CHAPTER 4 THERMOCHEMISTRY

ENERGY CHANGES IN CHEMICAL REACTION

-

Thermochemistry is the study of changes in heat energy which take place during
chemical reaction.

Exothermic - A chemical reaction that GIVES OUT/ RELEASES heat to the surroundings.
Endothermic - A chemical reaction that ABSORBS heat from the surroundings.

Bond breaking requires less energy than bond formation. So, the energy released to form the
bond is higher / greater than the energy absorbed to break the bonds. Then, excess heat
energy is released to the surroundings. Thus, during the reaction temperature of the mixture
increases, The total energy of product is lower than the total energy of reactant.
EXAMPLE OF EXOTHERMIC REACTION
Most of the chemical reaction is exothermic such as
-

Acid Base Neutralisation

Combustion

Acid and metal

Bond breaking requires more energy than bond formation. So, the energy released to form the
bond is lower / less than the energy absorbed to break the bonds. Then, heat energy is
absorbed from the surroundings. Thus, during the reaction temperature of the mixture
decreases. The total energy of product is higher than the total energy of reactant.

Activation energy is the energy barrier that must be overcome by the colliding
particles of the reactants in order for reaction to occur / to become the products.
H = The change in the amount of heat in a chemical reaction is called the heat of
reaction.

Example of endothermic reaction

1. Salt dissolves in water

2. Salt crystallization

3. Thermal decomposition of salt

4. Reaction between acid with sodium hydrogen carbonate and potassium hydrogen
carbonate;

6. Photosynthesis
7. Process of melting, evaporation and boiling.

HEAT OF PRECIPITATION
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The heat of precipitation is the heat change when one mole of a precipitate is formed
from their ions in aqueous solution. Precipitate is insoluble salt .
The preparation of precipitate can only be double decomposition.

FORMULA TO DETERMINE THE HEAT CHANGE

Heat released/absorbed, H = mc
Symbol
m
c

[unit = J or kJ]
Description

mass of solution
specific heat capacity of solution
temperature change

Unit
1cm3 = 1 g
4.2 J g-1 oC-1
o
C

Example 1: Precipitation for lead(II) sulphate

Chemical equation;
H = -50 kJmol-1

Pb(NO3)2 + K2SO4 PbSO4 + 2KNO3

Ionic equation;
Pb2+ + SO42- PbSO4

H = -50 kJmol-1

Energy level diagram

Energy

Pb2+ + SO42 H = - 50 kJmol-1

PbSO4

50 kJ heat released when 1 mol of lead(II) ions react with 1 mol of sulphate ions to form 1
mol precipitate of lead(II) sulphate.
The heat of precipitation for PbSO4 = 50 kJmol-1

Example
When 50 cm3 calcium nitrate solution, Ca(NO3)2 2 mol dm-3 is added to 50 cm3 sodium
carbonate solution, Na2CO3 2.0 mol dm-3, precipitate of calcium carbonate, CaCO3 is
produce. Temperature of the mixture solution decrease 3.0 oC. Calculate the heat of
precipitation of calcium carbonate.
[Specific heat capacity of solution: 4.2 J g-1 oC-1, Density of solution: 1 g cm-3]
Chemical equation;
Ca(NO3)2 + Na2CO3 CaCO3 + 2NaNO3
Ionic equation:
Ca2+ + CO3 CaCO3

Step 1: Calculate the number of mole of precipitate formed

MV
1000

No. of mol Ca(NO3)2 =

No. of mol Na2CO3

MV
1000

2 X 50
1000

2 X 50
= 1000

= 0.1 Mol

= 0.1 Mol

1 mol Ca2+ react with 1 mol CO32- 1 mol calcium carbonate

Therefore;
0.1 mol Ca2+ react with 0.1 mol CO32- 0.1 mol CaCO3
Thus;
No. of mol CaCO3 = 0.1 mol

Step 2 : Calculate the total heat absorb in exp.

