1

Entropy


alt
Entropy

Bilal Hameed Entropy

 2 construct and use an energy cycle involving enthalpy change of solution, lattice energy and enthalpy change
of hydration
3 carry out calculations involving the energy cycles in 23.2.2
4 2 and of ionic radius on the numerical magnitude of an
explain, in qualitative terms, the effect of ionic charge
enthalpy change of hydration

23.3 Entropy change, S

Learning outcomes
Candidates should be able to:

alt
1 define the term entropy, S, as the number of possible arrangements of the particles and their energy in a
given system
2 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
3 calculate the entropy change for a reaction, S, given the standard entropies, S , of the reactants and
products,
Cambridge International AS & SA Level
= SChemistry
(products)
9701–syllabus
S (reactants)
for 2022, 2023 and 2024. Subject content
(use of S = Ssurr + Ssys is not required)

Back to contents
23.4 page
Gibbs free energy change, G www.cambridgeinternational.org/alevel 35
Learning outcomes
Candidates should be able to:
1 state and use the Gibbs equation G = H – T S
2 perform calculations using the equation G = H – T S
3 state whether a reaction or process will be feasible by using the sign of G
4 predict the effect of temperature change on the feasibility of a reaction, given standard enthalpy and
entropy changes

24 Electrochemistry
24.1 Electrolysis
Learning outcomes
Candidates should be able to:
1 predict the identities of substances liberated during electrolysis from the state of electrolyte (molten or
aqueous), position in the redox series (electrode potential) and concentration
2 state and apply the relationship F = Le between the Faraday constant, F, the Avogadro constant, L, and the
charge on the electron, e
3 calculate:
(a) the quantity of charge passed during electrolysis, using Q = It
(b) the mass and/or volume of substance liberated during electrolysis
4 describe the determination of a value of the Avogadro constant by an electrolytic method

24.2 Standard electrode potentials E ; standard cell potentials E cell and the Nernst equation
Learning outcomes
Candidates should be able to:
1 define the terms:
(a) standard electrode (reduction) potential
(b) standard cell potential
2 describe the standard hydrogen electrode
3 describe methods used to measure the standard electrode potentials of:
(a) metals or non-metals in contact with their ions in aqueous solution
Entropy Bilal Hameed
(b) ions of the same element in different oxidation states
4 calculate a standard cell potential by combining two standard electrode potentials
5 use standard cell potentials to:
 3

3. 1 Entropy

alt
The dissolving of sodium chloride (common salt) in water is an
endothermic process that occurs spontaneously at room temperature.
The idea of an endothermic reaction occurring spontaneously goes
against our daily experiences that things do not seem to move
spontaneously from lower to higher energy states (a book does not jump
from a lower shelf to a higher one but will fall to a lower shelf if the shelf it
is on breaks).
This suggests that it is not just a consideration of energy changes involved
that can be used to predict whether a reaction occurs spontaneously.

3. 2 Entropy
In a sodium chloride solution the Na+ and Cl− ions are dispersed
throughout the solution and are moving around, which is a much more
disordered, or random, arrangement than a separate crystal of sodium
chloride and a beaker of pure water.

This property of disorder is called entropy, and it is possible to assign

values to the entropy of a system and the entropy change for a reaction.
An endothermic reaction can only occur if it involves an increase in
entropy.

Entropy is given the symbol S. The units of entropy are JK−1mol−1.

3. 3 Entropy change
It is possible to work out values for standard entropies for substances;
for example, the standard entropy of H2(g) is 131 J K−1 mol−1, and the
standard entropy of NaCl(s) is 72.4 J K−1 mol−1.

An entropy change is represented by the symbol ∆Sϴ

A positive value for ∆Sϴ indicates an increase in entropy, i.e. an increase

in disorder. For example:
H2O(l) ⟶ H2O(g) ∆Sϴ = +119 JK−1 mol−1.
The disorder of the system has increased, as the molecules of water in
the gas phase are moving around much more.

Bilal Hameed Entropy

Bilal Hameed Marginalizer
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2

3. 4 Entropy change
A negative value for ∆Sϴ indicates a decrease in entropy, i.e. a decrease

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in disorder. For example

NH3(g) + HCl(g) ⟶ NH4Cl(s) ∆Sϴ = —285 JK−1mol−1

Two molecules of gas being converted into a solid results in a decrease

in disorder, i.e. a decrease in entropy.

This is an approximate rule of

thumb, which is useful when
considering the same substanc
different states or similar substa
When considering very differe
substances, it must be used wit
3. 5 Predict the sign of an entropy change caution. For instance, S for
(NH4)2SO4(s) is 220 J K−1 mol−
Gases have higher entropy than liquids, which have higher entropy than whereas that for CCl4(l) is
solids. 214 J K−1 mol−1 and that for H
is 187 J K−1 mol−1.
The table below shows the values of standard entropies for elements
across period 2 in
Table 5.4 the the
shows periodic table.
values of standard entropies for elements across
period 2 in the periodic table. Lithium to carbon are all solid elements
Lithiumand
tohave
carbon are solid
low entropy elements
values at 298 K,and have low
but nitrogen entropy
to neon are allvalues
gases at 298
K, but and
nitrogen to neon
have much higherare gases
entropy and have much higher entropy values.
values.

