22 Entropy and enthalpy

OCR Chemistry A Support

Entropy, enthalpy, and free energy

Specification reference
• 5.2.2

Introduction
Entropy is the driving force behind reactions. For a reaction to occur spontaneously
it needs to produce a positive entropy change for the Universe. In this worksheet
you will reinforce what you already know about entropy and see how the free energy
change is linked closely to entropy.

Learning outcomes
After completing this worksheet you should be able to:
• understand what is meant by the term entropy
• understand the relative entropies of the different states of matter
• understand that when a reaction takes place, the entropy of the system and the
surroundings change
• understand how the total entropy change for a chemical reaction can be
calculated
• know what is meant by a spontaneous reaction
• know that for a reaction to be spontaneous the total entropy change or entropy of
the Universe must be positive.

Background
Entropy is the term used to describe the disorder or dispersal of energy. The greater
the entropy, the greater the amount of disorder, and the greater the dispersal of
energy. The symbol for entropy is S and its units are J K−1 mol−1.
In terms of states of matter, the trend for increasing entropy is as follows:
Solid Liquid Gas
Increasing entropy
Therefore, if liquid water boils to give steam, the entropy has increased. The entropy
change in going from ice to liquid water is much smaller, showing how much more
disordered the gaseous state is compared to solid and liquid states.

Task 1
State whether the entropy of the systems shown below have increased or
decreased.
a CO2(s) → CO2(g)

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b NH4NO3(s) + aq → NH+4 (aq) + NO3− (aq)

c CaCO3(s) → CaO(s) + CO2(g)
d N2(g) + 3H2(g) → 2NH3(g)

(4 marks)
Once it starts, a spontaneous reaction proceeds without any outside intervention.
For a reaction to occur spontaneously, the total entropy of the Universe must
increase. In terms of a chemical reaction the Universe consists of the chemical
system (i.e. the reactants and products and its surroundings).

STOTAL = SSYS + SSURR (surr = surroundings)

The SSYS can be calculated from the molar entropies of the substances in the
system.
Entropy, like enthalpy, is a state function which means that whatever the route taken
to carry out a change, the entropy change will be the same:
S = S(final) − S(start).
In terms of a chemical reaction: SSYS = S(products) − S(reactants).
For example, the reaction between hydrogen and oxygen to give water:
The molar entropy (Sθ) in J K−1 mol−1 for each substance is given below it.

2H2(g) + O2(g) → 2H2O(l)

Sθ 130.6 204.5 70

SSYS = S(products) − S(reactants).

S(products) = 2  70 J K−1 mol−1 = 140 J K−1 mol−1
S(reactants) = 2  130.6 + 204.5 = 465.7 J K−1 mol−1
SSYS = 140 − 465.7 = −325.7 J K−1 mol−1
Note that the value for the molar entropies of both hydrogen and water are multiplied
by 2 because in the equation there are 2 moles of each.

Task 2
Calculate the molar entropy change for the following reactions.
The molar entropy (Sθ) in J K−1 mol−1 for each compound is given below it.

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For some of these reactions, a good guide is for you to estimate whether the
number of gas molecules has increased or decreased. If it has decreased, then the
entropy change will have a negative value, and vice versa.
1 H2(g) + Cl2(g) → 2HCl(g)
130.6 223 186.7
(1 mark)

2 C(s) + CO2(g) → 2CO(g)

5.7 213.6 197.9
(1 mark)

3 C6H14(l) → C6H12(l) + H2(g)

295.9 204.4 130.6
(1 mark)

4 CH4(g) + H2O(g) → CO(g) + 3H2(g)

186.2 188.7 197.9 130.6
(1 mark)

5 N2(g) + 3H2(g) → 2NH3(g)

191.4 130.6 192.5
(1 mark)

If the reaction takes place and the enthalpy change is H rθ , the entropy of the
−H rθ
surroundings is given by , where T is the absolute temperature for the
T
reaction.
Does this make sense? Yes! Because if it is an exothermic reaction, heat is
released to the surroundings, and this would increase the amount of disorder in the
surroundings because particles move around more quickly and occupy many more
different spaces. With the minus sign in front of the negative enthalpy, the entropy
change for the surroundings is positive.
The overall equation for entropy change is:

