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 m2 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
H = -ve
products
reaction pathway

Energy profile diagram for exothermic reaction

Endothermic Reactions

Enthalpy of products > enthalpy of reactants, H is

positive

Energy is absorbed by the system from the surrounding

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 : H2O(s)

H2O(l)

H = +6.01 kJ

1 mole of H2O(l) is formed from 1 mole of H2O(s) at 0C,

H = +6.01 kJ

However, when 1 mole of H2O(s) is formed from 1 mole of

H2O(l), the magnitude of H remains the same with the
opposite sign of it.
H2O(l) H2O(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, Hf

The change of heat when 1 mole of a compound is

formed from its elements at their standard states.
H2 (g) + O2(g) H2O (l)

Hf = 286 kJ mol1

The standard enthalpy of formation of any element in

its most stable state form is ZERO.
H (O2 ) = 0
H (Cl2) = 0

Enthalpy of Combustion, Hc

The heat released when 1 mole of substance is

burned completely in excess oxygen.

C(s) + O2(g) CO2(g)

Hc = 393 kJ mol1

Enthalpy of Atomisation, Ha

The heat change when 1 mole of gaseous atoms is formed

from its element

Ha is always positive because it involves only breaking of

bonds
e.g:

Na(s)
Cl2(g)

Na(g)
Cl(g)

Ha = +109 kJ mol-1
Ha = +123 kJ mol-1

Enthalpy of Neutralization, Hn

The heat change when 1 mole of water, H2O is formed from the
neutralization of acid and base .

HCl(aq)+ NaOH(aq) NaCl(aq) +H2O(aq)

Hn = 58 kJ mol1

Enthalpy of Hydration, Hhyd

The heat change when 1 mole of gaseous ions is

hydrated in water.
e.g:
Na+(g) Na+(aq) Hhyd = 406 kJ mol-1
Cl-(g)

Cl-(aq)

Hhyd = 363 kJ mol-1

Enthalpy of Solution, Hsoln

The heat change when 1 mole of a substance is
dissolves in water.
e.g:
KCl(s) K+(aq) + Cl(aq) Hsoln = +690 kJ mol-1

Enthalpy of Sublimation, Hsubl

The heat change when one mole of a substance
sublimes (solid into gas).
H subl

I2 (s)

I2(g)

Hsubl =

+106 kJ mol1

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

Simple 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

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 1C1).
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 (JC1)

Heat released by
substance

Heat absorbed
by calorimeter

q = mcT
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
qreaction= mcT or CT

Example 1
In an experiment, 0.100 g of H2 and excess of O2 were compressed
into a 1.00 L bomb and placed into a calorimeter with heat capacity
of 9.08 x 104 J0C1. The initial temperature of the calorimeter was
25.0000C and finally it increased to 25.155 0C. Calculate the
amount of heat released in the reaction to form H2O, expressed in kJ
per mole.

Solution
Heat released = Heat absorbed by the
calorimeter
q

= CT
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ
H2(g) + O2(g) H2O(c)

mole of H2 = 0.100
2.016
= 0.0496 mol

moles of H2O

mole of H2

0.0496 mol of H2O released 14.1 kJ energy

1 mol H2O released

14.1
= 0.0496

Heat of reaction, H

= 284 kJ
= - 284 kJ mol1

kJ

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
Heat released

Heat absorbed by
aluminium
calorimeter

q = mwcwT + mcccT
= (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

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.
H1

A
H 2

H 3

H1 H2 H3

Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C

O
CO
(S)
2( g )
2( g )

1 O
H O
2
2( g )
2( g )
2 ( g)
iii .C H
7 O
2CO
3H O
2
2 6( g )
2( g )
2( g )
2 ( g)
ii.H

H - 393kJmol- 1
H -286kJmol- 1
H -1560kJmol

-1

Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C

O
CO
(S)
2( g )
2( g )

1 O
H O
2
2( g )
2( g )
2 ( g)
iii .C H
7 O
2CO
3H O
2
2 6( g )
2( g )
2( g )
2 ( g)
ii.H

H - 393kJmol- 1
H -286kJmol- 1
H -1560kJmol

-1

ii. Write the enthalpy of formation reaction for C2H6

H ?
f
C 3H
C H
( s)
2( g )
2 6( g )

iii. Add the given reactions so that the result is the desired
reaction.
(i ) 2

2C( S ) 2O2( g ) 2CO2( g )

H1 2 -393 kJ

(ii ) 3

3 H 2( g ) 3 O2( g ) 3 H 2O( g )
2

H 2 3 -286kJ

reverse (iii) 2CO 2(g) 3 H 2O( g ) C 2 H 6( g ) 7 O2( g ) H3 1560kJ

2
_______________________________________________________________
H f ?
2C( s ) 3 H 2( g ) C 2 H 6( g )
- 84kJ
H f H1 H 2 H3
-84kJ

Energy Cycle Method

Draw the energy cycle and apply Hesss Law to calculate the
unknown value.

