CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

Exam-style questions and sample answers have been written by the authors. In examinations, the way marks are awarded
may be different.

Coursebook answers
Chapter 23
Science in context Self-assessment questions
Students are introduced to entropy via the Second 1 a Raise 2 (for two gas jars) to the power
Law of Thermodynamics. Entropy changes do not of the number of molecules (4):
account fully for the essential features of rubber 24 = 2 × 2 × 2 × 2 = 16
because loosely held molecules should slide past
each other and untangle as well as uncoiling when b As there are 16 ways, the probability of
a pulling force is applied. Polymers such as rubber any one of these arrangements is 1 in 16.
(elastomers) seem to have a ‘molecular memory’ c i spontaneous (because there are
which enables them to return to their original more ways of spreading out the
arrangement. The reason for this elastic recovery sugar molecules when they dissolve)
is that the coiled chains in unstretched rubber
ii spontaneous (because there are
are looped round each other so they are more or
more ways of spreading out the
less knotted together in some places. This effect
ammonia molecules when they
is greatly enhanced in synthetic elastomers by
mix with the air molecules)
replacing the ‘knots’ with cross links. These
permanently anchor the chain at various points. iii not spontaneous (because ice
The best elastomers have only a small amount of forms at 0 °C and the energy
cross linking so that they can successfully combine transferred from the surroundings
large movement of parts of the chain whilst not at 10 °C gives the molecules
interfering with the cross-linked parts. enough energy to move semi-
independently of each other and
Students are then asked to think of some so there are a greater number of
environmental issues relating to rubber production. ways of arranging the energy in
They should be reminded of some of the similar the liquid than in the solid)
issues mentioned in Chapters 3, 6 and 16.
iv spontaneous (because there
These include: is enough energy given to the
• pollution of waterways by run-off of pollutants molecules at 20 °C for some of
from the large quantities of water used in washing them to escape, thus allowing
the rubber (the ammonia and phosphates used more spreading out of molecules
will cause eutrophication) in the vapour than in the liquid)
• toxic hydrogen sulfide may be breathed in by v not spontaneous (because the
workers strength of the bonding between
water molecules alone is greater
• harmful acids may get into the soil and water or than the strength between water
affect workers handling the sheets of rubber and oil molecules; so the oil
• wood smoke produces particulates which are molecules cannot mix and spread
harmful to health and can cause cancer between the water molecules)
• collection and transport of rubber from lots of vi not spontaneous (because the
small areas requires lorries and therefore further temperature is not high enough
pollution from dust / combustion of diesel fuel. to break bonds in the limestone
(calcium carbonate); the ions in the
calcium carbonate remain ordered)

