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12A Entropy

SPECIFICATION
‒ Entropy
‒ Magnitude of entropy
‒ Entropy changes in reactions
‒ Calculating entropy change of system
‒ Total entropy change
‒ Gibbs free energy change
‒ Limitations of Gibbs free energy change

Source: Edexcel Spec

Edexcel A-Level Chemistry 12A Entropy

Enthalpy and entropy changes are used to predict the feasibility of a reaction at a
particular temperature. In this article, entropy is discussed in detail. A new tem, Gibbs
free energy change is introduced which helps in predicting whether a reaction will be
spontaneous.

A. Entropy
Entropy is the measure of randomness or disorder of a system. A system in chemistry
denotes the chemical reaction itself. In an exothermic reaction, the chemical reaction
releases energy to the surroundings. In an endothermic reaction, the chemical reaction
absorbs energy from the surroundings. The surroundings include the solvent, test tube,
air around the apparatus such as test tube and thermometer. Entropy can also be
defined as the dispersal of energy, either from the system to surroundings or from the
surroundings to the system. The system is more stable when it is more disordered.
Spontaneous reactions tend to continue to occur naturally once initiated. Methane gas
reacting with oxygen is an example of spontaneous reaction. This reaction is initiated
with ignition. Once initiated, the reaction continues until methane or oxygen is
completely used up. Diffusion is an example of spontaneous change. Consider two
flasks joint by a stopcock. One flask contains hydrogen gas, and another contains
oxygen gas. When the stopcock is released, both gases mix up and are disordered. This
is an example for increase in entropy of the system as the molecules can be arranged in
many different ways.

Figure 1: The spontaneous mixing of H2 atoms with O2 atoms

Edexcel A-Level Chemistry 12A Entropy

B. Magnitude of entropy
The entropy values of each substance is calculated at standard conditions. This also
ensures that the comparison is fair. Entropy of one mole of a substance calculated at
standard conditions is called as standard molar entropy. It is denoted by the symbol S ⦵.
Its units are J/(K mol). All standard molar entropies are positive. Some general
conclusions drawn by comparing various entropy values are:
i. Simpler compounds with fewer atoms have lower entropy values when compared to
complex ones with greater number of atoms. For example: the entropy of carbon
monoxide is less than that of carbon dioxide. For example: the entropy of carbon
monoxide (197.6 J/(mol K)) is less than that of carbon dioxide (213.6 J/(mol K)) .
ii. For similar substances, the entropy of harder substances is less. For example:
diamond (2.4 J/(mol K)) has a lower entropy when compared with graphite (5.4
J/(mol K)).
iii. In general, gases have higher entropy value than liquids and liquids have higher
entropy values when compared to solids.
iv. When a substance melts, its entropy value increases as shown in figure. This is
due to the increased randomness in the system. In liquid state, particles are
comparatively freer to move and there is no regular lattice structure. Similarly, when
a substance vaporises, its entropy value increases. This is also due to increased
random movement in the system.

Figure 2: Entropy change during melting and boiling

Edexcel A-Level Chemistry 12A Entropy

C. Entropy changes in reactions

In a chemical reaction, when there is a change in the number of gaseous molecules, the
entropy also changes. When the number of gaseous molecules increases, the entropy
increases too. This is due to the high entropy values of gases when compared to other
states of matter. For example: In the reaction,
MgCO3 (s) → MgO (s) + CO2(g)
the entropy increases as a gas is produced. Solids have low entropy values. The entropy
change of this system is positive.
When the number of gaseous molecules decreases, the entropy decreases too. For
example: In the reaction,
NH3 (g) + HCl (g) → NH4Cl (s)
the entropy decreases as the number of gaseous molecules have reduced. The entropy
change of this system is negative.

D. Calculating entropy change of system

Entropy change of a system is calculated using the entropy values of reactants and
products according to the relationship below,
ΔS⦵system= S⦵products - S⦵reactants
It is important to look at the stoichiometry of the equation while using this relationship.
Example 1: Calculate the entropy change of the system for the reaction,
2Na (s) + Cl2 (g) → 2NaCl (s)
Given that:
S⦵[Na(s)] =51.2 J/K mol, S⦵[Cl2(g)]=165.0 J/K mol and S⦵[NaCl(s)]=72.10 J/K mol
Solution:
ΔS⦵system= S⦵products - S⦵reactants
ΔS⦵system= (2×72.10) – (165 + (2×51.2))
ΔS⦵system=-123.2 J/K mol
Edexcel A-Level Chemistry 12A Entropy

