Chapter 4: Thermochemistry

4.1 Energy Changes in Chemical Reactions

1) Energy is released or absorbed during chemical reactions.

2) During chemical reactions, rearrangements of particles occur and this involves the breaking and
forming of bonds.

3) Heat energy is absorbed to break the bonds and energy is given out when bonds are formed.

4) Two types of reactions in this chapter:

a) Endothermic reaction – more energy is absorbed than given out. Reaction take in the heat
from surroundings. (Temperature of surrounding decrease)

b) Exothermic reaction – more energy is released than absorbed. Reaction release heat to
surroundings. (Temperature of surrounding increase)

5) The amount of heat given out or absorbed is called the heat of reaction, ∆H.

Exothermic Reaction
1) Reaction where heat energy is given out to the surroundings

(notes: surrounding = container, solvent, air, thermometer).

2) Energy content of the products is lower than

reactants.

3) Example of exothermic reactions:

a) Combustion of fuel

b) Burning of metal

c) Neutralisation

d) Rusting of iron

e) Reaction between metal ant acid

f) Reaction between carbonate and acid

g) Freezing / condensation (physical)

Endothermic reaction

1) Reaction where heat energy is taken in / absorbed

from its surrounding

2) Energy content of product is higher than reactants

3) Example of endothermic reaction

a) Thermal decomposition of nitrate salts /

carbonate salt.

b) Reaction between acid and hydrogen carbonates.

c) Photosynthesis

d) Melting / boiling

Exercise (1)
Draw the energy level diagram for the following reactions.

a) CH 4  20 2 
 CO 2  2 H 2 O , -1
∆H= -890 kJ mol

CH 3 COOH  KOH 
 CH 3 COOK  H 2 O -1
b) , ∆H= -55 kJ mol

CaCO3 
 CaO  CO2 -1
c) , ∆H= +570 kJ mol
Heat of Reactions

1) Heat of reaction is the heat change when number of moles of reactants as shown in the chemical
equation reacts in standard conditions to form products.
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(notes: standard conditions: T=25°C, P=1 atm / 101.3 kPa, M = 1.0 mol dm

2) For example, the reaction between hydrogen and oxygen as show below:
2H 2 ( g )  O 2 ( g ) 
 2 H 2 O() , ∆H= -572 kJ
a) -572 kJ is the heat of reaction. (-) sign shows that the reaction is exothermic.

b) 572 kJ of heat is released to the surroundings when 2 moles of hydrogen react with one
mole of the oxygen to form 2 moles of water.

c) If the quantity of reactants is reduced / increased to double, then the heat produced is also
reduced / increase to double as show below.

3) In general, there are four types of reactions is discussed in later on:

a) Heat of precipitation b) Heat of neutralisation

c) Heat of displacement d) Heat of combustion

Exercise (2)
a) Consider the equation below.

1 1
CH 4 ( g )  O 2 ( g ) 
 CO 2 (g)  2H 2 O()
2 2 , ∆H= -445 kJ.

How much heat is produced when 2 moles of methane are burnt in 5 moles of oxygen
 b) When sulphur burns in oxygen gas, sulphur dioxide gas is produced.

S( s)  O 2 ( g ) 
SO 2 ( g ) , ∆H= -297 kJ

Calculate the heat change when 20g of sulphur is burnt completely in excess oxygen.

[RAM: 0,16 ; S,32]

25
C 8 H18 ()  O 2 (g) 
 8 CO 2 (g)  9H 2 O()
c) 2 , ∆H= -5512 kJ

Calculate the mass of octane required for combustion to produce 1378 kJ of heat.

[RAM: H, 1 ; C, 12]

Determining the heart of reactions.

1) In general, ∆H = mC∆Ө, where

m = mass of solution (in g)
-1  -1
c = specific heat capacity of the solution (in Jg C )
∆Ө = temperature change in the solution (in °C)
 2) Consider the following example:
3 3
When 30 cm of potassium hydroxide solution is added to 25 cm of nitric acid, the results are as
follows.
Initial T of nitric acid = 28°C
Initial T of potassium hydroxide = 28°C
Highest T of mixture = 38°C
Calculate the heat change in this reaction.
-3 -1  -1
[Density of solution : 1 g cm . Specific heat capacity: 4.2 Jg C ]

4.2 Heat of Precipitations

1) Heat of precipitation – heat change when one mole of a precipitation is formed from its ions in
aqueous solution under standard conditions.