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK
2 a Bromine is a liquid, so its molecules
are able to rotate / slide over each
other so there is more disorder (higher
entropy) than in iodine, which is a
solid, in which the molecules cannot move.
b Both are gases but methane, CH4, is
a more complex molecule with two
different types of atom. Complex
molecules tend to have greater entropy
values than simpler molecules.
c Mercury is a liquid, so its atoms are
able to rotate / slide over each other so
there is more disorder (higher entropy)
than in sodium, which is a solid, in
which the atoms cannot move.
d Although SO3 has only one oxygen
atom more than SO2, which makes
SO3 a slightly more complex molecule,
SO2 has a much greater entropy
because it is a gas, whereas SO3 is a
liquid. The particles in gases move
freely from place to place and so there
is more disorder are many more ways
of spreading out the energy than
in liquids whose particles can only
rotate / slide over each other and vibrate.
3 a The entropy of the reactants is greater.
Two gases (high entropy and two
molecules) are being converted to a
solid (low entropy and one molecule).
b Difficult to decide. The product SO2 is
a gas, which is likely to have a higher
entropy than oxygen because it is a
more complex molecule. However,
there are two molecules on the left and
only one on the right. The entropy of
the solid sulfur, however, is low.
(The entropies in J K−1 mol−1:
S  [S(s)] = 31.8
S  [O2(g)] = 205
S  [SO2(g)] = 248.1
show that the sum of the entropies of
the reactants and the entropy of the
product are similar.)
c The entropy of the reactants is greater.
One of the reactants, carbon dioxide,
is a gas, so has a very high entropy.
This outweighs the entropies of the
products which are both solids. Solids
have low entropies.
2 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020
d The entropy of the reactants is greater.
One of the reactants, chlorine, is a
gas, so has a very high entropy. This
outweighs the entropies of the single
product which is a solid. Solids have
low entropies.
e The entropy of the products is greater.
Two gases are produced (2 moles
of gases) both of which have high
entropy. The reactants have only one
gas (1 mole of gas). The entropies of
the solids are much smaller than those
of the gases and so can be ignored.
f Difficult to decide. There are equal
numbers of moles of gases on each
side of the equation. We would have
to know the individual values of the
entropies of each molecule.
g The entropy of the products is greater.
Reactants: potassium has low entropy
because it is a solid; water has medium
entropy because it is a liquid.
Products: aqueous potassium
hydroxide has medium entropy (not
only is it a liquid, but potassium ions
and hydroxide ions are spread out
randomly in the solution); hydrogen
has high entropy because it is a gas.
If we assume that water and aqueous
potassium hydroxide have similar
entropies, the production of hydrogen
gas causes the entropy of the products
to be greater.
h The entropy of the products is greater
because carbon dioxide is a gas and
therefore has more disorder than
either magnesium carbonate or the
magnesium oxide.
4 a ∆Ssystem

= ∑ Sproducts

– ∑ Sreactants

= 2 × S  [H2O(l)] + S  [O2(g)] −
 2 × S  [H2O2(l)]
= (2 × 69.90) + 205.0 − 2 × 109.6
= 344.8 − 219.2
∆Ssystem

= + 125.6 J K−1 mol−1
b ∆Ssystem

= ∑ Sproducts

– ∑ Sreactants

= S  [N2O(g)] + 2 × S  [H2O(g)] − S 
[NH4NO3(s)]
= 219.7 + 2 × 109.6 − 151.1
 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

= 438.9 − 151.1 d enthalpy change = +34.30 × 1000

∆S

system = +287.8 J K mol −1 −1
= +34 300 J mol−1
 
c ∆Ssystem

= ∑ Sproducts

– ∑ Srectants

temperature in K = −3 + 273 K = 270 K
= 2 × S [MgO(s)] − {2 × S [Mg(s)] +
  ∆H reaction

∆Ssurroundings

=
 S  [O2(g)]} T

= 2 × 26.90 − {(2 × 32.70) + 205.0}   =
– ( +34 300)
270
= 53.8 − 270.4
  = −127.0 J K−1 mol−1
∆Ssystem = −216.6 J K−1 mol−1


6 a ∆S 
system = ∑ Sproducts

– ∑ Sreactants


d ∆Ssystem

= ∑ Sproducts

– ∑ Srectants


= 2 × S  [NaCl(s)] − {2 × S  [Na(s)] + = S  [H2S(g)] − {S  [S(s)] + S  [H2(g)]}

 S  [Cl2(g)]} = 205.7 − {31.80 + 130.6}
= 2 × 72.10 − {(2 × 51.20) + 165.0} = 205.7 − 162.4
= 144.2 − 267.4 ∆Ssystem = +43.3 J K−1 mol−1


∆S 
= −123.2 J K mol −1 −1
∆H 
system
∆Ssurroundings

= reaction
e ∆S 
system = ∑S 
products –∑ S 
rectants
T
– ( −20.6 × 1000)
= 3 × S  [MgO(s)] + 2 × S  [Fe(s)]   = 298
− {3 × S  [Mg(s)] + S  [Fe2O3(s)]}
  = +69.1 J K−1 mol−1
= (3 × 26.90) + (2 × 27.30) −
∆Stotal

