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CIE A Level Chemistry Your notes
23.3 Entropy Change, ΔS
Contents
Entropy & Entropy Change
Calculating Entropy Changes
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Entropy & Entropy Change
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Defining Entropy
The entropy (S) of a given system is the number of possible arrangements of the particles and their
energy in a given system
In other words, it is a measure of how disordered a system is
When a system becomes more disordered, its entropy will increase
An increase in entropy means that the system becomes energetically more stable
For example, during the thermal decomposition of calcium carbonate (CaCO3) the entropy of the
system increases:
CaCO3 (s) → CaO (s) + CO2 (g)
In this decomposition reaction, a gas molecule (CO2) is formed
The CO2 gas molecule is more disordered than the solid reactant (CaCO3), as it is constantly moving
around
As a result, the system has become more disordered and there is an increase in entropy
Another typical example of a system that becomes more disordered is when a solid is melted
For example, melting ice to form liquid water:
H2O (s) → H2O (l)
The water molecules in ice are in fixed positions and can only vibrate about those positions
In the liquid state, the particles are still quite close together but are arranged more randomly, in that
they can move around each other
Water molecules in the liquid state are therefore more disordered
Thus, for a given substance, the entropy increases when its solid form melts into a liquid
In both examples, the system with the higher entropy will be energetically the most stable (as the
energy of the system is more spread out when it is in a disordered state)
Entropy between physical states
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Melting a solid will cause the particles to become more disordered resulting in a more energetically
stable system
Examiner Tip
Make sure you don’t confuse the system with your surroundings!
The system consists of the molecules that are reacting in a chemical reaction
The surroundings are everything else such as the solvent, the air around the reaction, test-tube, etc
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Entropy Changes
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All elements have positive standard molar entropy values
The order of entropy for the different states of matter are as follows:
gas > liquid > solid
There are some exceptions such as calcium carbonate (solid) which has a higher entropy than
mercury (liquid)
Simpler substances with fewer atoms have lower entropy values than complex substances with more
atoms
For example, calcium oxide (CaO) has a smaller entropy than calcium carbonate (CaCO3)
Harder substances have lower entropy than softer substances of the same type
For example, diamond has a smaller entropy than graphite
Change in state
The entropy of a substance changes during a change in state
The entropy increases when a substance melts (change from solid to liquid)
Increasing the temperature of a solid causes the particles to vibrate more
The regularly arranged lattice of particles changes into an irregular arrangement of particles
These particles are still close to each other but can now rotate and slide over each other in the
liquid
As a result, there is an increase in disorder
The entropy increases when a substance boils (change from liquid to gas)
The particles in a gas can now freely move around and are far apart from each other
The entropy increases significantly as the particles become very disordered
Similarly, the entropy decreases when a substance condenses (change from gas to liquid) or freezes
(change from liquid to solid)
The particles are brought together and get arranged in a more regular arrangement
The ability of the particles to move decreases as the particles become more ordered
There are fewer ways of arranging the energy so the entropy decreases
Graph of entropy against temperature
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The entropy of a substance increases when the temperature is raised as particles become more
disordered
The entropy also increases when a solid is dissolved in a solvent
The solid particles are more ordered in the solid lattice as they can only slightly vibrate
When dissolved to form a dilute solution, the entropy increases as:
The particles are more spread out
There is an increase in the number of ways of arranging the energy
The crystallisation of a salt from a solution is associated with a decrease in entropy
The particles are spread out in solution but become more ordered in the solid
Entropy changes during the dissolving of a solid
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When a solid is dissolved in a solvent to form a dilute solution, the entropy increases as the particles
become more disordered
Entropy changes in reactions
Gases have higher entropy values than solids
So, if the number of gaseous molecules in a reaction changes, there will also be a change in entropy
The greater the number of gas molecules, the greater the number of ways of arranging them, and thus
the greater the entropy
For example the decomposition of calcium carbonate (CaCO3)
CaCO3 (s) → CaO (s) + CO2 (g)
The CO2 gas molecule is more disordered than the solid reactant (CaCO3) as it can freely move
around whereas the particles in CaCO3 are in fixed positions in which they can only slightly vibrate
The system has therefore become more disordered and there is an increase in entropy
Similarly, a decrease in the number of gas molecules results in a decrease in entropy causing the
system to become less energetically stable
For example, the formation of ammonia in the Haber process
N2 (g) + 3H2 (g) ⇋ 2NH3 (g)
In this case, all of the reactants and products are gases
Before the reaction occurs, there are four gas molecules (1 nitrogen and 3 hydrogen molecules) in
the reactants
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After the reaction has taken place, there are now only two gas molecules (2 ammonia molecules) in
the products
Since there are fewer molecules of gas in the products, there are fewer ways of arranging the Your notes
energy of the system over the products
The system has become more ordered causing a decrease in entropy
The reactants (N2 and H2) are energetically more stable than the product (NH3)
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Calculating Entropy Changes
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Entropy Change Calculations
The standard entropy change (ΔSsystemθ) for a given reaction can be calculated using the standard
entropies (Sθ) of the reactants and products
The equation to calculate the standard entropy change of a system is:
ΔSsystemθ = ∑Sproductsθ - ∑Sreactantsθ
(where ∑ = sum of)
For example, the standard entropy change for the formation of ammonia (NH3) from nitrogen (N2) and
hydrogen (H2) can be calculated using this equation
N2 (g) + 3H2 (g) ⇋ 2NH3 (g)
ΔSsystemθ = (2 x ΔSθ(NH3)) - (ΔSθ(N2) + 3 x ΔSθ(H2))
Worked example
Calculate the entropy change of the system for the following reaction:
2Mg (s) + O2 (g) → 2MgO (s)
Sθ [Mg (s)] = 32.60 J K–1 mol–1
Sθ [O2 (s)] = 205.0 J K–1 mol–1
Sθ [MgO (s)] = 38.20 J K–1 mol–1
Answer:
ΔSsystemθ = ΣΔSproductsθ - ΣΔSreactantsθ
ΔSsystemθ = (2 x 38.20) - (2 x 32.60 + 205.0)
ΔSsystem
θ = –193.8 J K-1 mol-1
Examiner Tip
Use the stoichiometry of the equation and the correct state of the compounds when calculating the
entropy change of a reaction
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