CAPE 2015: SUGGESTED ANSWERS

MODULE 1: FUNDAMENTALS IN CHEMISTRY

1. (a)(i) Define the term bond energy

[1

mark]
The bond energy represents:
The quantity of energy evolved when the bond is formed.
Also, the bond energy is the amount of energy absorbed when the bond is
broken.
(ii) The bond lengths and bond energies of carbon-carbon single, double and
triple bonds are listed below.
C-C

C=C

C=C (triple)

Bond lengths

1.54

1.34

1.20

Bond energy

348 KJ mol-1

614 KJ mol-1

839 KJ mol-1

State the relationship between the strength of a covalent bond and its length
[1 mark]
The shorter the bond, the stronger it is. That means that more energy will be
required to break it.
This is why the carbon-carbon triple bond is the shortest, and thus has the
highest bond energy (839 KJ mol-1)
(b) Bond energies can be used to estimate the enthalpies of reactions in which
bonds are broken and new bonds are formed. Consider the gas-phase reaction
between methane (CH4) and chlorine to produce methylchloride (CH 3Cl) and
hydrogen chloride
(i) Write a balanced equation to represent the reaction above
[2 marks]
CH4 (g) + Cl2 (g)

CH 3Cl (g) + HCl (g)

(ii) Using bond energy values from Table 1, calculate the enthalpy change of
reaction Hrxn for the equation required in (b) (i)
[3 marks]

What really happened:

CH4 (g) + Cl2 (g)
By looking at the equation:

CH 3Cl (g) + HCl (g)

What was broken: (*Energy is taken in to break a bond)

One of the C-H bonds from CH4 = (+410 KJ)
The Cl-Cl bond = (+244 KJ)
What was formed: (*Energy is released when a bond is formed)
A new C-Cl bond was formed = (-340 KJ)
A H-Cl bond was formed = (-431 KJ)
We now construct a cycle based on what happened:
CH4 (g) + Cl2 (g)

H2

CH 3Cl (g) + HCl (g)

H1

H3

H2

CH3 + H + Cl + Cl

H3

Using H1 = H2 + H3 = (654) + (-771) = -117 KJ

(iii) Is the reaction in (b)(i) exothermic or endothermic?
[1 mark]
It would be exothermic, since H is negative
(iv) On the axes provided below, draw the energy profile diagram for the reaction in

Energy (KJ mol1

)

(b)(i) [2 marks]
This of course depends on your H value

Reactants
CH4 (g) +
Cl2 (g

EA

Products
H

CH3Cl (g) +
HCl (g)
of reaction
(c) A student is asked Progress
to determine
the enthalpy of the neutralization reaction
between 75cm3 of 1.00M hydrochloric acid and 75 cm 3 of 1.00 M potassium

hydroxide solution. Outline the experimental steps (including calculations) required

to obtain and accurate value.
[Assume that the densities of the solutions of acid and base and their heat
capacities are equal to the density (1 g cm -3) and heat capacity (4.18 J g-1oC-1) of
water]
Steps:

Measure 75cm3 of 1.00M hydrochloric acid into a polystyrene cup

Stir gently for three minutes, taking the temperature reading every minute
for 3 minutes
Record the constant temperature as the initial temperature
Add 75cm3 of 1.00M potassium hydroxide and stir for the next seven minutes,
recording the temperature of the mixture at 1 minute intervals. Record the

highest temperature as the final temperature

The temperature change (T) = initial temp=final temp
Calculations:
Using EH = mcT where m= mass of solution= (75 +75 = 150g) and c = 4.18
J g-1oC-1
The number of moles of HCl (or NaOH) used:
1000 cm3 = 1 mole
1cm3= 1/1000
75 cm3 = 1/1000 x 75 = 0.075 moles
We say 0.075 moles = EH (from above)
So 1 mole = EH/0.075 (this would be the molar enthalpy of neutralization)
MODULE 2: KINETICS AND EQUILIBRIA
2. (a) Define EACH of the following terms:
(i)
Standard electrode potential of a half-cell

[2

marks]
The potential of that half cell relative to a standard hydrogen half-cell
under standard conditions.
(ii)

Standard cell potential of an electrochemical cell

[2

marks]
The sum of the potential of two half cells connected together in such a way
that reduction occurs in one half cell and oxidation in the other
OR
This is the maximum potential difference obtained when two half cells are
connected together under standard conditions
OR

This is a cell potential against which the cell potential of other elements can
be measured

(b) Consider the following (unbalanced) equation which describes the process that is
taking place in an electrochemical cell under standard conditions:
Al (s) + Sn2+ (aq) Al3+ (aq) + Sn (s)
As you can see, Al is being oxidized (change from 0 to +3). Oxidation occurs at the
anode (An Ox)
Also, Sn is being reduced (change from +2 to 0). Reduction occurs at the cathode
(Red Cat)
(i)

Write the ionic half-equation for the reaction taking place at EACH of the
electrodes [2 marks]

ANODE: Al (s) (aq) Al3+ (aq) + 3e

CATHODE: Sn2+ (aq) + 2e Sn (s)
(ii)