= Ssystem

+ Ssurroundings

{(3 × 32.70) + 87.40}
= 135.3 − 185.5       = +43.3 + (+69.1)
∆Ssystem

= −50.2 J K−1 mol−1 ∆Stotal = +112 J K−1 mol−1


5 a enthalpy change = −393.5 × 1000 b ∆Ssystem


= Sproducts
 
– Sreactants
= −393 500 J mol−1 = S  [C2N2(g)] − {2 × S  [C(s)] +
temperature in K = 0 + 273 K = 273 K  S  [N2(g)]}
∆H reaction


∆Ssurroundings

= = 242.1 − {2 × 5.700 + 191.6}
T
– (–393 500) = 242.1 − 203.0
= 273
∆Ssystem = +39.10 J K−1 mol−1


= +1441 J K mol −1 −1
∆S  ∆H reaction


b enthalpy change = +307.9 × 1000 surroundings =

T
= +307 900 J mol−1 – ( +307.9 × 1000)
   = 298
temperature in K = 330 + 273 = 603 K
∆H reaction
    = −1033 J K−1 mol−1
∆Ssurroundings

=
T
∆Stotal = Ssystem + Ssurroundings
  
– (–307 900)
 = 603    = +39.10 − 1033
 = +510.62 J K−1 mol−1 ∆Stotal = −994 J K−1 mol−1


c enthalpy change = −271.1 × 1000 c ∆Ssystem


= Sproducts
 
– Sreactants
= −271 100 J mol−1
  [P4O10(s)] − {4 × S  [P(s)] + 5 × S 
= S
temperature in K = 298 K [O2(g)]}
∆H reaction

∆Ssurroundings

= = 228.9 − {4 × 41.10 + 5 × 205.0}
T

– (–271100)
= 228.9 − 1189.4
=
∆Ssystem = −960.5 J K−1 mol−1

298
= +909.7 J K−1 mol−1 ∆H 
∆Ssurroundings

= reaction
T

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– ( −2984 × 1000) iii zero; this is because at equilibrium

             =
298 
Stotal (forward reaction) = Stotal


             = +10 013 J K−1 mol−1 (backward reaction)

8 a Step 1: convert the value of ∆H r to

∆Stotal = Ssystem + Ssurroundings
  

J mol−1 −184.6 × 1000 = −184 600 J mol−1

           = −960.5 + 10 013
Step 2: calculate ∆Ssystem

∆Stotal

= 9053 J K−1 mol−1
∆Ssystem

= ∑ Sproducts

– ∑ Sreactants


d ∆S = ∑S – ∑S
  
system products reactants
= 2 × S  [HCl(g)] − (S  [H2(g)] +
= 3 × S [CO2(g)] + 4 × S [H2O(l)] −
 
 S  [Cl2(g)])
{ S  [C3H8(g)] + 5 × S  [O2(g)]} = 2 × 186.8 − (130.6 + 165.0)
= (3 × 213.6) + (4 × 69.90) − {269.9 + = 373.6 − 295.6
5 × 205.0}
∆Ssystem

= +78.0 J K−1 mol−1
= 920.4 − 1294.9
Step 3: calculate ∆G 
∆S

= −374.5 J K mol −1 −1
∆G = ∆H reaction – T ∆Ssystem
system   

∆Ssurroundings ∆H 
  = −184 600 − (298 × +78.0)

= reaction
T
∆G  = −207 844 J mol−1
– ( −2219.2 × 1000)
  = 298   = −208 kJ mol−1 (to 3 significant
  = +7447 J K−1 mol−1 figures)
As the value of ∆G  is negative, the
∆Stotal = Ssystem + Ssurroundings
  
reaction is spontaneous at 298 K.
= −374.5 + 7446.9 b Step 1: convert the value of ∆H r to
∆S 
total = +7072 J K mol −1 −1
J mol−1 −890.3 × 1000 = −890300 J mol−1
7 a ∆S 
surroundings is calculated from Step 2: calculate ∆Ssystem

