Form 5 Chapter 4: Thermochemistry

The Law of Conservation of Energy

- Energy can neither be created nor destroyed but it can be changed from one form to the
other form.

Thermochemistry
- Study of changes in heat energy during chemical reactions. There are two types of
chemical reaction:
1) Exothermic reaction – a chemical reaction that gives out heat to the surrounding.
2) Endothermic reaction – a chemical reaction that absorbs heat from the surrounding.

Surroundings do not involve in the reactions. Example: water, container, the air, solvent and
thermometer.

Exothermic reaction
1. Chemical energy –> Heat energy
2. The heat energy is transferred to the surrounding.
3. Temperature of the surrounding increases.

Example of Chemical Reactions:

 Respiration
 Burning of metal
 Reaction of an alkaline metals (Group 1) with water
 Reaction of a reactive metal with acid
 Neutralization reaction between acid and alkali
 Reaction of a carbonate with acid
 Combustion of carbon compound
 Displacement reaction of metals
 Rusting of iron

Example of Physical Processes:

 Freezing process
 Condensation process
 Dissolving an alkali in water
 Dissolving an concentrated acid in water

Endothermic reaction
1. Heat energy –> Chemical energy
2. The heat is absorbed from the surrounding.
3. Temperature of the surrounding decreases.

Example of Chemical Reactions:

 Photosynthesis
 Decomposition of nitrate salts
  Decomposition of carbonates salts
 Reaction between acid with hydrogen carbonates

Example of Physical Processes:

 Melting process
 Boiling process
 Sublimation process
 Dissolving of ammonium salts in water
 Dissolving of potassium salts in water
 Dissolving of thiosulphate  in water

Heat of Reaction

Enthalpy (H) – absolute energy content of a substance.

Change in energy content (ΔH) – absolute energy content cannot be determined, but ΔH can be
determined when the reactants are converted to the products.

Heat of reaction (ΔH) – the amount of heat energy released or absorbed during a chemical
reaction. Measured in kJ.

Energy Level Diagram

Exothermic reaction:
ΔH = H product – H reactant = negative value.
Example: CH4(g) + 2O2(g) –> CO2(g) + 2H2O(l) ΔH = -890 kJ

Endothermic reaction:
ΔH = H product – H reactant = positive value.
Example: N2(g) + 3H2(g) –> 2NH3(g) ΔH = +91.8kJ

Energy Change during Formation and Breaking of Bonds

Bond breaking
 Usually chemical bonds of the reactant.
 Heat energy is absorbed = endothermic change

Bond forming
 Usually new chemical bonds of the product.
 Heat energy is given out = exothermic change

Relationship between energy change and the formation and breaking of bonds

 In a chemical reaction, if the heat energy absorbed in bond breaking is lower than the
heat energy given out in bond forming, the reaction is an exothermic reaction.
 Example:
 ΔH (bond breaking) = +600 kJ, ΔH (bond forming) = -800 kJ
ΔH (heat of reaction) = [(+600) + (-800)] kJ= -200 kJ

 In a chemical reaction, if the heat energy absorbed in bond breaking is higher than the
heat energy given out in bond forming, the reaction is an endothermic reaction.
 Example:
ΔH (bond breaking) = +800 kJ, ΔH (bond forming) = -600 kJ
ΔH (heat of reaction) = [(+800) + (-600)] kJ= +200 kJ

Applications of Exothermic and Endothermic Reaction in Everyday Life

Hot pack
 Contains of anhydrous calcium chloride / anhydrous magnesium sulphate / wet iron
powder and sodium chloride / calcium oxide.
 Uses: reduce swelling and muscles or joint sprain.

Cold pack or Ice pack

 Contains of ammonium nitrate / potassium nitrate / sodium thiosulphate.
 Uses: reduce swelling, muscles or joint sprain and reduce fever.

** Must Know!
1. Calculate the number of moles of salt precipitated / metal displaced / water produced /
fuel used;
2. Calculate the heat energy released (ΔH); and
3. Calculate the heat of precipitation / heat of displacement / heat of neutralization / heat of
combustion.