Increase in number of moles

of gas: ∆S +ve (entropy
increases).
To predict the sign of the entropy change in a reaction, we must
consider whether there is an increase or decrease in disorder in the system.
As gases have significantly higher entropy than solids and liquids, the most
Decrease in number of mole
important factor in determining whether a chemical reaction involves an
3. 6 Predict
increase the
or decrease sign isof
in entropy an entropy
whether change
there is an increase or decrease
of gas: ∆S −ve (entropy
decreases).
in the number of moles of gas (Table 5.5).
Gases have higher entropy than liquids, which have higher entropy than
solids.
This is an approximate rule of thumb, which is useful when considering
the same substance in different states or similar substances. When
considering very different substances, it must be used with caution.
For instance, Sϴ for (NH4)2SO4(s) is 220 JK−1mol−1, whereas that for CCl4(l)
is 214 JK−1mol−1 and that for HCl(g) is 187 JK−1mol−1.

If the number of moles of gas is the same on both sides of an equation,

as in this one:

F2(g) + Cl2(g) 2ClF(g)

the prediction could be made that the entropy change for this reaction
would be approximately zero.

Entropy Bilal Hameed

Marginalizer Bilal Hameed
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3. 7 Predict the sign of an entropy change

To predict the sign of the entropy change in a reaction, we must consider

alt
whether there is an increase or decrease in disorder in the system.
As gases have significantly higher entropy than solids and liquids, the
This is an approximate rule of
most important factor in determining whether a chemical reaction
thumb, which is useful when
involves an increase or decrease in entropy is whether theretheissame
considering ansubstance in
different states or similar substances.
increase or decrease in the number of moles of gas. When considering very different
substances, it must be used with
Increase in number of moles of gas: ∆Sϴ +ve (entropy increases).
caution. For instance, S for
−1
(NH4)2SO4(s) is 220 J K mol−1,
whereas that for CCl4(l) is
Decrease in number of moles of gas: ∆Sϴ −ve (entropy
214 J K−1decreases).
mol−1 and that for HCl(g)
is 187 J K−1 mol−1.

Table 5.4 shows the values of standard entropies for elements across
period 2 in the periodic table. Lithium to carbon are all solid elements
and have low entropy values at 298 K, but nitrogen to neon are all gases
and have much higher entropy values.

3. 8 Entropy changes for some reactions

Increase in number of moles
gas: ∆S +ve (entropy
If the number of moles of gas is the same on bothof sides
increases).
of an
To predict the sign of the entropy change in a reaction, we must
equation, the prediction could be made that the
consider whether there is an increase or decrease in disorder in the system. entropy change for this
As gases have significantly higher entropy than solids and liquids, the most
reaction would be approximately zero. For example:
important factor in determining whether a chemical reaction involves an
Decrease in number of moles
of gas: ∆S −ve (entropy
F2(g) + Cl2(g) ⟶ 2ClF(g)
increase or decrease in entropy is whether there is an increase or decrease
in the number of moles of gas (Table 5.5).
∆Sϴ decreases).
≈0

If the number of moles of gas is the same on both sides of an equation,

as in this one:

F2(g) + Cl2(g) 2ClF(g)

the prediction could be made that the entropy change for this reaction
3. 9 Skill Check 1
would be approximately zero.

Predict the sign of ∆S for each process.

(a) H2O(g) → H2O(l)

(b) Solid carbon dioxide sublimes.

(c) 2N2O(g) → 2N2(g) + O2(g)

Bilal Hameed Entropy

Bilal Hameed Marginalizer
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3. 10 Skill Check 2
Without doing any calculations, predict whether the entropy of the

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system increases or decreases as a result of these changes:
(a) KCl(s) + aq → KCl(aq)
(b) H2O(l) → H2O(g)
(c) Mg(s) + Cl2(g) → MgCl2(s)
(d) N2O4(g) → 2NO2(g)
(e) NaHCO3(s) + HCl(aq) → NaCl(aq) + H2O(l) + CO2(g)

3. 11 Skill Check 3
Work out whether each of the following processes involves an increase
or decrease in entropy:
(a) C2H2(g) + 2H2(g) ⟶ C2H6(g)

(b) 2C2H6(g) + 7O2(g) ⟶ 4CO2(g) + 6H2O(l)

(c) COCl2(g) ⟶ CO(g) + Cl2(g)

(d) 2C(s) + O2(g) ⟶ 2CO(g)

3. 12 Skill check 4
For each of the following changes, say whether you think the entropy change of
the substances (the system) will be A = positive, B = negative or C =
approximately zero
(a) Cu(s) → Cu(l)
(b) I2(g) → I2(s)
(c) Heating water from 20°C to 50°C.
(d) NH4Cl(s) → NH3(g) + HCl(g)
(e) C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
(f) NaCl(s) → Na+(aq) + Cl−(aq)
(g) H+(aq) + OH−(aq) → H2O(I)

Entropy Bilal Hameed

Marginalizer Bilal Hameed
 reaction: reaction:
4NH
4NH3(g) + 3O2(g) 3
(g) 2N
+ 3O 2(g)
2(g) + 6H22N2(g) + 6H2O(l)
O(l)
7
5

−1
A −1−240 kJ mol
A −240 kJ mol C −1532 kJCmol−1532
−1 kJ mol−1
B −1−332 kJ mol−1
B −332 kJ mol D −1900 kJDmol−1900 kJ mol
−1 −1
3. 13 Skill check 5
8 Which of8theWhich of the following
has reactions has that
a ∆Sis negative?
value that is negative?

alt
following reactions a ∆S value
A 2H2O2(aq) A 2H 2O
2H 2(aq)+ O22H
2O(l) (g)2O(l) + O2(g)
B CaCO3(s)B CaCO CaO(s)3(s)
+ COCaO(s)
2(g) + CO2(g)
CaCO3(s) + 2HCl(aq)
C CaCO3(s)C+ 2HCl(aq) CaCl2(aq) + CO CaCl 2(aq)
2(g) + H+2O(l)
CO2(g) + H2O(l)
D 2C4H10(g) 2C4H
D+ 13O 2(g)
10(g) + 13O
8CO 2
2
(g)
(g) + 8CO
10H 2
(g)
O(l)
2 + 10H2O(l)

