THERMOCHEMISTRY

1 Exothermic reaction
- Is a chemical reaction that gives out heat to the surroundings.
- Chemical energy is converted to heat energy.
- The surroundings gain heat and as a result, the temperature of the surroundings
increases.
- Others examples of exothermic reactions are shown below:
(a) Respiration
(b) Rusting of iron
(c) Reaction between Group 1 elements with water
Example: 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
(d) Neutralisation reaction between acid and alkali
Example: HCl(aq) + NaCl(aq) NaCl(aq) + H2O(l)
(e) Reaction of a dilute acid with metal carbonate
Example: 2HCl(aq) + CaCO3(aq) CaCl(aq) + H2O(l) + CO2(g)
(g) Displacement reaction of metals
Example: Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
- Some physical processes also release heat as shown below:
(a) Dissolving of alkali in water
Example: NaOH(s) Na+(aq) + OH-(aq)
(b) Dilution of concentrated acids
Example: H2SO4(l) 2H+(aq) + SO42-(aq)
(c) Condensation and freezing process

2 Endothermic reaction
- Is a chemical reaction that absorbs heat from the surroundings.
- Heat energy is converted to chemical energy and store it in the products.
- The surroundings lose heat energy and as a result the temperature of the surrounding
decreases.
- Others examples of endothermic reactions are shown below:
(a) Photosynthesis
(b) Reaction between sodium hydrogen carbonate and dilute acid
Example: NaHCO3(s) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g)
(c) Decomposition of carbonate salts
Example: PbCO3(s) PbO(s) + CO2(g)
(d) Decomposition of nitrate salts
Example: 2Zn(NO3)(s) 2ZnO(s) + 4NO2(g) + O2(g)
(e) Decomposition of hydrated salt, such as hydrated copper(II) sulphate
Example: CuSO4.5H2O(s) CuSO4(s) + 5H2O(l)
- Some physicals processes also absorb heat as shown below:
(a) Dissolving of ammonium salts such as ammonium chloride, ammonium
nitrate and ammonium sulphate in water
Example: NH4Cl(s) NH+(aq) + Cl-(aq)
(b) Melting and boiling process
3 Heat of Reaction and Energy Level Diagrams
- The total energy stored in a chemical substance is known as energy content.
- It is impossible to measure the energy content for a particular substance but the
changes in energy content that occurs when the reactants are converted to the
products can be determined and is given the symbol, ΔH.

The changes in energy content = The amount of heat energy given

out/absorbed during chemical reaction

- ΔH heat of reaction (the changes in energy)

Δ(delta) means “change of” and H is the “heat content” or enthalpy

of the sytem

- The amount of heat change in a specific reaction, however, depends on how much
of each reactant is present.
- The more reactants are used, the more heat energy is given out/absorbed in the
reaction. Thus, it is necessary to clearly states the amounts of reactants involved for
the definition of the heat of reaction.

The heat of reaction (ΔH): is defined as the heat change which occurs when
the numbers of moles of reactants indicated by the equation react together.

- For a general reaction, A + B C + D

H reactants H products

ΔH = (Energy content of products) – (Energy content of reactants)

ΔH = H products – H reactants
The unit of ΔH is kilojoules, kJ

 When an exothermic reaction occurs, heat energy is released to the surroundings.

Thus, the total energy content of the products is less than that of the reactants.

H products < H reactants

ΔH = H products – H reactants
= negative value
 ΔH of an exothermic reaction is given a negative sign.
For example, when 1 mole of sodium hydroxide solution reacts with 1 mole of
hydrochloric acid, the reaction releases 57.3 kJ heat energy.
Thus, ΔH = -57.3 kJ
 A chemical equation together with ΔH is called the thermochemical equation.
For example, NaOH(aq) + HCl(l) NaCl(aq) + H2O(l)
ΔH = -57.3 kJ
 The heat energy changed in an exothermic reaction can be shown on an energy level
diagrams.
Energy

Reactants

ΔH = negative

Products

Figure 1: The energy level diagram for an exothermic reaction

 For example, the energy level for the reaction between sodium hydroxide solution
and hydrochloric acid is shown in Figure 2.

Energy

NaOH(aq) + HCl(aq)

ΔH = -57.3 kJ

NaCl(aq) + H2O(l)

Figure 2: Energy level diagram for the reaction between sodium hydroxide
solution and hydrochloric acid

 When an endothermic reaction occurs, heat energy is absorbed from the surroundings.
Thus, the total energy content of the products is higher than the reactants.

