A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 1

ENTHALPY OF ATOMISATION
a) The standard enthalpy of atomisation of an element is the energy required ()
to produce 1 mole ()
of gaseous atoms ()
from the element in its standard state / most stable state under standard conditions ()
The standard enthalpy of atomisation of a compound is the energy required ()
to convert 1 mole ()
of the gaseous compound ()
into gaseous atoms under standard conditions ()
b) Enthalpy of atomisation of hydrogen = HH bond dissociation enthalpy (1)
c) (i)

920/2 = 460 kJ mol-1 (1)

(ii) Data book value includes values for the OH bond in other molecules (1)
d) (i)

C(s) + 2H2(g) CH4(g) (1 mark for formulae & balance; 1 for state symbols)

(ii) H for bond breaking: 715 + (4 218) = +1587 kJ mol-1 (1)

H for bond making: -4 Hbe (CH) (1)
Hof (CH4) = -74.9 = + 1587 - 4Hbe (CH) (1)
Hbe (CH) = (1587 + 74.9)/4
= 415 kJ mol-1 (1)
Or

+715 kJ mol-1

C(g)
+2H2(g)

4(+218) kJ mol-1

-74.9
kJ mol-1

CH4(g)

C(g)
4H(g)

4Hbe (C

H)

(2) Deduct 1 mark for each error

Or accept an enthalpy diagram (2)

By Hesss law,
-74.9 + 4Hbe (CH) = +715 + 872 (1)
Hbe (CH) = (715 + 872 + 74.9)/4 = 415 kJ mol-1 (1)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 2

HYDRATION ENTHALPIES OF IONS

a) Heat evolved / enthalpy change ()

when 1 mole () of gaseous ions ()
is hydrated by an infinitely large quantity of water ()
b) (i)

Change

Decreases (1)

Reason

Increasing size / ionic radius (1)

(ii) Change

Increases (1)

Reasons

Increasing charge (1) and decreasing size / ionic radius (1)

(iii) Change

Decreases (1)

Reason

Increasing size / ionic radius (1)

c) H+ is very small (1)

It has a high charge density on its surface (1)
and strongly attracts water molecules (1)
A bond is formed / H+ + H2O H3O+ (1)
Or

d) (i)
HCl (g)

+431
kJ

H+(g) + Cl(g) + emol -1

-364
kJ mol-1

+1310
kJ mol-1

H(g) + Cl(g)

H+(g)
H conversion

-1200
kJ mol-1

+1310
kJ mol-1

-364
kJ mol-1

H(g)

+ Cl-(g)

+ Cl(g)

+431
kJ mol-1

H+(g) + Cl-(g)

-1200
kJ mol-1

HCl (g)
H+(aq)

-364
kJ mol-1

H conversion

H+(aq) + Cl-(aq)

+ Cl-(g)

-364
kJ mol-1

H+(aq) + Cl-(aq)

Mark cycle or diagram out of 3: (1) for correct stages, (1) for arrows correctly pointed and (1) for correct labels on
arrows.
(ii) H conversion

= +431 + 1310 + (-364) + (-1200) + (-364) (1)

= -187 kJ mol-1 (1)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 3

LATTICE ENTHALPY
a) Enthalpy / heat required to separate the gaseous ions (1)
in 1 mole of solid (1)
to an infinite distance from one another (1)
Or enthalpy / heat released when gaseous ions (1)
infinitely far apart (1)
join together to give 1 mole of solid (1)
b) (i)

Change

Decreases (1)

Explanation

Ionic radii increase (1)

Hence charge density / charge : radius ratio of the cations decreases (1)

(ii) Melting point

Decrease (1)

Solubility in water
c) (i)

Increase (1)

Ba2+(g) + 2F-(g) + aq ()
Hohyd

-1275 kJ mol-1 ()

Ba2+(aq) + 2F-(g) + aq ()
Holattice +2352 kJ mol-1 ()

2 Hohyd

2 (-530) = -1060 kJ mol-1 ()

Ba2+(aq) + 2F-(aq) ()
2+

Hosoln ()

Ba (F )2 (s) + aq ()

By Hesss law, Hosoln

= +2352 1275 1060 (1)

= +17 kJ mol-1 (1)

(ii) Hosoln for BaF2(s) is endothermic while the value of Hosoln for BaCl2(s) is exothermic (1)
dissolving of BaF2(s) is thermodynamically less favourable (1)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 4

BORN-HABER CYCLES I
a) Born-Haber cycle

Li+(g) + e- + F(g) (1)