9 Which of9theWhich of the

following willfollowing
have the will have
largest the of
value largest value
lattice of lattice enthalpy?
enthalpy?
A NaCl A NaClB MgO B MgOC CaO C CaO D MgBr2 D MgBr2

Using
10data
10 Using the giventhe data given
below, below,
calculate the calculate the value
value of ∆G of ∆G
, for the , for the
following following
reaction reaction
at 298 K: at 298 K:
SO2(g)SO
SO2(g) + Cl2(g) + Cl2(g)
2Cl2(l)
SO2Cl2(l)
−1 −1 J K−1 mol−1
∆H = −97.3
−1 kJ mol
∆H = −97.3 kJ mol and ∆S = −254.4 and ∆SJ K−1
= mol
−254.4

A −21.5 kJ A −21.5 kJ mol−1

mol−1 C −173.1 kJCmol−173.1
−1 kJ mol−1
−1 714 kJ mol−1 −97.0 kJ mol−1
B 75 714 kJBmol75 D −97.0 kJ D
mol−1
3. 14 Calculating entropy changes
Values of ∆Sϴ may be worked out from standard entropies, Sϴ:

entropy change = total entropy of products — total entropy of

reactants

∆Sϴ = ΣSproducts — ΣSreactants

3. 15 Calculating entropy changes Values of ∆S may be worked out from standard entropies, S :

entropy change
Calculate the standard entropy change for the following reaction: = total entropy of products − total entropy of reactants

N2(g) + 3H2(g) ⟶ 2NH3(g) ∆S = ∑S products − ∑S reactants

Calculate the standard entropy change for the following reaction:

N2(g) + 3H2(g) 2NH3(g)

∆S = (2 × 193) − [192 + (3 × 131)]

∆Sϴ = (2 × 193) — [192 + (3 × 131)]
∆Sϴ = —199 J K−1 mol−1
The standard entropy values are
∆S = −199 J K−1 mol−1
multiplied by the appropriate
coefficients in the equation.
That there is a decrease in entropy corresponds to the prediction made
above based on the number of moles of gas.

24 Work out whether each of the following processes

involves an increase or decrease in entropy:
a C2H2(g) + 2H2(g) C2H6(g)
b 2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l)
c COCl2(g) CO(g) + Cl2(g)
d 2C(s) + O2(g) 2CO(g)
25 Use the entropy values in the table to calculate the
standard entropy change in each of the following
reactions:
Bilal Hameed a CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Entropy
Bilal Hameed b 2Cu(NO3)2(s)
Marginalizer
2CuO(s) + 4NO2(g) + O2(g)
c 4BCl3(l) + 3SF4(g) 4BF3(g) + 3SCl2(g) + 3Cl2(g)
 8
6

3. 16 Skill Check 6
Calculate the entropy change for the following reaction under standard

alt
conditions:

3O2(g) → 2O3(g)
S° (O3) = 237.7 J K−1 mol−1
S° (O2) = 204.9 J K−1 mol−1

3. 17 Skill Check 7
Calculate the entropy change when 1 mol of graphite is oxidised to carbon
dioxide under standard conditions.

C(s) + O2(g)→ CO2(g)

S° (graphite) = 5.7 J K−1 mol−1
S° (O2) = 102.5 J K−1 mol−1
S° (CO2) = 213.6 J K−1 mol−1

3. 18 Skill Check 8
What is ∆Sϴ for the following reactions?

(a) CaCO3(s) ⟶ CaO(s) + CO2(g)

[Sϴ /Jmol–1K–1: CaCO3(s) 92.9; CaO(s) 39.7; CO2(g) 213.6]

(b) C2H4(g) + H2O(l) ⟶ C2H5OH(l)

[Sϴ /Jmol–1K–1: H2O(l) 69.9; C2H5OH(l) 160.7; C2H4(g) 219.5]

Entropy Bilal Hameed

Marginalizer Bilal Hameed
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Example
3. 19 Skill Check 9
Table 13.2.4 Use the values in Table 13.2.4 to calculate the total entropy change when
Use the values in the table below to calculate sodium chloride dissolves in water under standard conditions.
S 1/J mol−1the
K−1 total entropy change

alt
when sodium chlorideNaCl(s)
dissolves in water under standard conditions.
NaCl(s) → Na+(aq) + Cl−(aq) ∆H 1 = +3.8 kJ mol−1
+72.1 Example system

NaCl(s) → Na
Na
Table
+(aq) + Cl−(aq)
+(aq)
13.2.4
+321 ∆H= +3.8 kJ mol
Notes
−1 on the method
Use the values in Table 13.2.4 to calculate the total entropy change whe
Cl−(aq) +56.5 Calculate the entropy
sodium chloride changeinofwater
dissolves the surroundings usingconditions.
under standard the formula:
S 1/J mol−1 K−1 ∆H 1
∆S surroundings
1
=−
NaCl(s) +72.1 NaCl(s) → Na+(aq) T+ Cl−(aq) ∆Hsystem1 = +3.8 kJ mol−1
Remember to convert the value of the enthalpy change to J mol−1.
Na+(aq) +321 Notes on the method
Answer
Cl−(aq) +56.5 Calculate the entropy change of the surroundings using the formula:
38001J mol−1
∆S
∆Ssurroundings
11
surroundings= =− − ∆H = −12.8 J mol−1 K−1
298
T K
∆S system
Remember
1
=toΣS [products]
convert
1
− ΣS of
the value 1
the enthalpy change to J mol−1.
[reactants]