Heat of Precipitation (Form 4, Chapter 8 Salts)

1. Heat of precipitation – the heat change when one mole of a precipitate is formed from
their ions in aqueous solution.
2. Precipitation reaction = double decomposition which is used to prepare insoluble salts.
3. Heat change of a solution = mcθ Joule [m = mass of the solution (g), c = specific heat
capacity of the solution (J g-1˚C-1), θ = temperature change in the solution (˚C)]
4. Heat change in a reaction, mcθ = n x ΔH
5. Heat of reaction / Heat of precipitation, ΔH = mcθ / n
Example 1:
Chemical reaction: Pb(NO3)2(aq) + 2KI(aq) –> PbI2(s) + 2KNO3(aq)
Ionic reaction: Pb2+(aq) + 2I-(aq) –> PbI2(s)
Heat of precipitation of PbI2 = – Heat change / Number of moles of PbI2
Example 2:
Chemical reaction: BaCl2(aq) + Na2SO4(aq) –> BaSO4(s) + 2NaCl(aq)
Ionic reaction: Ba2+(aq) + SO42-(aq) –> BaSO4(s)
Heat of precipitation of BaSO4 = – Heat change / Number of moles of BaSO4
 
Heat of Displacement (Form 4, Chapter 6 Electrochemistry & Form 5, Chapter 3 Oxidation and
Reduction)
1. Heat of displacement – the heat change when one mole of a metal is displaced from its
salt solution by a more electropositive metal.
2. Heat change of the reaction mixture / Heat energy released / Heat given out in the
reaction = mcθ Joule
3. Heat change in a reaction, mcθ = n x ΔH
4. Heat of reaction / Heat of displacement, ΔH = mcθ / n
Example 1:
Chemical equation: Mg(s) + FeCl2(aq) –> MgCl2(aq) + Fe(s)
Ionic equation: Mg(s) + Fe2+(aq) –> Mg2+(aq) + Fe(s)
Example 2:
Chemical equation: Zn(s) + CuSO4(aq) –> ZnSO4(aq) + Cu(s)
Ionic equation: Zn(s) + Cu2+(aq) –> Zn2+ (aq) + Cu(s)
Heat of Neutralisation (Form 4, Chapter 7 Acids and Bases)
1. Heat of neutralisation – the heat change when one mole of water is formed from the
reaction between an acid and an alkali.
2. Neutralisation – a reaction between an acid reacts with a base (alkali) to form a salt and
water.
3. Hydrogen ion from acid reacts with hydroxide ions from alkali to form water. H+(aq) +
OH-(aq) –> H2O(l)
4. Neutralisation reaction gives out heat and always an exothermic reaction.
Example 1: (Strong acids – monoprotic acid and strong alkalis)
Chemical equation: HCl(aq) + NaOH(aq) –> NaCl(aq) + H2O(l)
Ionic equation: H+(aq) + OH-(aq) –> H2O(l)
Heat of neutralisation of strong acids and strong alkalis are the same (ΔH = -57.3 kJ mol-1)
Example 2: (Strong acids – diprotic acid and strong alkalis)
Chemical equation: H2SO4(aq) + NaOH(aq) –> Na2SO4(aq) + 2H2O(l)
Ionic equation: 2H+(aq) + 2OH-(aq) –> 2H2O(l)
Heat of neutralisation of strong acids and strong alkalis are the same (ΔH = -57.3 kJ mol-1)
Example 3: (Weak acids and strong alkalis)
Chemical equation: CH3COOH(aq) + NaOH(aq) –> CH3COONa(aq) + H2O(l)
Ionic equation: H+(aq) + OH-(aq) –> H2O(l)
Heat of neutralisation of weak acids and strong alkalis are lower (ΔH = -55.0 kJ mol-1) than heat
of neutralisation of strong acids and strong alkalis (ΔH = -57.3 kJ mol-1).
Example 4: (Strong acids and weak alkalis)
Chemical equation: HCl(aq) + NH4OH(aq) –> NH4Cl(aq) + H2O(l)
Ionic equation: H+(aq) + OH-(aq) –> H2O(l)
Heat of neutralisation of strong acids and weak alkalis are lower (ΔH = -51.5 kJ mol-1) than heat
of neutralisation of strong acids and strong alkalis (ΔH = -57.3 kJ mol-1).
Example 5: (Weak acids and weak alkalis)