H products > H reactants

ΔH = H products – H reactants
= positive value
  ΔH of an exothermic reaction is given a positive sign.
For example, when 1 mole of sodium hydrogen carbonate solution reacts with 1 mole
of hydrochloric acid, the reaction absorbs 11.8 kJ heat energy.
Thus, ΔH = +11.8 kJ
 The thermochemical equation for this reaction is:
NaHCO3(aq) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g)
ΔH = +11.8 kJ
 The heat energy changes in an endothermic reaction can be shown on an energy level
diagram.

Energy

Products

ΔH = positive

Reactants

Figure 3: The energy level diagram for an endothermic reaction

 For example, the energy level for the reaction between sodium hydrogen carbonate
solution and hydrochloric acid is shown in Figure 4.

Energy

NaCl(aq) + H2O(l) + CO2(g)

ΔH = +11.8 kJ

NaHCO3(aq) + HCl(aq)

Figure 4: Energy level diagram for the reaction between sodium hydrogen
carbonate solution and hydrochloric acid

4 Types of heat of reactions

(a) Heat of precipitation

(b) Heat of displacement Defined as the heat change when 1 mole of reactant reacts or
(c) Heat of neutralization one mole of product is formed. Therefore, the unit of ΔH for
these reactions is kJmol-1.
(d) Heat of combustion
 Heat of precipitation
- Precipitation reaction occurs when we add two solutions together to form a
precipitate.
- For example, when lead(II) nitrate solution and potassium sulphate solution are added
together, a white precipitate, lead(II) sulphate is formed.
- The heat of precipitate is the heat change when 1 mole of a precipitate is
formed from their ions in aqueous solution.
o For example, 50.4 kJ of heat energy is given out when 1 mole of lead(II)
sulphate, PbSO4 is formed. Thus, the heat of precipitation of lead(II) sulphate,
PbSO4 is -50.4 kJ mol-1.
o Thermochemical equation:
Pb2+(aq) + SO42-(aq) PbSO4(s)
ΔH = -50.4 kJ mol-1
o The energy level diagram is shown below:

Energy

Pb2+(aq) + SO42-(aq)

ΔH = -50.4 kJ mol-1

PbSO4(s)

Figure 5: Energy level diagram for the precipitation of lead(II) sulphate

Solve numerical problems related to heat of precipitation

- In a chemical reaction involving solutions, the heat change of the solution can be
determined by 2 method:
(a) Using the formula mcθ if the value of m (mass or volume of solution) and the
values of θ (change in temperature) are known.
Thus, the heat change of a solution = mcθ

(b) Using the heat of reaction, ΔH if the value of ΔH and the number of moles (n) of
the reactant are given.
Thus, the heat change in a reaction = n x ΔH kJ

For example, Pb2+(aq) + SO42-(aq) PbSO4(s) ΔH = -42 kJ mol-1

When 2 moles of PbSO4 formed, the heat given out = 2 x 42 kJ = 84 kJ
When 0.5 moles of PbSO4 formed, the heat given out = 0.5 x 42 kJ = 21 kJ
- Since the heat change calculated by the 2 methods should be equal by theory, then
mcθ = n x ΔH x 1000 Joule
 Heat of displacement
- Displacement reaction occurs when a more electropositive metal displace a less
electropositive metal from its salt solution.
- For example, when zinc powder is added into lead(II) nitrate solution, lead is
displaced and zinc nitrate solution is formed.
- The heat of displacement is the heat change when one mole of a metal is
displaced from its salt solution by a more electropositive metal.
o For example, 112 kJ of heat energy is given out when one mole of lead, Pb is
displaced from lead(II) nitrate, Pb(NO3) solution by zinc. Thus, the heat of
displacement of lead is -112 kJ mol-1.
o Thermochemical equation:
Zn(s) + Pb2+(aq) Pb(s) + Zn2+(aq)
ΔH = -112 kJ mol-1
o The energy level diagram is shown below:
Energy

Zn(s) + Pb2+(aq)

ΔH = -112 kJ mol-1

Pb(s) + Zn2+(aq)