2) Some example of precipitation reactions:

Chemical equation Ionic equation

a) BaCl 2 (aq)  Na 2SO 4 (aq)

→ BaSO 4 (s)  2NaCl (aq)

AgNO 3 (aq)  HCl (aq)
b)
AgCl (s)  HNO3 (aq)
→
Pb(NO3 ) 2 (aq)  2KI (aq)
c)
PbI 2 (s)  2KNO3 (aq)
→

3) Example of experiment: To determine the heat of precipitate of silver chloride.

Exercise (3)
3 -3 3 -3
a) 50 cm of 0.5 mol dm silver nitrate solution at 29.5°C is added to 50 cm of 0.5 mol dm
potassium chloride solution which is at T=28.5°C. The mixture is stirred and the highest
temperature reached is 32.0°C.

Calculate the heat of precipitate of silver chloride. (Ans: -50.4)

-1  -1 -3
[Specific heat capacity: 4.2 Jg C , Density of solution= 1 g cm ]

b) The thermochemical equation for the precipitation of lead (11) sulphate is given below.
2
Pb 2 (aq)  SO 4 (aq) 
 PbSO 4 (s) , ∆H= -50.4 kJ
3 -3 3 -3
When 100 cm of 0.5 mol dm lead (11) nitrate solution is added to 100 cm of 0.5 mol dm
sodium sulphate solution, lead (11) sulphate is precipitated. What is the temperature change in
the reacting mixture? (Ans: 3°C)

3 -3 3 -3
c) When 50 cm of 2.0 mol dm lead (11) nitrate solution is added to 50 cm of 2.0 mol dm
potassium sulphate solution, there is an increase of 10°C in temperature.
What is the change in temperature if
3 -3 3 -3
i. 100 cm of 2.0 mol dm lead (11) nitrate solution is added to 100 cm of 2.0 mol dm
potassium sulphate solution?
3 -3 3 -3
ii. 50 cm of 1.0 mol dm lead (11) nitrate solution is added to 50 cm of 1.0 mol dm
potassium sulphate solution?
3 -3 3 -3
iii. 50 cm of 2.0 mol dm lead (11) nitrate solution is added to 50 cm of 1.0 mol dm
potassium sulphate solution?
3 -3 3
iv. 50 cm of 2.0 mol dm potassium sulphate solution is replaced by 50 cm of 2.0
mol dm -3 sodium sulphate solution?
4.3 Heat of Displacement

1) Heat of displacement – heat change when one mole of a metal is displaced from its salt solution
by a more electropositive metal under standard conditions.

2) The heat of displacement of metal id different when it is displaced by different metals in the
electrochemical series.

3) Example of experiment: To compare the heat of displacement of copper by zinc with the heat of
displacement of copper by magnesium.
Exercise (4)

a) In an experiment to determine the heat of displacement of iron by magnesium, excess

3 -3
magnesium powder is added to 50 cm of 0.2 mol dm iron (11) sulphate solution. The
results of the experiment are shown below:

Initial T of iron (11) sulphate solution = 30.5°C

Highest T of the mixture = 40.0°C
-1
Calculate the heat of displacement of iron. (Ans: -199.5 kJ mol )
-1  -1 -3
[Specific heat capacity: 4.2 Jg C , Density of solution= 1 g cm ]

3 -3
b) 1.4 g of iron powder is added to 200 cm of 0.5 mol dm copper (11) sulphate solution at
an initial temperature of 29.0 °C. The thermochemical equation is as follows.

Fe (s)  CuSO 4 (aq) 

 FeSO4 (aq)  Cu (s) , ∆H= -150 kJ

What is the highest temperature of the mixture? [Ans: 33.5 °C]

4.4 Heat of Neutralisation

1) Heat of neutralisation – heat change when one mole of water is formed from the reaction
between an acid and an alkali under the standard conditions.