∆Ssystem = Sproducts – Sreactants

  
−∆H reaction

/ T . So, as the temperature,
T, increases, the value of ∆Ssurroundings
   [CO2(g)] + 2 × S  [H2O(l)] −
= S
gets less negative if the value of  S  [CH4(g)] + 2 × S  [O2(g)]
∆H reaction

is positive. The enthalpy = 213.6 + (2 × 69.9) − (186.2) − (2 × 205.0)
change of the surroundings may = 353.4 − 596.2
then be sufficiently low so that ∆Ssystem

= −242.8 J K−1 mol−1
∆Ssystem

+ ∆Ssurroundings

is a positive
Step 3: calculate ∆G 
entropy change.
∆G = ∆H reaction – T ∆Ssystem
  

b i a system in which there is

exchange of energy with the   = −890 300 − (298 × −242.8)
surroundings but no loss or gain ∆G  = −817 946 J mol−1
of matter to or from the surroundings
= −818 kJ mol−1 (to 3 significant
 
ii The volume of gas is decreased, figures)
so the carbon dioxide molecules
As the value of ∆G  is negative, the
are closer together. The closer the
reaction is spontaneous at 298 K.
molecules, the lower the degree of
randomness or disorder and the c Step 1: convert the value of ∆H r to
lower the entropy. So the position J mol−1
of equilibrium shifts towards the −510.9 × 1000 = −510 900 J mol−1
left, where there are fewer gas
Step 2: calculate ∆Ssystem

molecules. The calcium carbonate
∆Ssystem = ∑ Sproducts – ∑ Sreactants
  
and calcium oxide play little part
because their entropy is very low. = S  [Na2O2(s)] − {(2 × S  [Na(s)] + S 
[O2(g)])}

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

= 95.0 − (2 × 51.2) + 205.00) As the value of ∆G  is positive, the

= 95.0 − 307.4 reaction is not spontaneous at 298 K.
∆Ssystem

= −212.4 J K−1 mol−1 9 B (−39.4 kJ mol−1)
Step 3: calculate ∆G  10 a ∆Greaction

= ∆Gproducts

– ∆Greactants


∆G

= ∆H reaction

– T ∆Ssystem

∆Greaction

= 2 × ∆Gf [H2O(l)] +
  = −510 900 − (298 × −212.4) ∆Gf [O2(g)] − 2 × ∆Gf [H2O2(l)]


∆G  = −447 604.8 J mol−1 = 2 × (−273.2) + 0 − 2 × (−120.4)

 
 = −448 kJ mol−1 (to 3 significant = −546.4 − (−240.8)
 
figures) ∆Greaction

= −305.6 kJ mol−1
As the value of ∆G is negative, the 
The value of ∆Greaction

is negative. So
reaction is spontaneous at 298 K. under standard conditions, hydrogen
d Step 1: convert the value of ∆H r to peroxide should spontaneously
J mol−1 decompose to water and oxygen.
−641.3 × 1000 = −641 300 J mol−1 b ∆Greaction

= ∆Gproducts

– ∆Greactants


Step 2: calculate ∆Ssystem


∆Greaction

= ∆Gf [N2O(g)] + 2 × ∆Gf
∆S =S [H2O(g)] − ∆Gf [NH4NO3(s)]
  
system products –S
reactants

= S [MgCl2(s)] − (S  [Mg(s)] +

 = (+104.2) + 2 × (−228.6) −
S  [Cl2(g)]) (−184.0)
= 89.6 − (37.2 + 165.0) ∆Greaction