Answer = 321 J mol−1 K−1 + 56.5 J mol−1 K−1 − 72.1 J mol−1 K−1
−1 K−1
= +305 J mol
3800 J mol−1
∆S surroundings
1 =− = −12.8 J mol−1 K−1
∆S total
1 = ∆S system
1
+ 2981K
∆S surroundings
∆S system
1
= ΣS 1[products] − ΣS 1[reactants]
= +305 J mol K − 12.8 J mol K = +292 J mol−1 K−1
−1 −1 −1 −1

3. 20 Skill Check 10 = 321 J mol−1 K−1 + 56.5 J mol−1 K−1 − 72.1 J mol−1 K−1
The total entropy change is positive. Sodium chloride dissolving in water
is a feasible process.
= +305 J mol−1 K−1
Use the values in the table below to calculate the total entropy change
∆S total
1
when ammonium nitrate dissolves in water under standard conditions. = ∆S system
1
+ ∆S surroundings
1

Test yourself
= +305 J mol−1 K−1 − 12.8 J mol−1 K−1 = +292 J mol−1 K−1
8The
a) total entropy
Use the change
values is 13.2.5
in Table positive.
to Sodium
calculatechloride
the totaldissolving
entropy in water
NH4NO3(s) → NH
Table 4+(aq) + NO3−(aq) ΔH = +28.1 kJismol
13.2.5
−1
a feasible process.
change when ammonium nitrate dissolves in water under standard
S 1/J mol−1 K−1 conditions.
NH4NO3(s) 151 NH4NO3(s) → NH4+(aq) + NO3−(aq) ∆H 1 = +28.1 kJ mol−1
NH4 +(aq) 113
Test yourself
b) Comment on the fact that ammonium nitrate dissolves in water
NO3−(aq) 146 even though the process is endothermic.
8 a) Use the values in Table 13.2.5 to calculate the total entropy
Table 13.2.5 change when ammonium nitrate dissolves in water under standard
S 1/J mol−1 K−1 conditions.
NH4NO3(s) 151
13.2.4 Free
NH NO 4
energy
(s) → NH3(aq) + NO
4
+
3
− (aq) ∆H 1 = +28.1 kJ mol−1
NH4+(aq) A chemical
113 changeon
b) Comment is feasible
the factifthat
the ammonium
total entropy change
nitrate is positive.
dissolves There
in water
NO3 −(aq) 146 is no doubt about
even this.
though theThe problem
process is is that using
endothermic. entropy to decide on the
direction change involves three steps: working out the entropy change of
the system, working out the entropy change of the surroundings, and then
putting the two together to calculate the total entropy change. This can be
3. 21 Skill Check 11 13.2.4 Free energy
laborious and so chemists are grateful to the American physicist Willard
Gibbs, who discovered
A chemical an easierif way
change is feasible of unifying
the total entropyallchange
that chemists know
is positive. The
The equation for the reaction between carbon dioxide and
about hydrogen isthe extent and direction of change.
is nopredicting
doubt about this. The problem is that using entropy to decide on t
shown below. direction change involves three steps: working out the entropy change
the system, working out the entropy change of the surroundings, and th
CO2(g) + 4H2(g) → CH4(g) + 2H2O(g)
putting the two together to calculate the total entropy change. This can
laborious
The table below shows the standard entropy values of the and soinchemists are grateful to the American physicist Willa
substances
Gibbs, who discovered an easier way of unifying all that chemists kno
the reaction above. 376 13.2 Entropy
about predicting the extent and direction of change.

469983_13.2_Chem_Y1-2_367-386.indd 376 13/04/

Calculate the standard entropy change for the reaction.

376 13.2 Entropy

469983_13.2_Chem_Y1-2_367-386.indd 376

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3. 22 Skill Check 12
Substance Sϴ / J K−1
Use the entropy values in the table to calculate the

alt
CH4(g) mol−1186

standard entropy change in each of the following reactions: O2(g) 103

CO2(g) 214
(a) CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(l) H2O(l) 70
Cu(NO3)2(s) 193
CuO(s) 43
NO2(g) 240
BCl3(l) 206
SF4(g) 292
BF3(g) 254
SCl2(g) 282
Cl2(g) 83

3. 23 Skill Check 12
Substance Sϴ / J K−1

(b) 2Cu(NO3)2(s) ⟶ 2CuO(s) + 4NO2(g) + O2(g) CH4(g) mol−1186

O2(g) 103
CO2(g) 214
H2O(l) 70
Cu(NO3)2(s) 193
CuO(s) 43
NO2(g) 240
BCl3(l) 206
(c) 4BCl3(l) + 3SF4(g) ⟶ 4BF3(g) + 3SCl2(g) + 3Cl2(g)
SF4(g) 292
BF3(g) 254
SCl2(g) 282
Cl2(g) 83

3. 24 Spontaneity
Spontaneous reaction: one that occurs without any outside influence, i.e.
no input of energy.
If sodium and oxygen are put together in an isolated container (one with
no connection to the outside world) at 25 °C, they will react
spontaneously to produce sodium oxide:
4Na(s) + O2(g) ⟶ 2Na2O(s)

This reaction will occur by itself – nothing has to be done to make the
reaction occur. This is an example of a spontaneous reaction.

Entropy Bilal Hameed

Marginalizer Bilal Hameed
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3. 25 Spontaneity
If methane and oxygen are put into an isolated container at 25 °C, they will

alt
react together spontaneously to form carbon dioxide and water.
This reaction, although it is spontaneous, is not a very fast reaction at
room temperature (unless a spark is supplied) and would have to be left
for a very long time before a significant amount of carbon dioxide and
water could be detected.
Similarly, the conversion of diamond to graphite at room temperature is a
spontaneous process, but luckily occurs immeasurably slowly!
A spontaneous reaction does not have to happen quickly.

