9.

0 THERMOCHEMISTRY
Concept of Enthalpy
Important Terms
Heat is energy transferred between two bodies of
different temperatures

System is any specific part of the universe

Surroundings is everything that lies outside the
system

Open system is a system that can exchange
mass and energy with its surroundings

Closed system is a system that allows the
exchange of energy with its surroundings

Isolated system is a system that does not allow
the exchange of either mass or energy with its
surroundings

Energy is the ability to do work
SI unit of energy is kg m
2
s
-2
or Joule (J)
Non SI unit of energy is calorie (Cal)
1 Cal = 4.184 J

Thermochemistry
A study of heat change in chemical reactions.
Two types of chemical reactions:
Exothermic
Endothermic
Exothermic reactions
- Enthalpy of products < Enthalpy of reactants, H is
negative.

- Energy is released from the system to the
surroundings.

Consider the following reaction:
A
(g)
+ B
(g)
C
(g)
H = ve
(reactants) (product)

reactants
enthalpy
reaction pathway
= -ve H
products
Energy profile diagram for exothermic reaction
Enthalpy of products > enthalpy of reactants, H is
positive

Energy is absorbed by the system from the surrounding

Endothermic Reactions
Consider the following reaction
A
(g)
+ B
(g)
C
(g)
H = + ve
(reactants) (product)
Energy profile of diagram endothermic reactions
Enthalpy, H
The heat content of a system or total energy in the
system

Enthalpy, H of a system cannot be measured when
there is a change in the system.

Example: system undergoes combustion or ionisation.
Enthalpy of Reaction, H and
Standard Condition
Enthalpy of reaction:
The enthalpy change associated with a chemical
reaction.

Standard enthalpy, H
The enthalpy change for a particular reaction that
occurs at 298K and 1 atm (standard state)
Thermochemical Equation
The thermochemical equation shows the enthalpy changes.

Example : H
2
O
(s)
H
2
O
(l)
H = +6.01 kJ

1 mole of H
2
O(l) is formed from 1 mole of H
2
O(s) at 0C,
H = +6.01 kJ

However, when 1 mole of H
2
O(s) is formed from 1 mole of
H
2
O(l), the magnitude of H remains the same with the
opposite sign of it.
H
2
O
(l)
H
2
O
(s)
H = 6.01 kJ
Types of Enthalpies
There are many kind of enthalpies such as:
Enthalpy of formation
Enthalpy of combustion
Enthalpy of atomisation
Enthalpy neutralisation
Enthalpy hydration
Enthalpy solution
Enthalpy of Formation, H
f
The change of heat when 1 mole of a compound is
formed from its elements at their standard states.

H
2

(g)
+ O
2(g)
H
2
O
(l)
H
f
= 286 kJ mol
1

The standard enthalpy of formation of any element in
its most stable state form is ZERO.
H (O
2
) = 0 H (Cl
2
) = 0
Enthalpy of Combustion, H
c
The heat released when 1 mole of substance is
burned completely in excess oxygen.

C
(s)
+ O
2(g)
CO
2(g)
H
c
= 393 kJ mol
1
Enthalpy of Atomisation, H
a
The heat change when 1 mole of gaseous atoms is formed
from its element

AH
a
is always positive because it involves only breaking of
bonds
e.g:

Na
(s)
Na
(g)
AH
a
= +109 kJ mol
-1

Cl
2(g)
Cl
(g)
AH
a
= +123 kJ mol
-1

Enthalpy of Neutralization, H
n

The heat change when 1 mole of water, H
2
O is formed from the
neutralization of acid and base .

HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+H
2
O
(aq)
H
n
= 58 kJ mol
1

Enthalpy of Hydration, AH
hyd


The heat change when 1 mole of gaseous ions is
hydrated in water.
e.g:
Na
+
(g)
Na
+
(aq)
AH
hyd
= 406 kJ mol
-1
Cl
-
(g)
Cl
-
(aq)
AH
hyd
= 363 kJ mol
-1
Enthalpy of Solution, H
soln

The heat change when 1 mole of a substance is
dissolves in water.
e.g:
KCl
(s)
K
+
(aq)
+ Cl

(aq)
AH
soln
= +690 kJ mol
-1


Enthalpy of Sublimation, H
subl

The heat change when one mole of a substance
sublimes (solid into gas).
I
2
(s)
I
2
(g)

A
subl
H

AHsubl

= +106 kJ mol
1


Calorimetry
A method used in the laboratory to measure the
heat change of a reaction.
Apparatus used is known as the calorimeter
Examples of calorimeter
Simple calorimeter
Bomb calorimeter
The outer Styrofoam cup
insulate the reaction
mixture from the
surroundings (it is
assumed that no heat is
lost to the surroundings)
Heat release by the
reaction is absorbed by
solution and the
calorimeter
Simple calorimeter
A bomb calorimeter

Important Terms in Calorimeter
Specific heat capacity, c
Specific heat capacity, c of a substance is the amount of
heat required to raise the temperature of one gram of the
substance by one degree Celsius (Jg
1
C
1
).
Heat capacity, C
Heat capacity,C is the amount of heat required to raise
the temperature of a given quantity of the substance by
one degree Celsius (JC
1
)
q = mcT
Heat released by
substance
=
Heat absorbed
by calorimeter
q = heat released by substance
m= mass of substance
C= specific heat capacity
T = temperature change
Basic Principle in Calorimeter
Heat released
by a reaction
=
Heat absorbed
by surroundings
Surroundings may refer to
the:
i. Calorimeter itself or;
ii. The water and calorimeter
q
reaction
= mcT or CT

Example 1

In an experiment, 0.100 g of H
2
and excess of O
2
were compressed
into a 1.00 L bomb and placed into a calorimeter with heat capacity
of 9.08 x 10
4
J
0
C
1
. The initial temperature of the calorimeter was
25.000
0
C and finally it increased to 25.155
0
C. Calculate the
amount of heat released in the reaction to form H
2
O, expressed in kJ
per mole.

Solution
Heat released = Heat absorbed by the
calorimeter

q = CT
= (9.08 X 10
4
J
0
C
-1
) X (0.155
0
C)
= 1.41 X 10
4
J
= 14.1 kJ

H
2
(g) + O
2
(g) H
2
O(c)

mole of H
2
= 0.100
2.016
= 0.0496 mol

moles of H
2
O = mole of H
2

0.0496 mol of H
2
O released 14.1 kJ energy

1 mol H
2
O released = kJ

= 284 kJ
Heat of reaction, H = - 284 kJ mol
1

0496 . 0
1 . 14
Example 2

1. Calculate the amount of heat released in a reaction in
an aluminum calorimeter with a mass of 3087.0 g and
contains 1700.0 mL of water. The initial temperature of
the calorimeter is 25.0C and it increased to 27.8C.

Given:
Specific heat capacity of aluminum = 0.553Jg
-1
C
-1
Specific heat capacity of water = 4.18 Jg
-1
C
-1
Water density = 1.0 g mL-1
T = (27.8 -25.0 )C = 2.8C

Solution



q = m
w
c
w
T + m
c
c
c
T
= (1700.0 g)(4.18 Jg
-1
C
-1
)(2.8 C) +
(3087.0 g)(0.553 Jg-1 C-1)(2.8C)
= 24676.71 J
= 24.7 kJ

Heat absorbed by
water
Heat absorbed by
aluminium
calorimeter
Heat released

= +
HESSS LAW
Hess Law
Hesss Law states that when reactants are converted to
products, the change in enthalpy is the same whether the
reaction takes place in one step or in the series of steps.
The enthalpy change depends only on the nature of the
reactants and products and is independent of the route
taken.

A
1
H A
B
C

A
3
H

A
2
H

A + A = A
3 2 1
H H H
i. List all the thermochemical equations involved
Algebraic Method
1 -
-1560kJmol H
) ( 2
3
) ( 2
2
) ( 2
2
7
) ( 6 2
.