= −169.0 kJ mol−1
∆Ssystem

= −108.1 J K−1 mol−1 The value of ∆Greaction

is negative.
So under standard conditions,

Step 3: calculate ∆G 
ammonium nitrate will spontaneously
∆G = ∆H reaction – T ∆Ssystem
  
decompose to N2O(g) and H2O(g).
  = −641 300 − (298 × −108.1) c ∆Greaction

= ∆Gproducts

– ∆Greactants


∆G 
= −609 086.2 J mol −1
∆Greaction

= 2 × ∆Gf [MgO(s)] −
=
 −609 kJ mol (to 3 significant −1
{2 × ∆Gf [Mg(s)] + ∆Gf [O2(g)]}


figures)  = 2 × (−569.4) − (0 + 0)
As the value of ∆G  is negative, the ∆G 
= −1138.8 kJ mol−1
reaction
reaction is spontaneous at 298 K.
The value of ∆Greaction

is negative. So
e Step 1: convert the value of ∆H r to under standard conditions, magnesium
J mol−1 will spontaneously react with oxygen.
+167.5 × 1000 = +167 500 J mol−1 
11 a Ecell = −0.13 + (+0.14) = +0.01 V
Step 2: calculate ∆S 
system electrons transferred = 2
∆Ssystem = ∑ Sproducts – ∑ S
  
reactants
substitute the values into the
= S  [Ag2O(s)] + S  [CO2(g)] − expression ∆G  = −nFEcell
.
 S  [Ag2CO3(g)]) ∆G  = −2 × 96 500 × (+0.01)
= 121.3 + 213.6 − 167.4  = −1.93 kJ mol−1
∆Ssystem

= +167.5 J K−1 mol−1 The value of ∆G  is very small

Step 3: calculate ∆G  and negative and Ecell is very small
and positive, so both reactants and
∆G = ∆H reaction – T ∆Ssystem
  
products are present and the products
  = +167 500 − (298 × +167.5) predominate. So Kc is just above 1
∆G  = −33 165 J mol−1
= 33, 2 kJ mol−1 (to 3 significant figures)

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK


b Ecell = +0.77 + (−0.8) = −0.03 V = (2 × 213.6) + (3 × 69.90) − {160.7
+ (3 × 205.0)}
electrons transferred = 1
= 636.9 − 775.7
substitute the values into the
expression ∆G  = −nFEcell
. ∆Ssystem

= −138.8 J K−1 mol−1
∆G  = −1 × 96 500 × (−0.03) 
−∆H reaction
∆Ssurroundings =

 = +2.9 kJ mol−1 T

The value of ∆G  is very small – ( –1367 × 1000 )

  =

and positive and Ecell is very small 298
and negative, so both reactants and = +4587.2 J K−1 mol−1
products are present and the reactants ∆Stotal

= ∆Ssystem

+ ∆Ssurroundings


predominate. So Kc is below 1 e.g. 0.01

= −138.8 + 4587.2

c Ecell = −1.66 + (+2.33) = +0.67 V
∆S 
total = + 4448 J K−1 mol−1
electrons transferred = 3
Correct multiplication of data and use
substitute the values into the of ∆Ssystem

= ∑ Sproducts

− ∑ Sreactants


expression ∆G  = −nFEcell
. i.e. 2 × 213.6 + 3 × 69.90 −
∆G  = −3 × 96 500 × (+0.67) {160.7 + 3 × 205.0}  [1]
 = −194 kJ mol−1 
Correct answer for Ssystem =
The value of ∆G  is large and   −138.8 J K mol / 139 (J K−1 mol−1)  [1]
−1 −1


negative and Ecell is large and positive, Correct application of relationship for
so the reaction goes more or less to ∆Ssurroundings

(× 1000, division by 298
completion. So Kc has a high value. and − sign in relationship)  [1]
∆Ssurroundings