3. 26 Spontaneity
Whether a reaction will be spontaneous or not under a certain set of conditions
can be deduced by looking at how the entropy of the Universe changes as the
reaction occurs.
The second law of thermodynamics states that for a process to occur
spontaneously it must result in an increase in the entropy of the Universe
(system & surroundings). The total entropy change is given by:
∆STotal = ∆Ssurroundings + ∆Ssystem
If the value of ∆STotal is positive, the total entropy (of the universe) increases and
the reaction occurs spontaneously.

3. 27 Spontaneity
The total entropy change is given by: ∆Stotal = ∆Ssurroundings + ∆Ssystem

The entropy change of the system is given by: ∆Ssystem = ΣSproducts — ΣSreactants

The entropy change of the surroundings is given by:

∆Ssurroundings = —∆Hreaction
T
∆Stotal = ∆Ssystem — ∆Hreaction
T

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Bilal Hameed Marginalizer
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3. 28 Gibbs free energy

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There is a more straightforward way in which we can take account of
both system and surroundings.

It involves a quantity called Gibbs free energy or, more simply, free
energy.The Gibbs free energy change is given by the relationship:
∆G = —T∆Stotal
∆Stotal = ∆Ssurroundings + ∆Ssystem
— ∆G = —∆Hreaction + ∆Ssystem
T T
∆G = ∆H —T∆S

3. 29 Gibbs free energy

∆G is called the change in Gibbs free energy, or just the free energy
change. Under standard conditions, we have ∆Gϴ, which is the
standard free energy change.

∆G is related to the entropy change of the Universe, and for a reaction

to be spontaneous, ∆G for the reaction must be negative.

∆G = ∆H —T∆S

The units of ∆G are kJmol−1 and T must be in K. The subscripts are now
omitted, as both ∆H and ∆S refer to the system (the chemical reaction).

3. 30 Calculating ∆G
We can calculate ∆G for C2H2(g) + 2H2(g) ⟶ C2H6(g) given the following
information:
∆H = —313 kJ mol−1 and ∆S = −233JK−1 mol−1

∆G = —313 — 298 × (233/1000) = —244 kJmol−1

Entropy Bilal Hameed

Marginalizer Bilal Hameed
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3. 31 Calculating ∆G: example

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Consider the decomposition of Mg(NO3)2(s):

2Mg(NO3)2(s) ⟶ 2MgO(s) + 4NO2(g) + O2(g)

Mg(NO3)2(s) MgO(s) NO2(g) O2(g)

∆H f /kJmol −1 —790 —602 34 0

Sϴ / J K−1 mol−1 164 27 240 205

3. 32 Calculating ∆G: example

To calculate the enthalpy change, we have been given ∆Hf and so can use:
∆H = [(2 × —602) + (4 × 34) + 0] — [(2 × —790)] = 512 kJmol−1
To calculate the entropy change we use:
∆Sϴ = ΣSproducts — ΣSreactants
∆S = [(2 × 27) + (4 × 240) + 205] — [(2 × 164)] = 891 JK−1 mol−1
∆G = ∆H —T∆S
∆G = 512 — 298 × (891/1000) = 246 kJmol−1
Thus, at 298 K the reaction is not spontaneous because ∆G is positive.

3. 33 Skill Check 13
The values of the standard changes for the following reaction

4CuO(s) → 2Cu2O(s) + O2(g)

are ΔH ° = +287.4 kJ mol−1 and ΔS ° = + 232.5 J K−1 mol−1
Calculate the standard Gibbs free energy change for the reaction.

Bilal Hameed Entropy

Bilal Hameed Marginalizer
 14
12

3. 34 Skill Check 14

alt
Given the data below, calculate ∆G for the following reaction and state
whether it is spontaneous or not at 298 K:

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) ∆H = −2219 kJ mol−1

∆S = −373.3 J K−1 mol−1

3. 35 Skill Check 15
Calculate ∆G at 298 K for:

C2H2(g) + 2H2(g) → C2H6(g)

given information: ∆H = −313 kJ mol−1 ∆S = −233 J K−1mol−1
Is the reaction spontaneous?

3. 36 Skill check 19
Calculate the Gibbs free energy change for the decomposition of zinc
carbonate at 298 K.
ZnCO3(s) ⟶ ZnO(s) + CO2(g) ∆H = +71.0 kJmol–1
Values for ∆S in JK–1mol–1:
CO2(g) = +213.6, ZnCO3(s) = +82.4, ZnO(s) = +43.6

Answer: +18.9 kJmol–1

Entropy Bilal Hameed

Marginalizer Bilal Hameed
 15
13

3. 37 Skill Check 16

alt
Consider the decomposition of Pb(NO3)2(s):

2Pb(NO3)2(s) → 2PbO(s) + 4NO2(g) + O2(g) ∆H = +598 kJ mol−1

∆G = +333 kJ mol−1
Work out the value for ∆S at 298 K.

