Chapter 3 Thermochemistry

3.1 Heat Change In Reactions

3.1 Heat Change In Reactions

Exothermic reactions

An exothermic reaction is a reaction that gives out

heat energy.

Heat given out from the reaction is transferred to the

surrounding, temperature of the surrounding rises.

Examples of exothermic reactions

Combustion of methane

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) + Heat

Reaction of magnesium with acid

Mg (s) + 2HCl (aq)  MgCl2 (aq) + H2 (g) + Heat

Neutralisation reaction

HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l) + Heat

Exothermic reaction

• Chemical energy in the reactants is

changed into heat energy
• Heat energy is transfer to surrounding
• Temperature of surrounding increases
• Reacting mixture and container become hot
3.1 Heat Change In Reactions

Endothermic reactions

An endothermic reaction is a reaction that absorbs

heat energy from the surrounding.

Thus the temperature of the surrounding decreases.

Examples of endothermic reactions

Thermal decomposition of lead(II) nitrate

xxxxxxxxx
2Pb(NO3)2(s)  2PbO(s) + 4NO2(g) + O2(g)

Thermal decomposition of Zinc carbonate.

xxxxxxxxx
ZnCO3 (s)  ZnO (s) + CO2 (g)

Dissolving ammonium salts in water

NH4Cl (s) + water  NH4Cl (aq)

Endothermic reaction

• Heat energy is absorbed from surrounding

• Heat energy is changed into chemical
energy
• Temperature of surrounding decreases
• Reacting mixture and container become
cold
ENERGY PROFILE DIAGRAM

In exothermic reactions, heat energy is

released to the surrounding.

Thus the products will have lower energy

content than the reactants.

The heat released causes a rise in

temperature of the surrounding.

Energy level diagram

In endothermic reactions, heat energy is
absorbed from the surrounding.
As the heat is absorbed from the
surrounding, the temperature of the
surrounding falls.
Thus the energy content of the products is
higher than the reactants.

Energy level diagram

Example:
Construct energy level diagram for exothermic and endothermic
reactions
1) Zn + CuSO4  ZnSO4 + Cu ΔH = -190KJ
2) 2HgO  2Hg + O2 ΔH = +182KJ
Application of exothermic and endothermic reactions
• Instant Cold Pack
Used to treat sports injuries. It have separate
compartments of water and solid ammonium nitrate,
NH4NO3 placed in a plastic bag. When the barrier between
the two is broken by squeezing the outer bag, the
ammonium nitrate dissolves in the water endothermically to
provide instant coldness. Heat is absorbed from the
surrounding such as the injured area of the athlete’s body.
3.2 Heat Of Reaction

Heat of precipitation

Is the heat energy changed when one mole of precipitate is

formed from its ions in an aqueous solution.

Energy change = mc θ

In which,
m = the mass of the aqueous reaction mixture
c = the specific heat capacity of the aqueous reaction mixture
θ= the change in temperature

Assumption:
1) The solution is dilute, it has the same density as water, 1 g cm-3
2) The solution has the same specific heat capacity as water 4.2 J g -1 OC-1
1) In an experiment, 50 cm3 of 1 mol dm-3 hydrochloric acid, HCl is added to
50 cm3 of 1 mol dm-3 of silver nitrate solution, AgNO3. The reacting mixture is
stirred and the highest temperature obtained is recorded. The results of the
experiment are shown below.

Initial temperature of hydrochloric acid, HCl = 28.0OC

Initial temperature of AgNO3 solution = 29.0OC
Highest temperature reached when two solution are mixed = 35.5OC

Calculate the heat of the precipitation of silver chloride.

[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of solution : 1 g cm-3 ]
2) The thermochemical equation for the precipitation of lead(II) sulphate is given below.
Pb2+ + SO42-  PbSO4 H = -50.4 kJ
When 100 cm3 of 0.5 mol dm-3 lead(II) nitrate solution is added to
100 cm3 of 0.5 mol dm-3 sodium sulphate solution, lead(II) sulphate is precipitated. What
is the temperature change in the reacting mixture in the experiment?
[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of solution : 1 g cm-3 ]
 Determining the heat of precipitation of silver chloride

1. 25 cm3 of 0.2 mol dm-3 silver nitrate solution is measured using a 50

ml measuring cylinder and then poured into a polystyrene cup.

2. The initial temperature of the solution is recorded using a

thermometer.
3. The measuring cylinder is washed and rinsed with the sodium
chloride solution.
4. Then 25 cm3 of 0.2 mol dm-3 sodium chloride solution is measured
using the measuring cylinder. Its initial temperature is recorded.
5. The sodium chloride solution is poured into the silver nitrate
solution.
6. The mixture is stirred using the thermometer and the maximum
temperature of the mixture is recorded.
 Determining the heat of precipitation of silver chloride

Initial temperature of AgNO3(aq) solution : 28.0 oC

Initial temperature of NaCl(aq) solution : 28.0 oC
Highest temperature of mixture : 32.0 oC
Heat Of Displacement

Heat of displacement

Is the heat energy changed when one mole of

metal is displaced from its salt solution by a
more electropositive metal.