1 -
-286kJmol H
) ( 2 ) ( 2
2
1
) ( 2
.
1 -
393kJmol - H
) ( 2 ) ( 2 ) (
.
= A + +
= A +
= A +
g
O H
g
CO
g
O
g
H C iii
g
O H
g
O
g
H ii
g
CO
g
O
S
C i
Step 1
i. List all the thermochemical equations involved
Algebraic Method
1 -
-1560kJmol H
) ( 2
3
) ( 2
2
) ( 2
2
7
) ( 6 2
.

1 -
-286kJmol H
) ( 2 ) ( 2
2
1
) ( 2
.
1 -
393kJmol - H
) ( 2 ) ( 2 ) (
.
= A + +
= A +
= A +
g
O H
g
CO
g
O
g
H C iii
g
O H
g
O
g
H ii
g
CO
g
O
S
C i
Step 1
ii. Write the enthalpy of formation reaction for C
2
H
6
) ( 6 2
?
) ( 2
3
) ( g
H C
f
H
g
H
s
C
= A
+
iii. Add the given reactions so that the result is the desired
reaction.

-84kJ
3
H
2
H
1
H
f
H
84kJ -
) ( 6 2
?
) ( 2
3
) (
2
___ __________ __________ __________ __________ __________ __________
1560kJ
3
H
) ( 2 2
7
) ( 6 2 ) ( 2
3
2(g)
2CO (iii)
-286kJ 3
2
H
) ( 2
3
) ( 2 2
3
) ( 2
3 3 ) (
kJ -393 2
1
H
) ( 2
2
) ( 2
2
) (
2 2 ) (
=
A + A + A = A

= A
+
+ = A + +
= A +
= A +
g
H C
f
H
g
H
s
C
g
O
g
H C
g
O H reverse
g
O H
g
O
g
H ii
g
CO
g
O
S
C i
Energy Cycle Method
Draw the energy cycle and apply Hesss Law to calculate the
unknown value.

2 C

( s )

+

3 H
2


( g )
C
2
H
6

( g )
2 C O
2

( g )
+
3 H
2
O
( g )
2 O
2


( g )
3 / 2

O
2

( g )
H
H
H
H
7 / 2

O
2

( g )
O
O
O
O
f
1
2
3
=

2 ( - 3 9 3 )
=

3 ( - 2 8 6 )
=

-

( - 1 5 6 0 )
1 -
kJmol -84
1560 858 - -786

3
H + )

2
H 3( + )

1
H 2( =

f
H
=
+ =
A
Example 1
The thermochemical equation of combustion of carbon
monoxide is shown as below.
C
(s)
+ O
2(g)
CO
(g)
= ?

given :
C
(s)
+ O
2(g)
CO
2(g)
H= -394 kJ mol
-1
CO
(s)
+ O
2(g)
CO
2(g)
H= -283 kJ mol
-1
Calculate the enthalpy change of the combustion of carbon to
carbon monoxide.

A H

A H

A H
Example 2
Calculate the standard enthalpy of formation of methane if the
enthalpy of combustion of carbon, hydrogen and methane are
as follows:
H [C
(s)
] = -393 kJ mol
-1
H [H
2(s)
] = -293 kJ mol
-1
H [CH
4(s)
] = -753 kJ mol
-1

A
c
H

A
c
H

A
c
H
Example 3
Standard enthalpy of formation of ammonia, hydrogen
chloride and ammonium chloride is -46.1 kJ mol
-1
, -92.3 kJ
mol
-1
, 314.4 kJ mol
-1
respectively. Write the thermochemical
equation for the formation of each substance and calculate
the enthalpy change for the following reaction.
NH
3
(g) + HCl (g) NH
4
Cl(s)
Exercise
1.Calculate the enthalpy of formation of benzene
if :
H (CO
2(g)
) = -393.3 kJ mol
-1
H (H
2
O
(l)
) = -285.5 kJ mol
-1
H (C
6
H
6(l)
) = -3265.3 kJ mol
-1