= +4587.2 (J K−1 mol−1)  [1]
Exam-style questions ∆Stotal

Correct =S 
use of ∆Stotal

= Ssystem

system
1 a i Graphite is softer than diamond. [1]
+∆Ssurroundings

+∆Ssurroundings
/ +4448
(J K−1 mol−1) [1]
Graphite has weak forces between
Correct units for entropy, J K−1 mol−1,
the layers but diamond has only
anywhere in question.  [1]
strong (covalent) bonding / greater
rigidity in bonding in diamond b C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O 
than graphite. [1] −174.9 2(−394.4) + 3(−237.2)[1]
ii ∆S 
system = ∑S 
products − ∑S 
reactants use of ΣG 
− ΣGreactants

products

= 2.40 − 5.70 = −3.30 J K−1 mol−1 [1] −1500.4 − (−174.9) [1]

iii The entropy change is negative. [1] = − 1325.5 kJ mole−1  [1]
b entropy of product greater (no marks c Use of ∆G  = ∆H  − T∆S  
  
[1]
alone but maximum 1 mark for −1325.5 × 1000 = ∆H  − 298 × 

question if not present) Graphite has (−138.3) (in joules) [1]

very low entropy because it is a solid
with only one type of atom and oxygen ∆H  = −1325500 + 41213.4 =
has high entropy because it is a gas.  [1] −1284286.6 J mol−1 / −1284.3 kJ mol−1 [1]

Carbon dioxide has high entropy [Total: 12]

because it is a gas and higher than 3 a Molecules in ice do not move from
oxygen as it is a more complex molecule / place to place / only vibrate. So
has three atoms rather than two.  [1] entropy is low.[1]
[Total: 6] Molecules in water can rotate / slide
2 a ∆S 
= ∑S 
− ∑S  over each other. So entropy is higher.  [1]
system products reactants
b When water is being heated the
= 2 × S [CO2(g)] + 3 × S o [H2O(l)]

molecules are moving faster and more
− {S  [C2H5OH(l)] + 3 × S  [O2(g)]} randomly.  [1]

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Entropy increases due to more ways of ∆Ssystem


= +171.9 J K−1 mol−1
spreading the energy. [1] ∆Ssurroundings


When water boils the entropy increases −∆H reaction



by a larger amount [1] =

T
because the molecules in gas have more – ( + 269 × 1000 )
random movement than in liquid / =
298
more ways of spreading the energy in = −902.7 J K−1 mol−1
gas compared with a liquid. [1]
∆Stotal = ∆Ssystem + ∆Ssurroundings
  

c Water is hydrogen bonded [1]

which gives it some structure so that = 71.9 + (−902.7)
entropy is lower.  [1] ∆S 
total = −730.8 J K−1 mol−1
Bromine only has temporary dipole- Correct answer for
induced dipole forces between molecules [1] ∆Ssystem

= +171.9 (J K−1 mol−1)  [1]
so movement of the molecules is more Correct application of relationship for
free so entropy is higher. [1] ∆Ssurroundings

(× 1000, division by 298
d When 2 g potassium chloride added and − sign in relationship)  [1]
it dissolves and the ions spread out ∆Ssurroundings

= (−902.7) (J K−1 mol−1)  [1]
randomly in the water / move freely
compared with the ionic lattice where Correct use of ∆S 
total = −730.8
they cannot move. [1] (J K−1 mol−1)  [1]

There are more ways of arranging the Correct units for entropy, J K−1 mol−1  [1]
particles of K+, Cl− and water so the c use of ΣGproducts

− ΣGreactants


entropy increases.  [1] (−525.1 + (−394.4)) − (−1137.60) [1]

Adding more potassium chloride = + 218.1 kJ mole [1] −1

increases the number of particles of d Reaction is not feasible at 298 K because

K+ and Cl− dissolved so there are more the value of ΔG  is large and positive [1]
ways of arranging the ions and so the
entropy increases.[1] e ∆Stotal

= ∆Ssystem

+ ∆Ssurroundings


The percentage increase in entropy 0 = 171.9 + ∆Ssurroundings



is smaller because there are already

So ∆Ssurroundings

must be −171.9 J K−1 mol−1
ions present. This reduces the number
of arrangements available to the ions By substitution:
compared with when dissolved in −∆H 
∆Ssurroundings