Part B: Short-answer questions Part C: Data-based question

1 a i Define the term standard enthalpy change
of formation. Substance Standard Absolute entropy,
(2 marks) enthalpy of S ʅ / kJ mol−1 K−1
formation,
H ̲ / kJ mol−1
ii Write an equation, including state symbols,
to show the formation of propane. C(s) 0.0 5.7
(1 mark) CO2(g) −393.5 213.6
3. 38 Skill Check 17 H2(g) 0.0 130.6
b i Use standard enthalpies of formation
Consider (Appendix
the decomposition of Mg(NO
3) to calculate 3)2(s)
the :
standard H2O(l) −285.9 69.9
enthalpy change of combustion ( H ̳) of O2(g) 0.0 205.0
2Mg(NO3)2(s) → 2MgO(s) + 4NO2(g) + O2(g)
propane, C3H8, for the following reaction. C3H7COOH(l) 226.3
Use the following data to work out ∆G and thus whether the reaction will
C3H8(g) 5O2(g) 3CO2(g) 4H2O(g)
be spontaneous at 25 °C. (5 marks) The enthalpy change for the combustion of butanoic
acid at 25°C is 2183.5 kJ mol 1. The combustion
ii Suggest, with a reason, whether the reaction is:
entropy change ( S ʅ) for the reaction C3H7COOH(l) 5O2(g) 4CO2(g) 4H2O(l)
would be positive or negative.
(2 marks) a Write the balanced equation for the formation of
butanoic acid from its elements.
iii Using standard entropy values in (1 mark)
Appendix 3, calculate the entropy
change for this reaction. b Using the above data, calculate the standard
(2 marks) enthalpy of formation, H ̲, for butanoic acid.
© IBO HL Paper 2 May 01 Q3 (3 marks)
3. 39 Skill Check 18
2 a Using the data below, c Calculate the standard entropy change, S ̲, for
Using the data below calculate for the reaction, at 25°C,
the formation of butanoic acid at 25°C.
Compound C4H8(g) CO2(g) H2O(g) O2(g) (3 marks)

s ʅ / J K−1 mol−1 306 214 189 205

d Calculate the standard free energy of formation,
G ̲, for butanoic acid at 25°C.
C4H8(g) + 6O2(g) → 4CO2(g) + 4H2O(g) ∆H° = −2545 kJ mol−1 (2 marks)
Calculate for the reaction, at 25°C,
(a) the
C4standard
H8(g) 6O entropy
2(g) change,
4CO2(g)∆S°. 4H2O(g)
1
e Is this reaction spontaneous at 25°C? Explain
Hʅ 2545 kJ mol your answer.
(b) theistandard free energy change, ∆G°. S ʅ. (1 mark)
the standard entropy change,
(2 marks) © IBO HL Paper 2 May 99 Q1

ii the standard free energy change, G ʅ.

(2 marks)

b Predict, giving a reason, the spontaneity of the

reaction at both high and low temperatures.
(2 marks)
Bilal Hameed © IBO HL Paper 2 May 07 Q6 f(mod), g Entropy
Bilal Hameed Marginalizer
 16
14

9 Describe how lattice enthalpies can be used3.to40 Skill

17 The Check
following20reaction is carried out at 25°C and
determine how closely the bonding in an ionic 1.01 102 kPa pressure.

alt
The following reaction is carried out at 25°C and 1.01 × 102 kPa pressure.
compound matches the ideal model of an ionic
SO3(g) H2O(l) H2SO4(l)
compound composed of spherical ions with their
charge distributed evenly across the surface. SO3(g) + H2O(l) → H2SO4(l)
Using the data in the table below, calculate H ʅ,
ʅ and
Using the data inSthe table ʅ for this
G below, reaction.∆H°, ∆S° and ∆G° for this reaction.
calculate
10 Considering the theoretical and experimental
lattice enthalpies shown in the table below,
compare the bonding in calcium fluoride and silver Substance H ̲(kJ mol−1) S ʅ(J K 1mol 1)
fluoride, and explain which compound most closely SO3(g) −396 256
matches the ideal model of an ionic compound.
H2O(l) −286 70
H2SO4(l) −814 157
Compound Theoretical Experimental
lattice lattice
enthalpy enthalpy
18 Ethyne reacts with hydrogen as follows:
(kJ mol 1) (kJ mol 1)
Strontium oxide 3205 3310 C2H2(g) H2(g) C2H4(g)
Silver fluoride 870 955 Use Appendix 3 to find H ʅrxn and S ʅ and hence
calculate G ʅ for this reaction.

11 Write the equations for the combustion of propane, 19 The addition reaction between steam and ethene
butane and pentane, and predict which reaction produces ethanol.
will have the greatest increase in entropy. 3. 41 Changing
a Write the temperature & ∆G
equation for this reaction
12 Using an example to illustrate your answer, b Use standard free energy values from table
Consider a reaction
explain why decomposition reactions are typically 4.4.2for
to which ∆HGisʅ positive
calculate and ∆S
for this reaction at is
273positive:
K.
accompanied by an increase in entropy. 20 The following reaction occurs between hydrogen
and iodine:
∆G = ∆H —T∆S
13 a Write the equation for the dissolution of
ammonium chloride in water.
2(g) temperatures,
In this case, atHlow I2(g) 2HI(g) the reaction is not spontaneous, as
b Use the equation you have written in part a to
T∆S is smallerathan Predict
∆H,theso change in entropy of this reaction.
∆G is positive.
predict how the entropy will change in this
b Using the following data, calculate H ʅrxn
reaction, giving a reason for your answer.
As the temperature andis S
raised,
ʅrxn. T∆S becomes larger, and as this is being
14 Using data from table 4.3.1, calculate the standard
subtracted from ∆H, ∆G becomes smaller.
entropy change for the substitution reaction Substance H ̲(kJ mol 1) S ̲(J K 1mol 1)
between ethane and chlorine: When T∆S is larger than ∆H, ∆G is negative.Therefore, as the
C2H6(g) Cl2(g) C2H5Cl(g) HCl(g) H2(g) 0 +131
temperature is increased,
I2(g) this reaction
0 becomes more spontaneous.
+261
15 Determine whether your prediction was accurate
HI(g) +25.9 206.3
in question 11 by calculating the standard entropy
change for the combustion of propane, butane
and pentane.
c Determine the lowest temperature for which
16 Explain why a reaction with a negative value of this reaction would be spontaneous.
H ʅ and a negative value of S ʅ is spontaneous
ENERGETICS

only at low temperatures.