HOf
2C (s )

3H2 (g)

C2H6 (g)

H O2 = 3(-286)
HO1

2O2 (g)

3/2 O2 (g)

= 2(-393)
2CO2 (g) + 3H2O (g)

7/2 O2 (g)
HO3 = - (-1560)

H f = 2( H1 ) + 3( H 2 ) + H3
-786 - 858 1560
1
-84 kJmol

Example 1
The thermochemical equation of combustion of carbon
monoxide is shown as below.
C(s) + O2(g) CO(g)
H = ?
given :
H
C(s) + O2(g) CO2(g)
H= -394 kJ mol-1

H
CO(s) + O2(g) CO2(g)
H= -283 kJ mol-1
Calculate the enthalpy change of the combustion of carbon to
carbon monoxide.

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

H [H2(s)]

= -293 kJ mol-1

H [CH4(s)]

= -753 kJ mol-1

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.
NH3(g) + HCl (g) NH4Cl(s)

Exercise
1.Calculate the enthalpy of formation of benzene
if :
H (CO2(g) ) = -393.3 kJ mol-1
H (H2O(l) ) = -285.5 kJ mol-1
H f H (C6H6(l) ) = -3265.3 kJ mol-1
H f
H f

Born-Haber
Cycle

Lattice Energy, Hlattice

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)
(lattice dissociation)

Na+(g) + Cl-(g)

Hlattice = +771 kJ mol-1

NaCl(s) Hlattice = -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 H is more negative.

H for MgO is more negative than H for Na2O

because Mg2+ is smaller in size and has bigger charge
than Na+, therefore
Hlattice (MgO) > Hlattice (Na2O)

Hydration Process of Ionic Solid

Na+ and Cl- ions in the solid crystal are separated from
each other and converted to the gaseous state (Hlattice)

The electrostatic forces between gaseous ions and polar

water molecules cause the ions to be surrounded by water
molecules (Hhydr)

Hsoln = Hlattice + Hhdyr

Na+ and Cl- ion in

the gaseous state

ic
t
t
La

r
e
n
E
e

He
at
of
Hy
d ra
tio

gy

Heat of Solution
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 :
Na(s)

i.
ii.
iii.
iv.
v.
vi.

1
2

Cl2(g) NaCl(s)

Given;
Enthalpy of formation NaCl
Enthalpy of sublimation of Na
First ionization energy of Na
Enthalpy of atomization of Cl
Electron affinity of Cl
Lattice energy of NaCl

=
=
=
=
=
=

-411 kJmol-1
+108 kJmol-1
+500 kJmol-1
+122 kJmol-1
-364 kJmol-1
?

Example: A Born-Haber cycle for NaCl

energy
Na+(g) + e

+ Cl(g)

Ionisation
Electron Affinity of
Energy of
Cl
Na
Na+(g) + Cl- (g)
Na(g) + Cl(g)

HaCl
Na(g) +
+ve
Cl2(g)

Lattice energy

HaNa

E=
0

-ve

Na(s) + Cl2(g)

From Hesss Law:

Hf

Hf NaCl
NaCl(s)

NaCl

= HaNa + HaCl +IENa +

EACl + Lattice Energy

Calculation:
H0f HS IE Ha(Cl) EA Hlattice
Hlattice H0f HS IE Ha(Cl) EA
Hlattice 411
kJ 108kJ 500kJ 122kJ 364kJ
Hlattice 777kJ

Exercise:

i.
ii.
iii.
iv.
v.
vi.

Construct a Born-Haber cycle to explain why ionic compound

NaCl2 cannot form under standard conditions. Use the data
below:
Enthalpy of sublimation of sodium
=
+108 kJmol-1
First ionization energy of sodium
=
+500 kJmol-1
Second ionization energy of sodium
=
+4562 kJmol-1
Enthalpy of atomization of chlorine
=
+121kJmol-1
Electron affinity of chlorine
=
-364 kJmol-1
Lattice energy of NaCl2
=
-2489 kJmol-1