiF.
Both the electron affinity and ionization energy are negative values,
according to the direction of the equation that represents each
process.

© McGraw-Hill Education. 9-44

Polar Covalent Bonds Long Description

The molecule is linear, but the electron density is greater about the F
atom instead of equally shared between the two atoms. Because the
F atom has more electron density, the F side of the molecule is said
to be electron rich, and the H side of the molecule is said to be
electron poor.

© McGraw-Hill Education. 9-45

 Electronegativity Long Description

Fluorine is the most electronegative element, so it attracts the

electron in the covalent bond more strongly than the H does. This
leads to an electron rich region on the F side of the molecule and an
electron poor region on the H side of the molecule.

© McGraw-Hill Education. 9-46

 The Electronegativities of Common
Elements Long Description
Generally, electronegativity increases across a row. As the metallic
character of an element decreases across a row, electronegativity,
the desire of an atom for a shared pair of electrons, increases.
Electronegativity generally decreases down a column. As the metallic
character of an element increases down a column, electronegativity
decreases. There are several exceptions to these general trends,
though, especially throughout the transition metals.

© McGraw-Hill Education. 9-47

Classification of Bonds by Difference in
Electronegativity Long Description
A plot of percent ionic character versus electronegativity difference
shows that pure covalent bonds (such as the Cl-Cl bond in Cl2) have
zero percent ionic character, but no bonds have 100% ionic
character. Many covalent compounds have some ionic character
(less than 25%), and many ionic compounds have at least 75% ionic
character.

© McGraw-Hill Education. 9-48

 Example 9.8 Long Description

The second structure has a triple bond between the two N atoms and
a single bond between N and O. The third structure has a single
bond between the two N atoms and a triple bond between N and O.

© McGraw-Hill Education. 9-49

Variation of Electronegativity with Atomic
Number Long Description
Generally, electronegativity increases across a row and decreases
down a column. There are several exceptions to these general
trends, though, especially throughout the transition metals. Halogens
are the most electronegative elements, and alkali metals are the
least electronegative elements.

© McGraw-Hill Education. 9-50

Average Bond Enthalpy in Polyatomic
Molecules Long Description
As the size of the atom increases, the bond energy decreases. An H-
F bond has an energy of 568.2 kJ/mol, while an H-Cl bond has an
energy of 431.9 kJ/mol because a Cl atom is larger than a F atom.
The H-Br bond is weaker than an H-Cl bond, and the H-I bond is
weaker still.
The type of bond also affects bond energy. A C-O single bond has an
energy of 351 kJ/mol, while a C-O double bond has an energy of 745
kJ/mol. A C-O triple bond has an energy of 1076.5 kJ/mol. So, when
two atoms are bonded, a triple bond is stronger than a double bond,
and a double bond is stronger than a single bond.

© McGraw-Hill Education. 9-51

 Bond Enthalpy
The enthalpy change required to break a particular bond in
1 mole of gaseous molecules is the bond enthalpy.

Bond Enthalpy
H2g   Hg  +Hg  ∆H° = 436.4 kJ

Cl2g   Clg  + Clg  ∆H° = 242.7 kJ

HClg   Hg  + Clg  ∆H° = 431.9 kJ

O2g   Og  + Og  ∆H° = 498.7 kJ

N2g   Ng  +Ng  ∆H° = 941.4 kJ

Order of Bond Enthalpies:

Triple Bond > ©Double Bond > Single Bond
McGraw-Hill Education. 9-52
Average Bond Enthalpy in Polyatomic Molecules
H2Og   Hg  + OHg  ΔH  = 502 kJ
OHg   Hg  + Og  ΔH  = 427 kJ
 The first step is more endothermic than the second.
Because the chemical environment changes.

Bond enthalpies of the same O – H bonds in H2O and CH3OH.

Thus, we speak of the average bond enthalpy of a particular bond.

502 + 427
Average OH bond enthalpy = = 464 kJ
2

For diatomic molecules measurable directly.

BUT for polyatomic molecules average over many compounds.
© McGraw-Hill Education. 9-53
 Bond Enthalpies (BE) and Enthalpy
Changes in Reactions
Chemical reactions involve the making and breaking of bonds.
Energy is required to break chemical bonds.
Chemical bond formation is accompanied by a release of energy.
• The enthalpy of reaction in the gas phase:
ΔH  = total energy input – total energy released
= BE  reactants  – BE products 

 If energy input > energy released, then, ∆H° (+) the reaction is endothermic

highly endothermic

 If released energy > absorbed energy, then, ∆H° (-) the reaction is exothermic

© McGraw-Hill Education. fairly exothermic 9-54

 Example 9.13
Calculate the enthalpy of reaction for the process:
H2 (g) + Cl2 (g)  2 HCl (g)
Types of Number of Bond enthalpy Energy change
bonds broken bonds broken kJ mol  kJ mol 
H  H H2  1 436.4 436.4
Cl  Cl Cl2  1 242.7 242.7

Types of Number of Bond enthalpy Energy change

bonds formed bonds formed kJ mol  kJ mol 
H  Cl HCl 2 431.9 863.8

The total energy input = 436.4 + 242.7 = 679.1 kJ/mol

The total energy released = 863.8 kJ/mol

ΔH  = total energy input – total energy released

= BE  reactants  – BE products 
= 679.1 – 863.8 = – 184.7 kJ/mol
© McGraw-Hill Education. 9-55
 Example 9.14
Estimate the enthalpy change for the combustion of hydrogen gas:
2 H2(g) + O2(g)  2 H2O(g)
Types of Number of Bond enthalpy Energy change
bonds broken bonds broken kJ mol  kJ mol 
H  HH2  2 436.4 872.8
O  O O2  1 498.7 498.7

Types of Number of Bond enthalpy Energy change

bonds formed bonds formed kJ mol  kJ mol 
O  HH2O  4 460 1840

The total energy input = 872.8 + 498.7 = 1371.5 kJ/mol

The total energy released = 1840 kJ/mol

ΔH  = total energy input – total energy released

= BE  reactants  – BE products 
estimation, because bond enthalpy
= 1371.5 – 1840 = – 468.5 kJ/mol of O-H is an average quantity!
© McGraw-Hill Education. 9-56