Energy change = mc θ

Eg: Zn + CuSO4  ZnSO4 + Cu H = -210kJ

When one mole of Copper is displaced from its salt
solution by zinc, 210 kJ of heat is given out.
1) Excess aluminium powder is added to 50 cm3 of 0.2 mol dm-3 lead(II) nitrate
solution. The mixture is stirred using a thermometer. The results of the
experiment are shown below
Initial temperature of lead(II) nitrate solution = 30.5 OC
Highest temperature of the mixture = 40.0 OC
Calculate the heat of the displacement of lead by aluminium.
[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of solution : 1 g cm-3 ]
2) In an experiment, 1.4 g of zinc powder is added to 200 cm3 of 0.5 mol dm-3
copper(II) sulphate, CuSO4 solution at an initial temperature of 29.0 OC.
The thermochemical equation is as follow:
Zn + CuSO4 ZnSO4 + Cu H = -150 kJ mol-1
what is the highest temperature of the mixture?
[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of solution : 1 g cm-
3
,RAM : Zn = 56]
 Heat Of Displacement

Determining the heat of displacement of copper - Procedure

1. 50 cm3 of 0.2 mol dm-3 copper(II) sulphate solution is measured

using a measuring cylinder and then poured into a plastic cup.

2. The initial temperature of the copper(II) sulphate solution is taken.

3. 1 gram of zinc powder (excess) is then poured into the CuSO 4

solution.

4. The mixture is stirred and the maximum temperature is recorded.

 Determining the heat of displacement of copper

Initial temperature of CuSO4(aq) solution = 28.0 °C

Maximum temperature of mixture = 36.0 °C

Heat Of Neutralisation

Heat of neutralisation

Heat energy changed when one mole of water is formed from

the reaction between an acid and an alkali.

HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l) ΔH = -57.3 kJ mol-1

Energy change = mcθ

In which,
m = the mass of the aqueous reaction mixture
c = the specific heat capacity of the aqueous
reaction mixture
θ = the change in temperature
Heat Of Neutralization

The heat of neutralisation involving a strong acid and a strong alkali

• A strong acid and a strong alkali ionizes completely in water.

HCl(aq)  H+(aq) + Cl-(aq)
KOH(aq)  K+(aq) + OH-(aq)
• When these solutions are added together the only change that occurs
is the formation of water molecules.
K+OH-(aq) + H+Cl-(aq)  K+Cl-(aq) + H2O(l)

• Hence the heat of neutralisation is the heat released from the

formation of 1 mole of water and its value is approximately 57.3 kJ mol -
1
.
H+(aq) + OH-(aq)  H2O(l) H= -57.3 kJ mol-1
• Hence the heat of neutralization of any strong acid and strong alkali is
the same. For example
NaOH(aq) + HNO3(aq)  NaNO3(aq) + H2O(l) H= -57.3 kJ mol-1

• Heat of neutralization of strong diprotic acid and strong alkali is double

up which is approximately 114.6 kJ mol-1. For example
2NaOH(aq) + H2SO4(aq)  Na2SO4(aq) + 2H2O(l) H= -114.6 kJ mol-1
Heat Of Neutralization

The heat of neutralisation involving a weak acid and a weak alkali

However when weak acids or alkalis are involved, the heat of neutralisation is
lower than 57.3 kJ mol-1.

These weak acids or alkalis are partially dissociated in water.

Some energy is needed to break the -O-H bonds to release the hydrogen ions
or the hydroxide ions before they can react.

Thus the net heat change will be less than 57.3 kJ/mol. For example the heat
of neutralization of ethanoic acid and sodium hydroxide is only 54 kJ mol -1.

Heat energy is required to break

this O-H bond before the H+ can
react with the OH- to form water.
Thus the net heat change is less
than 57.3 kJ mol .
• When weak acid and strong alkali / strong acid and weak alkali
is used, the heat released will be lesser than 57.3 kJ for every
mole of water. This is because weak acid / weak alkali
dissociate partially into ions.