+79.0 kJ mol-1 (1) -334.0 kJ mol-1 (1)

Li+(g) + e- + F2(g) (1)

Li+(g) + F-(g) (1)

+520.0 kJ mol-1 (1)

Li(g) + F2(g) (1)

+159.5 kJ mol-1 (1)

Holattice (1)

Li(s) + F2(g) (1)

-616.0 kJ mol-1 (1)

Li+F-(s) (1)
Lattice enthalpy of lithium fluoride
By Hesss law, 159.5 + 520.0 + 79.0 334.0 + Holattice = -616.0 (1)
Holattice = -616.0 159.5 520.0 79.0 + 334.0
= -1040.5 kJ mol-1 (1)
b) Calculation is based on the assumption that bonding is purely ionic (1)
In reality, bonding has some covalent character (1)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 5

BORN-HABER CYCLES II
a) (i)

Mg+(g) + e- + Cl(g) ()
-364
kJ mol-1 ()

+121
kJ mol-1 ()

Mg+(g)

+ Cl-(g) ()

Mg+(g) + e- + Cl2(g) ()
+736
kJ mol-1 ()

Mg(g) + Cl2(g) ()

-756
kJ mol-1 ()

+150
kJ mol-1 ()

Mg(s) + Cl2(g) ()
Hof (MgCl) ()

MgCl(s) ()

(ii) Hof (MgCl) = +150 + 736 + 121 + (-364) + (-756) (1)

= -113 kJ mol-1 (1)
(iii) The formation of MgCl2 is more exothermic than MgCl (1)
Hence MgCl2 is more stable / at a lower energy level than MgCl (1)
b) Lattice enthalpy of MgCl (1)
c) Second ionisation energy of magnesium (1)
Lattice enthalpy of MgCl2 (1)
d) Greater or less than Holattice (MgCl2)
Explanation

Less (1)

Mg+ has a smaller charge than Mg2+ (1) and is larger (1)
Or Mg+ has a lower surface charge density than Mg2+ (2)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 6

ENTROPY AND FREE ENERGY CHANGE

a) G o Standard free energy change / free energy change at 298 K and 1 atm ()
kJ mol-1 ()
T

Absolute temperature / temperature in kelvins ()

K ()

H o Standard enthalpy change / enthalpy change at 298 K and 1 atm ()

kJ mol-1 ()

S o Standard entropy change / entropy change at 298 K and 1 atm ()

J K-1 mol-1 ()
b) (i)

Decrease (1)
O2 gas (disordered) MgO solid (ordered) (1)

(ii) Increase (1)

Mg solid (ordered) H2 gas (disordered) (1)
(iii) Remain approximately the same (1)
Reactants and products are all gaseous ()
No change in the number of gas molecules ()
(iv) Increase (1)
Increased number of gaseous molecules (1)
c) (i)

Total entropy of products = (2 213.6) + (3 69.9) = 636.9 J K-1 mol-1 (1)

Total entropy of reactants = (160.7) + (0) = 160.7 J K-1 mol-1 (1)
So = 636.9 160.7 = 476.2 J K-1 mol-1 (1)

(ii) G o = -1367.3 (298 476.2 10-3) (1)

= -1509.2 kJ mol-1 (1)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 7

SOLUBILITY TRENDS OF GROUP 2 HYDROXIDES AND SULPHATES

a) Mg2+ is smaller than Ba2+ but each ion has the same charge (1)
Mg2+ has a higher charge density on its surface / higher charge : radius ratio (1)
the hydration forces are stronger for Mg2+ (1)
Mg2+ has a hydration enthalpy of greater magnitude (1)
b) Ba(OH)2 is more soluble than Mg(OH)2 (1)
c) From a), the magnitude of hydration enthalpy is greater for Mg2+ than Ba2+, which favours the solubility of Mg(OH)2
more than Ba(OH)2 (1)
However, because of the small size of Mg2+, Mg(OH)2 has a higher lattice enthalpy than Ba(OH)2 and this factor
favours Ba(OH)2 having the greater solubility (1)
Because OH- is small, lattice enthalpies of all hydroxides are relatively high, so that this factor is dominant (1)
d) (i)

The SO42- ion is very large (1)

compared even with Ba2+, so distance between ionic centres varies little down the group (1)

(ii) Decrease down the group (1)

(iii) Hydration enthalpy of M2+ decreases in magnitude / becomes less ve down the group ()
to produce a solubility decrease ()
Lattice enthalpy of sulphates decreases down the group ()
to produce a solubility increase ()
But lattice enthalpy does not vary very much / the rate at which lattice enthalpy decreases in magnitude is less
than that at which hydration enthalpy changes (1)
hydration enthalpy is the dominant factor (1)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 8