E. Total entropy change

The system either releases or absorbs energy to or from the surroundings depending
upon the nature of the reaction (exothermic or endothermic). The total entropy change is
given by the expression,
ΔS⦵total= ΔS⦵system + ΔS⦵surroundings
where ΔS⦵surroundings denotes the entropy change for the surroundings.
A reaction occurs spontaneously if its total entropy change is positive. A reaction with
negative total entropy change is unlikely to occur.
The entropy change for surroundings ΔS⦵surroundings is given by the expression,

ΔHreaction
⦵
ΔSsurroundings
⦵
=−
𝑇
where ΔH⦵reaction is the standard enthalpy change of reaction in kJ/mol and T is
temperature in K. In exothermic reactions, the energy is given out and the entropy of
surroundings increases and is ΔS⦵surroundings is positive. In endothermic reactions, the
energy is transferred from the surroundings and the entropy of surroundings decreases
and is ΔS⦵surroundings is negative.
The total entropy change is now rewritten as,
⦵ ⦵ ΔH ⦵
reaction
ΔS total = ΔS system −
𝑇

From the above equation, it can be inferred that a balance between ΔS⦵surroundings and
ΔS⦵system determine the feasibility of a reaction. Endothermic reactions with positive
ΔS⦵system are even feasible at room temperatures. For example: reaction between solid
hydrated barium hydroxide and solid ammonium chloride,
Ba(OH)2.8H2O + 2NH4Cl→ BaCl2 + 10H2O + 2NH3
The entropy change of the system (591 J/(K mol)) is positive and enthalpy change (164
kJ/mol) is positive. At 298 K, the ΔS⦵total is 40.7 J/(K mol) and hence, the reaction is
feasible.
Edexcel A-Level Chemistry 12A Entropy

F. Gibbs free energy change

Total entropy change is used to determine whether the reaction occurs spontaneously or
not. A simpler way to determine this is using Gibbs free energy change(ΔG), which takes
into both the system and surroundings. It is given by the expression,
ΔG= -TΔStotal
For a spontaneous change, ΔStotal is positive and T in Kelvin is always positive.
Therefore, Gibbs free energy is negative for spontaneous changes.
Rewriting this expression,
ΔG= ΔHreaction-TΔSsystem
The unit for Gibbs free energy is kJ/mol. It can be noted that entropy change of
surroundings is not considered in this expression.
The effect of temperature on Gibbs free energy is given in the table below.

Exothermic reaction Endothermic reaction

(ΔHreaction is negative) (ΔHreaction is positive)
Positive ΔG= (negative) - (T× positive) ΔG= (positive)- (T× positive)
ΔSsystem ΔG is negative ΔG is negative only at higher
temperatures
Negative ΔG= (negative)- (T× negative) ΔG= (negative)- (T× positive)
ΔSsystem ΔG is negative at lower ΔG is negative
temperatures only

The Gibbs free energy change during phase changes such as melting or boiling is zero.

Example 2: Calculate the Gibbs free energy of the reaction at standard temperature.
2Na (s) + O2(g)→ Na2O2 (s) ΔH⦵r =-510.0 kJ/mol
Given that: S⦵ [Na2O2(s)]=95 J/K mol, S⦵ [Na(s)]=95 J/K mol, S⦵ [O2(g)]=205 J/K mol
Solution:
ΔH = -510.0 kJ/mol = 510000 J/mol
ΔS⦵system= S⦵products - S⦵reactants = (95)- (205 + 2×95) = -300 J/K mol
ΔG= ΔHreaction-TΔSsystem = (510000) – (298 ×-300) = 599400 J/mol
As, ΔG is positive, this reaction is not spontaneous at 298 K.
Edexcel A-Level Chemistry 12A Entropy

G. Limitations of Gibbs free energy change

A mixture of hydrogen and oxygen gas has a negative Gibbs free energy change value
but they do not react with each other until it is ignited. This is because of the fact that the
activation energy to break the hydrogen-hydrogen bonds and oxygen-oxygen double
bonds are high and the particle collisions do not have enough energy. With ignition, the
molecules get enough energy to overcome the activation energy. Palladium acts as a
catalyst to this reaction by lowering the activation energy and in its presence, this
reaction can take place at room temperature.
2H2(g) + O2(g) → 2H2O (l) ΔG⦵=-237 kJ/mol
Even though this reaction has negative Gibbs free energy change, this reaction does not
occur spontaneously due to kinetic limitations.