=
water alone. [1] T
– ( +269 × 1000 )
[Total: 14] =
T
4 a ∆H f [BaCO3(s)] + ∆H reaction

= = −171.9 J K−1 mol−1
∆H f [BaO(s)] + ∆H f [CO2(s)]
 

So −171.9 × T = −269 000 and T = 1565 K

−1216.0 + ∆H reaction

= −553.5 + −393.5
∆H reaction

= +269.0 kJ mol−1 For ∆Ssurroundings

= −171.9 J K−1 mol−1
if  ∆Stotal

is zero  [1]
Correct application of Hess cycle.  [1]
Correct application of relationship
∆H reaction = +269 kJ mol−1 

[1]
for ∆Ssurroundings

(× 1000, division by 298
b ∆Ssystem

= Sproducts

− Sreactants


and − sign in relationship and value =

= S  [BaO(s)] + S  [CO2(g)] −
−171.9 (J K−1 mol−1)  [1]
S  [BaCO3(s)]
T = 1565 (K) / 1292 (°C)  [1]
= 70.40 + 213.6 − 112.1
Correct unit of temperature, i.e. K
= 284.0 − 112.1
(allow °C if answer 1292)  [1]
[Total: 14]

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 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

5 a i E
 ntropy of NaCl is low because it (allow 2C(s))
is ordered / ions only vibrate.  [1] correct reactants and product  [1]
Entropy of water is medium / higher correct state symbols  [1]
than for NaCl because it is less
ordered (or has degree of disorder).  [1] b i ∆G 
= ∆H 
reaction − T ∆S 
system  [1]
Dissolved ions have more disorder ii ∆G 
is negative.  [1]
so greater entropy because free to ∆H 
needs to be taken into
reaction
move.  [1] account.  [1]
Entropy of water decreases If value of ∆H is negative 
reaction
because of the hydration layer
enough, its value will overcome
around the ions. (Allow: entropy
the positive value of the −T ∆Ssystem

of water doesn’t change much.)  [1]
term / overcome the large negative
So entropy increases (dependent value of ∆Ssystem

. [1]
on suitable arguments indicating
entropy of solution greater than c ∆Greaction

= ∆Gproducts

− ∆Greactants


entropy of NaCl and water).  [1] (or correct use of relationship)  [1]
[If entropy decreases given as an = 2 × ∆G [CO2(g)] + 3 × ∆G [H2O(l)]
 

answer, max. 3 marks for question.] 1

  − { ∆G  [C2H6(g)] + 3 2 × ∆G  [O2(g)]}
ii Entropy of H2O(g) is high because = 2 × (−394.4) + 3 × (−237.2) − (−32.9 + 0)
the particles are disordered.  [1]
= −1500.4 + 32.9
Entropy of H2O(l) is medium /
lower because the particles are less Correct use of mole ratios, i.e. × 2 for
ordered than in H2O(g).  [1] carbon dioxide, etc.  [1]
So entropy decreases (dependent ∆Greaction

= −1467.5 kJ  [1]
on suitable arguments indicating [Total: 11]
entropy of vapour greater than 7 a ∆Ssystem

= ∑ Sproducts

− ∑ Sreactants


entropy of liquid).  [1]

(or correct use of relationship)  [1]
[If entropy increases given as an
= S [CaO(s)] + S [CO2(g)]
 
answer, max. 1 mark for question.]
− S  [CaCO3(s)]
b i Entropy increases from CH4 to
= 39.7 + 213.6 − 92.9
C4H10 and then decreases to C5H12. [1]
∆Ssystem

= +160.4 J K−1 mol−1  [1]
CH4 to C4H10 are in the same
state but there are more atoms / b ∆H reaction