Figure 6: Energy level diagram for the displacement of lead by zinc

Solve numerical problems related to heat of displacement

Example 1:
Excess zinc powder is added to 50 cm3 of 0.2 mol dm-3 copper(II) sulphate, CuSO4 solution in a polystyrene
cup. The results of the experiment are shown below:
Initial temperature of copper(II) sulphate,CuSO4 = 27.0 °C
Highest temperature of the mixture = 37.0 °C
(a) Write the ionic equation for the reaction.
(b) Calculate the mass of zinc which reacts with 50 cm3 of 0.2 mol dm-3 copper(II) sulphate, CuSO4
solution.
(c) Calculate the heat of displacement of copper by zinc
[molar mass of Zn = 65 g mol-1; Specific heat capacity of solution = 4.2 J g-1°C-1; density of solution = 1 g
cm-3]
Example 2:
The thermochemical equation for the reaction between magnesium and iron(II) sulphate, FeSO 4 solution is
as follow: Mg(s) + Fe2+ (aq) Mg2+(aq) + Fe(s) ΔH = -202 kJ mol-1
In a experiment, excess magnesium powder is added to 100 cm3 of iron(II) sulphate, FeSO4 solution at 29
°C in a polystyrene cup. It is found that 1.12 g of iron is displaced. Calculate
(a) The highest temperature reached
(b) The concentration of the iron(II) solution.
[Specific heat capacity of solution = 4.2 J g-1°C-1; density of solution = 1 g cm-3; molar mass of Fe = 56 g
mol-1]
 Heat of neutralization
- Neutralization is a reaction between and acid and base or alkali to produce salt and
water only.
- The chemical equations below represent some examples of neutralization reactions
(a) HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
(b) HNO3 + KOH(aq) KNO3(aq) + H2O(l)
(c) H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)
- In a neutralization between an acid and an alkali, the actual reaction that occurred is
between hydrogen ions, H+ from the acid and hydroxide ions, OH- from the alkali to
produce molecules of water, H2O.
- Ionic equation of neutralization: H+(aq) + OH-(aq) H2O(l)
- The heat of neutralization is the heat change when 1 mole of water is formed
from the reaction between an acid and an alkali.
- Neutralization is an exothermic reaction.
- The heat of neutralization between a strong acid and a strong alkali is -57.3 kJ mol-1.
All the neutralization reactions between a strong acid and a strong alkali can be
represented by the thermochemical equation below:
H+(aq) + OH-(aq) H2O(l)
ΔH = 57.3 kJ mol-1
- The energy level diagram is shown below:

Energy

H+(aq) + OH-(aq)

ΔH = -57.3 kJ mol-1

H2O(l)

Figure 7: Energy level diagram for the neutralization reaction

The heat of neutralization between a diprotic acid and a strong alkali

1) HCl and HNO3 are monoprotic acids. 1 mole of HCl or HNO3 produces 1 mole of
hydrogen ions, H+ when ionized in water.

HCl(aq) H+(aq) + Cl-(aq)

HNO3(aq) H+(aq) + NO3-(aq)

2) Therefore, the heat of neutralization between a strong monoprotic acid and a strong
alkali is always equal to -57.3 kJ mol-1. For example,

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

ΔH = -57.3 kJ mol-
1
3) H2SO4 is a diprotic acid. 1 mole of sulphuric acid produces 2 moles of hydrogen ions,
H+ when ionized in water.

H2SO4(aq) 2H+ (aq) + SO42-(aq)

The concentration of hydrogen ions, H+ of sulphuric acid is always double the

concentration of H+ of the HCl and HNO3 of the same concentration.
4) When 1 mole of H2SO4 is neutralized by NaOH solution, 114.6 kJ heat energy is
given out because there are 2 moles of water formed.

H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)

ΔH = -114.6 kJ mol-1
or 2H+(aq) + 2OH-(aq) 2H2O(l)
ΔH = -114.6 kJ mol-1

5) However, the heat given out by 1 mole of water formed is still 57.3 kJ as shown
below:
2 moles of H2O formed give out 114.6 kJ
114.6 𝑘𝐽
1 mole of H2O formed gives out = 57.3 𝑘𝐽
2
Therefore, the thermochemical equation can be written as:

H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)

