Entropy

change, ΔS
 Objectives
• define the term entropy, S, as the number of possible
arrangements of the particles and their energy in a
given system
• predict and explain the sign of the entropy changes
that occur:
• (a) during a change in state, e.g. melting, boiling and
dissolving (and their reverse)
• (b) during a temperature change
• (c) during a reaction in which there is a change in the
number of gaseous molecules
• calculate the entropy change for a reaction, ΔS, given
the standard entropies, S⦵, of the reactants and
products, ΔS⦵ = ΣS⦵ (products) – ΣS⦵ (reactants) (use of
ΔS⦵ = ΔSsurr⦵ + ΔSsys⦵ is not required)
 • 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
What is disordered, its entropy will increase
entropy • An increase in entropy means that the
system becomes energetically
? more stable
Example 1
• 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
 • 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
Example 2 • 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)
 • Make sure you don’t confuse your system
with the surroundings!
Exam • The system consists of the molecules that
are reacting in a chemical reaction
tip!!! • The surroundings are everything else such
as solvent, the air around the reaction,
test tube etc
Entrop • All elements have positive standard molar entropy
y values
• The order of entropy for the different states of matter
Change are as follows:
s • 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
 • Melting
Change • The entropy increases when a
substance melts (change
in state 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
Boiling

• 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 or freezes
• 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
Solid • The entropy also increases when a solid
dissolv is dissolved in a solvent
• The solid particles are more ordered in
ed in a the solid lattice as they can only slightly
liquid 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
 • Gases have higher entropy values than solids
• So, if the number of gaseous molecules in a
Entropy reaction changes, there will also be a change in
entropy
changes • The greater the number of gas molecules, the
in greater the number of ways of arranging them,
and thus the greater the entropy
reactions • For example the decomposition of calcium
carbonate (CaCO3)
• CaCO3(s) → CaO(s) + CO2(g)
• The system has therefore become
more disordered since a gas has been
formed 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
Entropy changes in reactions contd..

• 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
• 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 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)
Calculating Entropy Changes

• The standard entropy change (ΔSsystemꝋ ) for a given reaction can be calculated
using the standard entropies (Sꝋ ) of the reactants and products
• The equation to calculate the standard entropy change of a system is:
• ΔSsystemꝋ = ΣΔSproductsꝋ – ΣΔSreactantsꝋ

• For example, the standard entropy change for the formation of ammonia (NH 3)
from nitrogen (N2) and hydrogen (H2) can be calculated using this equation
• N2(g) + 3H2(g) ⇋ 2NH3(g)
• ΔSsystemꝋ = (2 x ΔSꝋ(NH3)) – (ΔSꝋ(N2) + 3 x ΔSꝋ(H2))
Example