H rθ
STOTAL = SSYS −
T

Gibbs free energy

H rθ
• The equation for the total energy change is: STOTAL = SSYS −
T
• Multiplying through by −T we get TSTOTAL = TSSYS − H rθ and that

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− TSTOTAL = −TSSYS + H rθ = H rθ − TSSYS

• If −TSTOTAL is negative, then this means that STOTAL is positive and the reaction
is spontaneous.
• Therefore, for the reaction to take place spontaneously then −TSTOTAL must
have a negative value. In the Gibbs equation, −TSTOTAL is represented by the
term G, which is the free energy change.
• What you must realise is that the value of G reflects the value of STOTAL or the
entropy change that the reaction brings to the Universe!
• The Gibbs equation is written as G = H – TSSYS
• The units of G are kJ mol−1.
• Similar to enthalpy and entropy, free energy is a state function and this means
that the following is true:
Greaction = Gproducts – Greactants
Making sense of G
Free energy has two components: H and −TSsys, and it is the balance between
them that determines whether G is negative or positive.
Consider the following reaction:

NH3(g) + HCl(g) → NH4Cl(s)

H is negative because the formation of the ionic solid, ammonium chloride, is
exothermic.
Two gaseous molecules combine to form a more ordered solid, and therefore the
entropy change of the system, SSYS, is negative.
This means that −TSSYS is positive because the entropy of the system decreases.
At low temperatures the negative enthalpy change dominates, and the value of G
is negative and the reaction is spontaneous.
At higher temperatures −TSSYS becomes dominant, and G is positive and the
reaction is no longer spontaneous.
When the reaction is endothermic and H is positive, SSYS is usually positive as
well because bonds are broken and more molecules are produced.
Here −TSSYS has a negative value. At low temperatures, once again H dominates
and, because it is positive, G is also positive and the reaction is not spontaneous.
When the temperature increases, the −TSSYS term becomes more dominant, and
so G is negative and the reaction is spontaneous.
If you check this using le Chatelier’s principle, there is agreement because this says
that increasing the temperature favours the endothermic reaction.
IMPORTANT
In calculations, entropy is in J K−1 mol−1 and enthalpy is measured in kJ mol−1.
Therefore, to make these calculations work
EITHER

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the enthalpy value is converted to J by multiplying it by 103; the final answer must
then be converted to kJ by dividing it by 103
OR
the entropy value is converted to kJ by dividing it by 103.

Task 3
Calculate the free energy change for the following reactions at the temperatures
given and comment on the spontaneous nature of the reaction.
1 H2O(l) ⇌ H2O(s)
H = −6.01 kJ mol−1
S = −22 J K–1 mol−1
Calculate G at:
a 283 K

(2 marks)

b 263 K

(2 marks)

2 CaCO3(s) ⇌ CaO(s) + CO2(g)

H = +178 kJ mol−1
S = +161 J K−1 mol−1
Calculate ∆G at:
a 298 K

(2 marks)

b 1300 K

(2 marks)

3 H2(g) + CO2(g) ⇌ H2O(g) + CO(g)

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H = +39 kJ mol−1
S = +43 J K−1 mol−1
Calculate G at:
a 298 K

(2 marks)

b 1300 K

(2 marks)

Questions
Exam-style question
Hydrazine (N2H4) was one of the first rocket fuels. It was used on the V1 rockets at
the end of the Second World War. At room temperature hydrazine is a liquid.
The equation for the combustion of hydrazine is shown below along with the values
for the entropies and standard enthalpies of formation:

N2H4(l) + O2(g) → N2(g) + 2H2O(l)

Sθ/J K−1 mol−1 121 205 191.6 69.9
ΔHfθ kJ mol−1 +50.6 −258.8

a i Calculate the entropy change for the reaction.

(2 marks)

ii Calculate the enthalpy change for the reaction.

(2 marks)

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iii Calculate the value for the free energy at 298 K.

(3 marks)

b i Give three reasons why hydrazine would make a good fuel.

(3 marks)

ii Hydrazine was found to be a dangerous and unstable fuel. Using your

calculated values for free energy, entropy, and enthalpy changes, explain
why this might be so.

(3 marks)

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