ΔH = -57.3 kJ mol-1

The heat of neutralization involve weak acids and weak alkalis

1) The heat of neutralization between a weak acid and a strong alkali is less than -57.3
kJ mol-1.
2) For example, the heat of neutralization between ethanoic acid, CH3COOH and
sodium hydroxide, NaOH solution is -55 kJ mol-1.
CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(l)
ΔH = -55 kJ mol-1
3) This is because most of the weak acids exist as molecules when they dissolve in
water. They only ionize partially in water to produce low concentration of H+.
4) Some of the heat given out during neutralization reaction is used to ionize the acid
molecules completely to produce H+. As the result, the value of ΔH is always less
than -57.3 kJ mol-1.
5) The heat of neutralization between a weak acid and a weak alkali is even much lower
because more energy is required to ionize both the weak acid and weak alkali
molecules.
6) For example, the heat of neutralization between ethanoic acid and ammonia solution
is -51.5 kJ mol-1.
Solve problems involving to heat of neutralization
Example 1:
40 cm3 of 0.5 mol dm-3 sodium hydroxide, NaOH solution is added to 25 cm3 of 1.0 mol dm-3 nitric acid,
HNO3 in a plastic cup. The results are shown below:
Initial temperature of NaOH solution = 28.0 °C
Initial temperature of HNO3 = 28.0 °C
Highest temperature of the mixture = 32.0 °C
(a) Which solution is in excess?
(b) Calculate the heat of neutralization between NaOH solution and HNO3?
[Specific heat capacity of solution = 4.2 J g-1°C-1; density of solution = 1 g cm-3]
Example 2:
When 50 cm3 of 1.0 mol dm-3 sodium hydroxide, NaOH is added to 50 cm3 of 1.0 mol dm-3 nitric acid,
HNO3 the temperature rise of the mixture is 7 °C. Predict the temperature rise in each of the following cases.
(a) 100 cm3 of 1.0 mol dm-3 sodium hydroxide, NaOH is added to 100 cm3 of 1.0 mol dm-3 nitric acid,
HNO3
(b) 50 cm3 of 2.0 mol dm-3 sodium hydroxide, NaOH is added to 50 cm3 of 2.0 mol dm-3 nitric acid, HNO3

 Heat of combustion
- Heat change when 1 mole of a substance is completely burnt in O2 under standard
condition.
At standard condition, the temperature is 25 °C and
atmospheric pressure is 1 atm

- The combustion of a substance is an exothermic reaction which is heat is given out to

the surroundings.
- For example, 394 kJ energy is given out when 1 mole of carbon burnt completely in
excess of O2. Thus, the heat of combustion of carbon is -394 kJ mol-1.
- The thermochemical equation of the combustion of carbon is shown below:
C(s) + O2(g) CO2(g) ΔH = -394 kJ mol-1

- Alcohol is a good fuel. The complete combustion of alcohol produces CO2, H2O and
releases a lot of heat.
- For example, the heat of combustion of ethanol is shown by the thermochemical
equation and the energy level diagram below:
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) ΔH = -1376 kJ mol-1

Energy

C2H5OH(l) + 3O2(g)

ΔH = -1376 kJ mol-1

2CO2(g) + 3H2O(l)

Figure 8: Energy level diagram for the heat of combustion of ethanol

 Relationship between the heat of combustion of alcohol and the number of carbon
atoms per alcohol molecule / relative molecular mass of alcohol

- The heat of combustion of alcohol increases from 1 member to the following member
as shown in Table 1.

Alcohol Molecular Heat of combustion

formula (kJ mol-1)
Methanol CH3OH -728
Ethanol C2H5OH -1376
Propanol C3H7OH -2026
Butanol C4H9OH -2678
Pentanol C5H11OH -3332

- During the combustion of alcohol, CO2 and H2O are formed.

- When the number of carbon atoms and hydrogen atoms per molecule of alcohol
increases heat of combustion also increases because when more carbon
atoms and hydrogen atoms are burnt, more CO2 and H2O are formed.
- The formation of chemical bonds in CO2 and H2O gives out heat energy. More CO2
and H2O formed will cause more chemical bonds to be formed, and more heat to be
given out.

Solve problems involving heat of combustion

Example 1:
The thermochemical equation for the complete combustion of butanol is shown below:
C4H9OH(l) + 6O2(g) 4CO2(g) + 5H2O(l) ΔH = -2678 kJ mol-1
Assume that there is no heat lost to the surroundings, calculate the mass of butanol needed to burn
completely in excess oxygen in order to raise the temperature of 500 cm3 of water by 44 °C.
[Specific heat capacity of solution = 4.2 J g-1°C-1; density of solution = 1 g cm-3; relative atomic mass: H,1:
C,12: O,16]
Example 2:
The heat of combustion of methanol CH3OH is -728 kJ mol-1. What is its fuel value?
[Relative atomic mass: H,1: C,12: O,16]