TEST QUESTION I
a) Step 1

Enthalpy of atomisation / sublimation of sodium (1)

Step 2

(First) ionisation energy of sodium (1)

Step 3

Hydration enthalpy of the sodium ion (1)

Step 4

Dissociation enthalpy of water (1)

Step 5

Negative() hydration enthalpy of the proton / hydrogen ion ()

Step 6

Negative () ionisation energy of hydrogen ()

Step 7

Negative () enthalpy of atomisation of hydrogen / half the bond dissociation enthalpy of the HH
bond ()
Na+(g) + OH-(aq) + H+(g)

b) (i)

+1090 kJ mol-1

-406 kJ mol-1

Na+(aq) + OH-(aq) + H+(g)

Na+(g) + OH-(aq)

+ H+(aq)

Hox

Na+(g) + H2O(l)

-1316 kJ mol-1

+500 kJ mol-1

Na(g) + H2O(l)
Na+(aq) + OH-(aq) + H(g)

-1

+109 kJ mol

Na(s) + H2O(l) Start

-218 kJ mol-1
-183.7 kJ mol

-1

Na+(aq) + OH-(aq) + H2(g)

Finish

4 marks (Deduct for each error or omission)

(ii) By Hesss law,
-183.7 = +109 + 500 + Hox + 1090 406 1316 218 (1)
Hox = -183.7 109 500 1090 + 406 + 1316 + 218
= +57.3 kJ mol-1 (1)
c) Predicted value
Explanation

-57.3 kJ mol-1 (1)

Because neutralisation / H+(aq) + OH-(aq) H2O(l)
is the reverse of the dissociation of water (1)

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 9

TEST QUESTION II
a) Mg(s) + O2(g) MgO(s) (2)
Award (1) for correctly balanced equation and (1) for correct state symbols.

b) (i)

Mg2+(g) + O2-(g)
Mg2+(g) + 2e- + O(g)
+1451
kJ mol-1

-142
kJ mol-1

+844
kJ mol-1

Mg2+(g) + e- + O-(g)
Mg+(g) + e- + O(g)
+738
kJ mol-1
-3884
kJ mol-1

Mg(g) + O(g)
+249
kJ mol-1

Mg(g) + O2(g)
+147
kJ mol-1

Mg(s) + O2(g)
Hof (MgO)

MgO(s)
(4) Deduct 1 mark for each error.

(ii) Hof (MgO) = [+147] + [+249] + [+738] + [+1451] + [-142] + [+844] + [-3884] (1)
= -597 kJ mol-1 (1)
c) S o = [27.0] [(32.7) + (205)] (1)
= -108.2 J K-1 mol-1 (1)
d) (i)

G o = Ho - TSo (1)
= [-597 x 103] [(298) x (-108.2)] (1)
= -564 800 J mol-1
= -564.8 kJ mol-1 (1)

(ii) Reaction has high activation energy (1)

Energy is required to form Mg2+ and O2- ions before lattice enthalpy can be released (1)
reaction is infinitely slow (1)
Maximum 2 marks

A2 Level

TOPIC 17 ANSWERS & MARK SCHEMES

QUESTIONSHEET 10

TEST QUESTION III

a) (i)

The enthalpy change when 1 mole of gaseous ions (1)

becomes hydrated by a large / infinitely large quantity of water (1)

(ii) The enthalpy change when 1 mole of the solid (1)

is dissolved in a large quantity of water / to give an infinitely dilute solution (1)
b) (i)

Mg2+(g) + 2Cl-(g)
Hohyd (Mg2+(g))
+2493
kJ mol-1

Mg2+(aq) + 2Cl-(g)

MgCl2(s)

-728
kJ mol-1

-155
kJ mol-1

(3) Deduct 1 mark for each error.

Mg2+(aq) + 2Cl-(aq)
(ii) Hosolution = Holattice + Hohyd(cation) + Hohyd(anion) (1)
(iii) -155 = +2493 + Hohyd(Mg2+(g)) + [-728] (1)
Hohyd (Mg2+(g)) = [-155] + [-2493] + [+728]
= -1920 kJ mol-1 (1)
c) (i)

Value becomes more negative (1)

(ii) Size of the metal cation increases (1)

charge density of the metal cation decreases (1)
(iii) Decrease in lattice enthalpy is much greater than decrease in hydration enthalpy (1)
Hosolution becomes more negative and solubility increases (1)