A
f
H

A
f
H

A
f
H
Born-Haber
Cycle
Lattice Energy, AH
lattice

is the energy required to completely separate one mole of a
solid (ionic compound) into gaseous ions

e.g:
NaCl(s) Na
+
(g) + Cl
-
(g) AH
lattice
= +771 kJ mol
-1
(lattice dissociation)

Na
+
(g) + Cl
-
(g) NaCl(s) AH
lattice
= -771 kJ mol
-1
(lattice formation)
The magnitude of lattice energy increases as
the ionic charges increase
the ionic radii decrease

There is a strong attraction between small ions and
highly charged ions so the AH is more negative.

AH for MgO is more negative than AH for Na
2
O
because Mg
2+
is smaller in size and has bigger charge
than Na
+
, therefore
AH
lattice
(MgO) > AH
lattice
(Na
2
O)
Na
+
and Cl
-
ions in the solid crystal are separated from
each other and converted to the gaseous state (AH
lattice
)

The electrostatic forces between gaseous ions and polar
water molecules cause the ions to be surrounded by water
molecules (AH
hydr
)
AHsoln = AHlattice + AHhdyr
Hydration Process of Ionic Solid
Heat of Solution
Na
+
and Cl
-
ion in
the gaseous state
Na
+
and Cl
-
ion in
the solid state
Hydrated Na
+
and Cl
-
ion
Born-Haber Cycle

The process of ionic bond formation occurs in a few stages. At
each stage the enthalpy changes are considered.
The Born Haber cycle is often used to calculate the lattice
energy of an ionic compound.
In the Born-Haber cycle energy diagram, by convention,
positive values are denoted as going upwards, negative values
as going downwards.
Consider the enthalpy changes in the formation of sodium
chloride.


Example :

Given;
i. Enthalpy of formation NaCl = -411 kJmol
-1
ii. Enthalpy of sublimation of Na = +108 kJmol
-1
iii. First ionization energy of Na = +500 kJmol
-1
iv. Enthalpy of atomization of Cl = +122 kJmol
-1
v. Electron affinity of Cl = -364 kJmol
-1
vi. Lattice energy of NaCl = ?
(s) 2(g)
2
1
(s)
NaCl Cl Na
Example: A Born-Haber cycle for NaCl
Na(s) + Cl
2
(g)
Na(g)
+ Cl
2
(g)
NaCl(s)
energy
E=0
Na(g) + Cl(g)
Na
+
(g) + e + Cl(g)
Na
+
(g)
+ Cl
-
(g)
AH
aNa

AH
aCl

Ionisation
Energy of Na
Electron Affinity of Cl
Lattice energy
AH
f NaCl

From Hesss Law:
AH
f

NaCl
= AH
aNa
+ AH
aCl
+IE
Na
+
EA
Cl
+ Lattice Energy
-ve
+ve
Calculation:
| |
( ) | |
kJ 777 H
kJ 364 kJ 122 kJ 500 kJ 108 kJ 411 H
EA H IE H H H
H EA H IE H H
lattice
lattice
) Cl ( a S
0
f lattice
lattice ) Cl ( a S
0
f
= A
+ + + + = A
+ A + + A A = A
A + + A + + A = A
Exercise:
Construct a Born-Haber cycle to explain why ionic compound
NaCl
2
cannot form under standard conditions. Use the data
below:
i. Enthalpy of sublimation of sodium = +108 kJmol
-1
ii. First ionization energy of sodium = +500 kJmol
-1
iii. Second ionization energy of sodium = +4562 kJmol
-1
iv. Enthalpy of atomization of chlorine = +121kJmol
-1
v. Electron affinity of chlorine = -364 kJmol
-1
vi. Lattice energy of NaCl
2
= -2489 kJmol
-1