3. 42 Changing temperature & ∆G
www.pearsoned.com.au/schools

∆G = Website
Weblinks are available on the Companion ∆Hto—T∆S
support learning and research
related to this chapter.
Now consider a reaction for which ∆H is positive and ∆S is negative. In
CHAPTER 4

this case, at low temperatures, the reaction is not spontaneous.

However, as ∆S is negative —T∆S in the equation is positive, and this
means that the value of ∆G will increase as the temperature is increased.
CHEMISTRY: FOR USE WITH THE IB DIPLOMA PROGRAMME 123
The consequence of —T∆S being positive is that this reaction will never
be spontaneous.

Entropy Bilal Hameed

Marginalizer Bilal Hameed
 17
15

3. 43 Changing temperature & ∆G

alt
Both the reactions considered here so far have been endothermic
reactions and it can be seen that:
an endothermic reaction can only occur spontaneously if it involves an
increase in entropy (and the temperature is sufficiently high).
An exothermic reaction (∆H negative) will always be spontaneous at some
temperature.

And if an exothermic reaction involves an increase in entropy (∆S

positive) then −T∆S will be negative. As ∆H is also negative, ∆G will
always be negative, and the reaction will always be spontaneous.

3. 44 Changing temperature & ∆G

Reactions for which ∆S is positive

become more spontaneous as
temperature increases, but reactions
for which ∆S is negative become
less spontaneous as temperature
increases.

26 Given the data below, calculate ∆G for the 29 Calculate ∆G for the following reaction, given
following reaction at 298 K and state whether it the ∆G f values in the table:
is spontaneous or not: C5H12(l) + 8O2(g) 5CO2(g) + 6H2O(l)
3. 45 Skill Check 21
C2H4(g) + H2(g) C2H6(g)
Consider the = −137
∆Hreaction of kJ mol−1 and with oxygen:
magnesium
∆S = −55.3 J K−1 mol−1
2Mg(s) + O2(g) → 2MgO(s) ΔH = −602 kJ mol−1
27 Given the data below, calculate ∆G for the
ΔS = −217 J K−1 mol
following reaction
−1 and state whether it is
spontaneous or not at 298 K:
(a) Why does the entropy of the system decrease? Is the reaction spontaneous at 298 K?
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
−1
(b) Show why∆H the
= reaction
−2219 kJof molmagnesium
and with oxygen is feasible at 298 the decomposition of Pb(NO3)2(s):
30 Consider
−1 −1
∆S = −373.3 J K mol
K despite the decrease in the entropy. 2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g)
−1
28 Calculate ∆G for the following reaction, given ∆H = +598 kJ mol ∆G = +333 kJ mol−1
the ∆G f values in the table: a Work out the value for ∆S at 298 K.
CaCO3(s) CaO(s) + CO2(g) b Assuming that ∆H and ∆S do not change
with temperature, calculate the temperature,
in °C, above which this reaction will become
spontaneous.
31 For each of the following reactions, predict
whether it becomes more or less spontaneous as
temperature increases:
a N2O4(g) 2NO2(g)
Bilal Hameed Entropy
Bilal Hameed bMarginalizer
N2(g) + 3H2(g) 2NH3(g)
c 2KNO3(s) 2KNO2(s) + O2(g)
d 2AgNO3(s) 2Ag(s) + 2NO2(s) + O2(g)
 18
16

3. 46 Skill Check 22

alt
Consider the reduction of iron(III) oxide by carbon:

2Fe2O3(s) + 3C(s) → 4Fe(s) + 3CO2(g) ΔH = +468 kJ mol−1

ΔS = +558 J K−1 mol−1
(a) Why does the entropy of the system increase for this reaction?
(b) Show that the reaction is not feasible at room temperature (298 K).
(c) Assuming that ΔH and ΔS do not vary with temperature, estimate the
temperature at which the decomposition becomes feasible.

3. 47 Skill Check 23
The values of the standard changes for the following reaction

4CuO(s) → 2Cu2O(s) + O2(g)

are ΔH ° = +287.4 kJ mol−1 and ΔS ° = + 232.5 J K−1 mol−1
(a) Calculate the standard free energy change for the reaction.
20 Further energy changes
(b) Calculate the temperature in °C at which the reaction becomes
feasible.
Worked example
For the reaction C2H4 (g) + HCl(g) → C2H5Cl(g), at 298 K,
∆H 1 = −96.7 kJ mol –1 and ∆G 1 = −25.9 kJ mol –1.
Calculate the value of ∆G 1 at 1000 K.
20 Answer Further energy changes
∆G = ∆H − T∆S
1 1 1