Chemical equation: CH3COOH(aq) + NH4OH(aq) –> NH4Cl(aq) + H2O(l)
Ionic equation: H+(aq) + OH-(aq) –> H2O(l)
Heat of neutralisation of strong acids and weak alkalis are lower (ΔH = -50.4 kJ mol-1) than heat
of neutralisation of strong acids and strong alkalis (ΔH = -57.3 kJ mol-1).
Heat of Combustion (Form 5, Chapter 2 Carbon Compounds)
 1. Heat of combustion – the heat change when one mole of a substance is completely burnt
in oxygen under standard conditions.
2. Combustion – redox reaction between substances (fuel) reacts rapidly with oxygen with
the production of heat energy.
3. Combustion reaction gives out heat and always an exothermic reaction.
4. Heat evolved in combustion of fuel = Heat absorbed by water.
5. Bomb calorimeter is used to determine the heat of combustion.
6. The more carbon and hydrogen atoms per molecules in a fuel, the more heat that is
released when 1 mol of fuel combusts.
There are differences in heats of combustion:
Chemical equation ΔH (kJ mol-1)
H2(g) + ½ O2(g) –> H2O(l) -286
C(s) + O2(g) –> CO2(g) -392
CH4(g) + 2O2(g) –> CO2(g) + 2H2O(l) -890
CH3OH(l) + 3/2 O2(g) –> CO2(g) + 2H2O(l) -728
C2H5OH(l) + 3O2(g) –> 2CO2(g) + 3H2O(l) -1376
C3H7OH(l) + 9/2 O2(g) –> 3CO2(g) + 4H2O(l) -2016
The selection of suitable fuel:
 Fuel value (the amount of heat energy given out when one gram of the fuel is completely
burnt in excess of oxygen): The higher the fuel value, the more energy is released.
 Effect on the environment: Production of soot which caused air pollution. Hydrogen fuel
is known as clean fuels (no soot or poisonous gases).
 Cost per gram of fuel.
Fuel values of common fuels
Substances Fuel value (kJ g-1)
Fruits 2
Egg 6
Coal 14
Glucose 15.5
Dry cow dung 15.5
Sugars 17
Wood 18
Gasoline 34
Butanol 36.6
Kerosene 37
Biodiesel (Vegetable oil) 42.2
Diesel fuel 46
Natural gas 53.6
Hydrogen 143
Qualities of a fuel are based on the following:
 Easily available
 Cheap in cost
 High fuel value
  Do not pollute the environment
 Less storage space
The Existence of Various Energy Sources
1. The Sun: solar cell (still expensive and inefficient)
2. Fossil Fuels: relatively high fuel value and convenient to use (non-renewable and cause
greenhouse effect and acid rain)
3. Water: hydroelectric power. It is clean, renewable, convenient and economical to use
(high cost of construction and destruction of the surrounding environment)
4. Biomass: plants and droppings of animals – biodiesel (large areas of land to grow plants)
5. Radioactive substances: uranium and plutonium (non-renewable and very destructive if
an accident occurs)
Important Definitions:
 Standard conditions: temperature (25˚C / 298 K), pressure (1 atm), concentration of
solution (1.0 mol dm-3), reactants and products are at their normal physical states.
 Heat of precipitation – the heat change when one mole of a precipitate is formed from
their ions in aqueous solution.
 Heat of displacement – the heat change when one mole of a metal is displaced from its
salt solution by a more electropositive metal.
 Heat of neutralisation – the heat change when one mole of water is formed from the
reaction between an acid and an alkali.
 Heat of combustion – the heat change when one mole of a substance is completely burnt
in oxygen under standard conditions.