Strong acid + strong alkali Heat of

Strong acid + weak alkali / weak acid + strong alkali neutralisation
Weak acid + weak alkali decreases
In an experiment to determine the heat of neutralisation, 50 cm3 of 1.0 mol dm-3
sulphuric acid at 28.5 oC is added to 50 cm3 of 2.0 mol dm-3 potassium
hydroxide solution which is also at 28.5 oC in a plastic cup with a cover. The
mixture is then stirred and the highest temperature reached is 41.5 oC.
Calculate the heat of neutralisation.
[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of solution : 1 g cm-3 ]
The thermochemical equation for the reaction between nitric acid, HNO3 and
potassium hydroxide, KOH solution is as follow:
HNO3(aq) + KOH(aq)  KNO3(aq) + H2O(l) ΔH = -57.3 kJ mol-1
When 150 cm3 of 2.0 mol dm-3 nitric acid, HNO3 is added to 250 cm3 of 1.0 mol
dm-3 potassium hydroxide, KOH solution what is the change in temperature?
[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of solution : 1 g cm-3 ]
Heat Of Neutralization
Determining the heat of neutralisation between a strong acid and a
strong alkali

1. 50 cm3 of 2.0 mol dm-3 sodium hydroxide is measured using a 100

ml measuring cylinder and poured into a plastic cup.

2. The initial temperature of the sodium hydroxide is determined

using a thermometer.
3. The measuring cylinder is washed with water and then rinsed with
the hydrochloric acid solution.
4. 50 cm3 of 2.0 mol dm-3 hydrochloric acid is measured using a 100 ml
measuring cylinder. Its initial temperature is recorded.

5. The HCl solution is then poured into the NaOH solution.

6. The mixture is stirred and the maximum temperature attained is

recorded.
Heat Of Neutralization
Determining the heat of neutralisation between a strong acid and a strong alkali

Initial temperature of NaOH solution = 28.0 oC

Initial temperature of HCl solution = 28.0 oC
Maximum temperature of mixture = 41.4 oC
Heat Of Combustion

Heat of combustion

Is the heat changed when one mole of a

substance is burnt completely in an excess of
oxygen, O2.

Energy change = mcθ

In which,
m = the mass of the aqueous reaction mixture
c = the specific heat capacity of the aqueous
reaction mixture
θ = the change in temperature
An experiment is carried out to determine the heat of combustion of methanol,
CH3OH. The results of the experiment are shown below.

Based on the results, calculate the heat of combustion for methanol, CH30H
and hence construct the energy level diagram for the combustion of methanol,
CH3OH.
[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of water : 1 g cm-
3
,Relative atomic mass: H, 1; C, 12; 0, 16]
Complete combustion of 1 mole of propanol, C3H7OH produces 2016 kJ of
heat.
Calculate the mass of propanol, C3H7OH needed to burn completely in
oxygen in order to raise the temperature of 250 cm3 of water by 25°C.
[Specific heat capacity of solution : 4.2 J g-1 OC-1. Density of water:1 g cm-3 ]
 Chapter 4 Thermochemistry
Heat Of Combustion

Determining the heat of heat of combustion of ethanol

1. A spirit lamp containing ethanol is weighed accurately.

2. 100 cm3 of water is measured using a measuring cylinder and poured
into a metal can.
3. The metal can is placed on a clay-pipe triangle supported by a tripod
stand. The initial temperature of the water is recorded.
4. The spirit lamp is lit and placed below the metal can.

5. The can is heated until the temperature of the water rises by about 50 oC.

6. The flame is put out and the final temperature of the water recorded.

7. The spirit lamp is weighed again.

 Chapter 4 Thermochemistry
Determining the heat of combustion of ethanol

Initial temperature of water = 28.0oC

Final temperature of water = 80.0oC
Mass of spirit lamp before combustion = 105.25 g
Mass of spirit lamp after combustion = 105.98 g
Fuel value
• Different types of fuels have different heats of combustion. Heat of
combustion is expressed in kilojoule per mole. In our daily life, it is
not very practical to measure the quantity of a fuel in mole. We
measure the quantity of a fuel by it mass. Thus, fuel value or heat
value is one of the criteria used in the selection of a fuel.

• The fuel value of a fuel is the amount of heat energy given out
when one gram of the fuel is completely burnt in excess of
oxygen.

• The unit for fuel value is kJ g-1.

• Fuel value =

• Example: The heat of combustion of ethanol, C2H5OH is -1376 kJ mol-1.

What is its fuel value?
[Relative atomic mass: H, 1; C, 12; 0, 16]
 Chapter 4 Thermochemistry
Heat Of Combustion

Sources of non-renewable energy

Natural gas Petroleum Coal

Disadvantages

Burning of fossil fuels releases acidic gases like

sulphur dioxide and nitrogen dioxide which
dissolve in rain water to form acid rain. Acid rain
corrodes metals, concrete and destroys forests.

CO2 released during combustion causes green

house effect. The temperature of the earth
increases. Lakes will dry up and more
incidences of skin diseases occur.
 Chapter 4 Thermochemistry
Heat Of Combustion

Sources of renewable energy

Advantage
No adverse effects on
environment and humans.

Biofuel

Solar

Geothermal

Disadvantage Hydroelectric
• Energy generated from the sun and wind
depends on their intensity.
• At night, we cannot generate solar energy. Wind
• On a calm day, the wind generator cannot
generate electrical energy.