Determining heat of neutralisation

1) The heat of neutralisation between strong acids and strong alkalis are always the same; that is
-1
-57.3 kJ mol .
Strong acid Strong alkalis Chemical equation

2) The value of the heat of neutralisation depends on:

a) The basicity of the acid (monoprotic, diprotic)

b) The strength of the acid

c) The strength of the alkalis

The basicity of the acid

Consider the following equation:

HCl (aq)  NaoH (aq) 

 NaCl (aq)  H 2 O () , ∆H= -57.3 kJ

H 2SO 4 (aq)  2NaoH (aq) 

 Na 2SO 4 (aq)  2H 2 O () , ∆H=
Explanation:
The strength of the acid

Consider the following equation:

CH 3 COOH (aq)  NaoH (aq) 

 CH 3 COONa (aq)  H 2 O ()
, ∆H= -55 kJ
Explanation:

The strength of the alkali

Consider the following equation:

HCl (aq)  NH 4 (aq)  OH- (aq) 


 NH 4 Cl (aq)  H 2 O () , ∆H= -51.5 kJ
Explanation:

Exercise (5)
3 -3
a) In an experiment to determine the heat of neutralisation, 50 cm of 1.0 mol dm
3 -3
sulphuric acid at 28.5 °C is added to 50 cm of 2.0 mol dm potassium hydroxide
solution which is also at 28.5 °C in a plastic cup with a cover. The mixture is then stirred
and the highest temperature reached is 41.5 °C. Calculate the heat of neutralisation. [Ans:
-1
-54.6 kJ mol ]
b) A student carried out an experiment to investigate the change in temperature during a
3
titration between sodium hydroxide solution and hydrochloric acid. 5.0 cm of n
mol dm -3 hydrochloric is added to 50.0 cm 3 of 2.0 mol dm -3 sodium hydroxide solution.
3
The mixture is stirred and the highest temperature is then recorded. Another 50 cm of
3
hydrochloric acid is quickly added and the process is repeated until a total of 50 cm of the
acid is added. The results of experiment are shown above.

a. What is the initial T of the sodium hydroxide solution and what is the highest T of the
mixture?

b. What is the volume of hydrochloric acid at the end point?

c. What is the value of n? (2.86)

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d. What is the heat of neutralisation? (-49.98 kJ mol )
4.5 Heat of combustion

1) Combustion is always an exothermic reaction

2) Heat of combustion – heat change when one mole of a substance is completely burnt in oxygen
under standard conditions.

3) Excess oxygen is necessary during combustion to make sure that the combustion is complete.

4) Value of heat of combustion for some fuels.

Heat of combustion
Fuel Use Equation during combustion -1
∆H ( kJ mol )
Heating,
Methane CH 4 (g)  20 2 (g) 
 CO2 (g)  2H 2 O () -890
cooking
1
Hydrogen Rocket fuel H 2 (g)  O 2 (g) 
 H 2 O () -286
2
Glucose Body fuel C 6 H12 O 6 (s)  60 2 (g) 
 6CO 2 (g)  6H 2 O () -2803
13
Butane Cooking C 4 H10 (g)  O 2 (g) 
 4CO 2 (g)  5H 2 O () -2877
2

5) The heat of combustion of a fuel can be determined accurately by using a bomb calorimeter

6) Example of experiment: To determine the heats of combustion for alcohols.

Heats of combustion of various alcohols.

1) One example of liquid fuel is alcohol. Different members of the alcohol family have differents
heats of combustion.

2) The heat of combustion of alcohol increase as the

a) Number of carbon atoms and hydrogen atoms per molecule increase.

Explanation:

b) Relative molecular mass increase

Exercise (6)

a) Complete combustion of 1 mole of butan -1-ol, C 4 H 9 OH produces 2678 kJ of heat.

Calculate the mass of butan -1-ol needed to burn completely in excess oxygen in order to
3
raise the temperature of 500 cm of water by 35 °C.
-1  -1 -3
[Specific heat capacity = 4.2 Jg C , density = 1 g cm ] (Ans : 2.03 g)
 b) An experiment is carried out to determine the heat of combustion of ethanol, C 2 H 5 OH .
The result of the experiment are shown below.
3
Volume of water used = 200 cm
Initial temperature of water = 29.0 °C
Highest temperature of water = 59.0 °C
Mass of spirit lamp and ethanol before combustion = 245.85 g
Mass of spirit lamp and ethanol after combustion = 244.95 g
Based on the result, calculate the heat of combustion of ethanol and construct the energy
level diagram for the complete combustion of ethanol.

Fuel value

1) Fuel value of fuel is the amount of heat energy given out when one gram of the fuel is
-1
completely burnt in excess of oxygen. Unit of fuel value is kJ g

Exercise (7)
-1
The heat of combustion of ethanol is -1376 kJ mol . Calculate the fuel value of ethanol.

[RAM = H, 1 ; C, 12 ; 0, 16]
-1
[Ans:29.9 kJ g ]