= ∆H f [products]
more electrons / more complex − ∆H f [products] (or correct use of
molecules as the series is ascended. [1]
relationship or enthalpy cycle)  [1]
C5H12 is a liquid, so the entropy
is relatively lower (compared with = ∆H f [CaO(s)] + ∆H f [CO2(g)]
gaseous molecules of similar size); [1]
  − ∆H f [CaCO3(s)]
less randomness / disorder in
liquid than in gas.  [1] = −631.5 + (−393.5) − (−1206.9)

ii Allow values between 280 and 310 ∆H reaction


= + 181.9 kJ mol−1  [1]
J K−1 mol−1 (actual value 295.9).  [1] c Use of ∆G  = ∆H reaction

− T ∆Ssystem

 [1]
[Total: 13]
Multiplication of ∆H 
reaction by 1000  [1]
6 a i T
 he free energy change when 1
Correct substitution of values from
mole of a compound  [1]
parts a and b  [1]
is formed from its elements under
e.g. ∆G  = ∆H reaction

+ T ∆Ssystem

standard conditions.  [1]
ii 2C(graphite) + 3H2(g) → C2H6(g) = (181 900 − (298 × 160.4)
 

8 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020

 CAMBRIDGE INTERNATIONAL AS & A LEVEL CHEMISTRY: COURSEBOOK

∆G  = + 134 100 (J mol−1) or c As the value of ∆G  is negative, the

+ 134 (kJ mol−1) (to 3 significant figures)  [1] reaction is spontaneous at 298 K.  [1]
Correct units in answer or other d Half the value for the answer to
relevant part of question.  [1] part b, i.e. −237 kJ mol−1  [1]
d As the value of ∆G is positive, the
Because in the equation there are 2
reaction is not spontaneous at 298 K.  [1] moles of water / free energy change
∆Ssystem alone is not a good guide to
 of formation refers to 1 mole of
whether a reaction is spontaneous or not.[1] substance formed.  [1]
Because the surroundings are not [Total: 11]
taken into account / only of ∆G  takes 9 a i + 0.75 V [1]
account of the surroundings as well as 
ii The sign of Ecell is fairly large and
the system.  [1]
positive [1]
[Total: 12]
b i use of ∆G  = −nFE cell

[1]
8 a ∆S 
system = ∑S 
products − ∑S 
reactants − 2 × 96500 × − 0.94 [1]
(or correct use of relationship)  [1] +181420 J mol / +181.4 kJ mol  [1]
−1 −1

= 2 × S  [H2O(l)] − (2 × S  [H2(g)]) ii The value of ∆G  is large and

+ (S  [O2(g)]) positive so the reaction is not
= 2 × 69.9 − [(2 × 130.6) + 205.0] feasible.[1]
= 139.8 − 466.2 The position of equilibrium
will be well over to the left / the
Correct use of mole ratios, i.e. × 2 for
reaction is not likely to happen,
water and hydrogen  [1]
so the value of Kc will be very
∆Ssystem

= −326.4 J K−1 mol−1  [1] low e.g. 10−5. [1]
b Use of ∆G 
= ∆H 
reaction − T ∆S 
system  [1] c i use of ΣG  − ΣG 

products

reactants
(− 77.6) − (+ 65.5)[1]
Multiplication of ∆H reaction

by 1000  [1]   

= − 143.1 kJ mole−1[1]
Correct substitution of values from
part a [1] ii use of ∆G  = −nFE cell


e.g. ∆G  = ∆H reaction ∆G 

+ T ∆Ssystem


E cell =− [1]
nF
= −561 600 + (298 × −326.4)
∆ G 
= −474 000 (J) or − 474 (kJ) ( −143.1  ×  1000 )
= − [1]
2  ×  96500
(to 3 significant figures)  [1]
Correct units in answer or other = 0.74 V[1]
relevant part of question.  [1] [Total: 12]
[Allow: kJ mol−1 or J mol−1 if referring
to oxygen in equation.]

9 Cambridge International AS & A Level Chemistry © Cambridge University Press 2020