Total volume of the mixture = 50 cm3 Ca(NO3)2 + 50 cm3 Na2CO3
= 100 cm3
Mass of solution

= 100 g

Temperature change

= 3 oC

H = mc
= 100 x 4.2 x 3
= 1260 J
Therefore, heat given out during the experiment is 1.26 kJ

Step 3 : Calculate the heat of precipitation

0.1 mol CaCO3 absorb at 1260 J of heat.
Therefore;
1 mol CaCO3 absorb heat

1260
0.1

J mol-1

12600 J mol-1

12.6 kJ mol-1

Thus
The heat of precipitation CaCO3, H = + 12.6 kJ mol-1

HEAT OF NEUTRALISATION
The heat of neutralisation is the heat change when one mole of water is formed from
the reaction between an acid and an alkali.

Ionic equation: H+ (aq) + OH- (aq) H2O (l)

Heat of neutralisation can be divided into two types;

i.

Reaction between strong acid with strong alkali.

ii.

Reaction between weak acid with weak alkali.

HEAT OF NEUTRALISATION BETWEEN STRONG ACID WITH STRONG

ALKALI
Example: HCl + NaOH NaCl + H2O H = -57.3 kJ mol-1
In neutralisation reaction between strong acid and strong alkali, the heat of neutralisation is
-57.3 kJmol-1
CH3COOH + NaOH CH3COONa + H2O

H = -55 kJ mol-1

In neutralization between weak acid and strong alkali, heat of neutralization is less than -57.3
kJmol-1.
HEAT OF COMBUSTION
The heat of combustion is the heat change when 1 mol of substance is completely burnt
in oxygen under standard conditions.
HEAT OF COMBUSTION OF VARIOUS ALCOHOLS

Name
Methanol
Ethanol
Propan-1-ol
Butan-1-ol

Molecular
formula
(CnH2n+1OH)
CH3OH
C2H5OH
C3H7OH
C4H9OH

No. of carbon
atom per
alcohol
molecule
1
2
3
4

Mass of
molecular
relative

Heat
combustion
H (kJ mol-1)

32
46
60
74

-725
-1376
-2015
-2676

If the number of carbon atom per molecule of alcohol is higher, the heat of
combustion also increases.

The difference in heat of combustion between alcohol member is almost the same
because each alcohol member difference is in one group of CH2

Example :

The heat from combustion of 0.28 g octane, C8H18 increasing temperature of 200 cm3 water
from 30 oC to 46 oC. Based on this information,
[ Ar: H, 1; C, 12; O, 16; 1 mole gas is occupy 24 dm3]
i.
ii.
iii.
iv.

calculate the heat of combustion for octane

value of fuel for octane
volume of oxygen that need
mass of water produce

Solution
Chemical equation;
C8H18 +

25
2

O2 (g) 8CO2 (g) +

9H2O (ce)

Calculate no. of mol of fuel,

mass
molar mass

No. of mol for octane =

0.28
114

Calculate the heat changes/total heat release in this experiment,

Temperature changes = (highest temp initial temp) oC
= ( 46 30) oC
= 16 oC
Heat release

= mc

(exothermic react.)

= 200 x 4.2 x 16 J
= 13440 J
= 13.44 kJ

Calculate the heat of combustion

Combustion 0.0025 of mol of octane releasing 13.44 kJ of heat.

Therefore;
Combustion of 1 mol octane releases;

= 0.0025 mol

13.44
0.0025

= 5376

kJ mol-1

kJ mol-1

Thus;
= - 5376 kJ mol-1

Heat of combustion for octane

= - 5376 kJ mol-1

Calculate the fuel value of octane

Mr octane, C8H18 = (8 x 12) + 18 =

114 gmol-1

Therefore;
1 mole of octane, C8H18

= 114 g

Thus;
Fuel value of octane =

Heat of combusti on of octane

molar mass

5376
114

kJ g-1

47.15 kJ g-1

Calculate the volume of oxygen,

1 mol octane

25
2

0.0025 mol octane need

mol oxygen to react completely

25
2

x 0.0025 mol oxygen;

= 0.0312 mol oxygen

The number of O2 used in the reaction = 0.0312 mol oxygen

= 0.0312 x 24 dm3

The volume of oxygen needed

= 0.7488 dm3
= 748.8

cm3

Calculate the mass of water produce

1 mole of octane react completely to produce 9 mole of water
0.0025 mol octane produce 0.0025 x 9 mol water;
= 0.0225 mol water
The number of mole of water = 0.0225 mol
Thus;
No. of mol for water
Mass of water

mass of water
Molar Mass

= 0.0225 x 18 g
= 0.405 g