At 298 K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1

3.
∆S
48
1. −70
Worked
= Skill
800 check −124
example
= −239 J mol K−1
298
For1000
At the reaction C2−96.7
K, ∆G 1 =
∆H 1 = −96.7 kJ mol –1
and
(
H4 (g) +– HCl(g)
∆G
= +142 kJ mol
1000 →
=
1 -1
)
−239
× C2H5Cl(g), at 298 K,
1000 –1
−25.9 kJ mol .
Calculate the value of ∆G 1 at 1000 K.
This shows that as the temperature increases, the addition reaction becomes less feasible.
Answer
∆G 1 = ∆H 1 − T∆S 1
Now
At try
298this
K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1
−70 800 −1 −1
∆S 1.= the temperature
1 Calculate = −239 J at
mol K ∆G1 for the addition of HCl to ethene becomes
which
298
zero.
2 When KNO3 dissolves
(
At 1000 K, ∆G = −96.7 – 1000 ×
1

in water
= +142 kJ mol -1
−239
1000 )
at 298 K, ∆H 1 = +34.8 kJ mol−1 and ∆G1 = +0.3 kJ mol−1.
a Calculate ∆S 1.
This shows that as the temperature increases, the addition reaction becomes less feasible.
b Calculate ∆G1 at 320 K.
c Comment on the effect of temperature on the solubility of KNO3.
3 Heptane
Now try is converted
this into methylbenzene industrially:
C7H16(l) → C7H8(l) + 4H2(g)
1 300
Calculate
K, ∆Hthe
1 temperature –1
= +211 kJ mol at and ∆G∆1G= +110
which for the
kJaddition
mol−1. of HCl to ethene becomes
1
At
zero.
2 When∆G
Estimate KNOat:
1
−1
3 dissolves in water at 298 K, ∆H = +34.8 kJ mol
1
and ∆G1 = +0.3 kJ mol−1.
a 600 K
a Calculate ∆S 1.
b 900 K
b Calculate ∆G1 at 320 K.
c Explain why your
c Comment estimated
on the effect ofvalues will be on
temperature unreliable.
the solubility of KNO3.
Entropy 3 Heptane is converted into methylbenzene industrially:
Bilal Hameed
Marginalizer Bilal Hameed
C7H16(l) → C7H8(l) + 4H2(g)
Applying free energy changes
At 300 K, ∆H 1 = +211 kJ mol–1 and ∆G1 = +110 kJ mol−1.
The free energy
Estimate ∆Gof
1 a reaction tells us whether the reaction proceeds spontaneously
at:
 At 298 K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1
−70 800
∆S 1.= = −239 J mol−1 K−1
298
(
At 1000 K, ∆G 1 = −96.7 – 1000 ×
= +142 kJ mol-1
−239
1000 ) 19
This shows that as the temperature increases,17
the addition reaction becomes less feasible.

Now try this

3. 49 Skill check 26
1 Calculate the temperature at which ∆G1 for the addition of HCl to ethene becomes
zero.
2 When KNO3 dissolves in water at 298 K, ∆H 1 = +34.8 kJ mol−1 and ∆G1 = +0.3 kJ mol−1.

alt
a Calculate ∆S 1.
b Calculate ∆G1 at 320 K.
c Comment on the effect of temperature on the solubility of KNO3.
3 Heptane is converted into methylbenzene industrially:
C7H16(l) → C7H8(l) + 4H2(g)
At 300 K, ∆H 1 = +211 kJ mol–1 and ∆G1 = +110 kJ mol−1.
Estimate ∆G1 at:
a 600 K
b 900 K
c Explain why your estimated values will be unreliable.

Applying free energy changes

The free energy of a reaction tells us whether the reaction proceeds spontaneously
and this depends on the signs and magnitudes of both ∆H 1 and ∆S 1 for the reaction.
As ∆H 1 and ∆S 1 can each be positive or negative, there are four possibilities.

∆H3.
1
50
and ∆SSkill
1
bothCheck
positive 27
These reactions are said to be entropy driven. These endothermic reactions, which
The following reaction is only spontaneous at ‘high’ temperatures:
may not be feasible at room temperature, become feasible if the temperature is raised
(Le Chatelier’s Principle). The following
N +O are some examples:
→ 2NO
2(g) 2(g) (g)
● melting and boiling
If ∆H° = +180.8 kJ mol−1 and ∆S° = +24.7 J K−1 mol-1 deduce the
● decomposition reactions
● temperature at which the reaction begins to be spontaneous.
electrolysis
● dissolving (in some cases).

It is easy to see why both ∆H 1 and ∆S 1 are positive for melting and boiling (see
Figure 20.10). The change is endothermic because intermolecular bonds are being
broken. There is an increase in the entropy because disorder increases from solid to
liquid to gas.
Most decomposition reactions (for example, the cracking of alkanes and the
thermal decomposition of calcium carbonate) are endothermic because the total bond
enthalpy in the products is less than that in the reactants. The energy required to
break relatively strong bonds is not recovered by the formation of fewer or weaker
bonds. Decomposition reactions are accompanied by an increase in entropy because
the change in number of molecules, ∆n, is positive.
3. 51 Skill Check 28
NH4NO3(s) + aq → NH4+(aq) + NO3−(aq) 339

Find the minimum temperature at which this reaction will be

9
spontaneous. 10/10/14 9:31 PM

∆H° = +28.05 kJ mol−1

∆S° = 108.7 J K−1 mol−1

Bilal Hameed Entropy

Bilal Hameed Marginalizer
 20
18

3. 52 Skill Check 29

alt
Electrolysis is usually used to extract aluminium metal. In principle, it
should be possible to extract the metal by heating its oxide with carbon.

(a) Write the equation for the reduction of aluminium oxide by carbon,
assuming that the carbon is converted to carbon monoxide.
(b) Calculate the standard enthalpy change for the reduction reaction.

3. 53 Skill Check 29 - Continued

(c) Calculate the standard entropy change for the reduction reaction.
(i) Calculate the standard free energy change for the reduction at 298 K.
(ii) What does your answer to part (d)(i) tell you about the feasibility of the
reaction at 298 K?
(d) Calculate the minimum temperature at which the reduction of aluminium
oxide by carbon becomes feasible.
(e) Suggest a reason why the reaction between aluminium oxide and
carbon does not happen to a significant extent until the temperature is
about 1000 degrees higher than your answer to part (d).

Entropy Bilal Hameed

Marginalizer Bilal Hameed