Write the cell diagram

[1

mark]
The cell notation would be: Al|Al3+ || Sn2+|Sn
(iii)

Draw a well labeled diagram of the electrochemical cell. Include the

direction of electron flow [6 marks]

Electron flow
V
Tin rod
(cathode)

Aluminium
rod (anode)
Salt bridge

(iv)

Solution B: 1
moldm-3 Sn2+ ions

Solution A: 1 moldm3
Al3+ ions

For EACH electrode shown in Table 2, select the E value to determine E

cell

[2 marks]
Electrode Reaction
Ag+ + e

Ag

E at 298 K (250C) (volts)

+0.80

Al3+ + 3e

Al

-1.66

Ba2+ + 2e

Ba

-2.90

Sn2+ +2e

Sn

-0.14

Sn2+

+0.15

Sn4+ +2e

Maybe I am not understanding correctly,

but.. is the question phrased

correctly? What were they asking for? The overall emf of the cell?
Al
Al3+ + 3e E = +1.66
2+
Sn +2e
Sn E = -0.14
2Al + 3Sn2+
2 Al3+ + 3Sn

(Multiply this eqn by 2)

(Multiply this eqn by 3)
E = (+1.66) + (-0.14) = +1.52 V

MODULE 3: CHEMISTRY OF THE ELEMENTS

3. The Group IV elements exhibit oxidation states of +2 and +4 in their
compounds.
(a) Complete Table 3 for the oxides of carbon and lead.
[4 marks]
TABLE 3: OXIDES OF GROUP IV ELEMENTS
CO

CO2

PbO

PbO2

Acid/Base
nature

neutral

Acidic

Amphoteric

Amphoteric

Thermal
stability

Unstable:
Readily
oxidized to
dioxide

Stable

Stable

Unstable:
decomposes
to form PbO

Oxidation
state of
Group IV
element

+2

+4

+2

+4

How to get there?

In CO2, the oxidation number of carbon would be:

x + (2 x -2) = 0
x -4 = 0
x = +4
(b) (i) Explain the relative stabilities of the +2 oxidation states of the oxides of
carbon and lead [4 marks]
Carbon is most stable in the +4 state (as CO 2) and least stable in the
+2 state (as CO)
Lead is most stable in the +2 state (as PbO) and least stable in the +4
state (as PbO2)

Stability

This is illustrated on the graph below: (Optional!)

+2
state

+4
state

Si

G
e

Sn

Group IV
Elements

Pb

Lead is a metal, and so prefers to lose two electrons to be stable. This gives
Pb an oxidation number of +2.
Carbon being a non- metal prefers to share electrons. It is less energetically
feasible for C to lose two electrons and exist in the +2 state
(ii) Use the electrode potential value in the electrode reaction for lead ions to
explain the relative stabilities of the +2 and +4 oxidation states of lead:
[2 marks]
Pb4+ + 2e

Pb2+ E =+1.80 V

The E value for Pb going from the +4 to the +2 state is large and positive.
This means it is very energetically feasible for Pb to be converted from the
+4 to the +2 state. This suggests that for Pb, the +2 state is much more
feasible than the +4.

(c) Describe what should be observed when

(i)

Concentrated sodium hydroxide is added to solid lead (IV) oxide

[1 mark]

**Since PbO2 is amphoteric, it will react with both acids and bases to form a
salt and water
A white precipitate (which is the salt) will be formed and may dissolve in the
(colorless) water which is also formed
(ii)

Concentrated hydrochloric acid is added to solid lead (IV) oxide

[2 marks]

Both lead (IV) chloride and water will be formed. Since lead chloride is
insoluble, there will be a white precipitate in a colorless liquid (water)
(d) Describe a test to identify Pb2+ ions in solution
[2 marks]

Potassium iodide (KI) can be added to the ions in solution. If Pb 2+ is present,

there will be a bright yellow precipitate.
Pb2+ (aq) + 2 I- (aq) PbI2 (s)

MODULE 1: FUNDAMENTALS IN CHEMISTRY

4. (a) The atoms of certain elements contain nuclei in which the ratio of
neutrons to protons is greater than 1. These nuclei tend to emit radiation in
order to bring the ratio closer to 1.
(i)

Describe the THREE types of radiation that an unstable atom may emit.
Include in your answer the symbols and penetrating power of EACH
type of radiation [6 marks]

EMISSION

SYMBOL

RELATIVE PENETRATING
POWER

Particles

Helium nuclei

4 2
He
2
Particles

Electrons

100

0e
1
Rays
(ii)

Electromagnetic waves

10,000

Americium-241 (Am-241) decays via alpha particle emission. Write the

nuclear equations to show the new element that forms when an atom

of

241

95

Am decays via the emission of 2 alpha particles

[2 marks]
+

241

233

2+ orbitals of principal
2+
(b) (i) Draw
quantum number
2.
Am the diagrams of the atomic
He2+
He2+
Pa

2
Include 95
x, y and z axes in your drawing

91

[2 marks]
Principal quantum number is the same as the shell number. In the second shell,
there are two orbitals: a 2s and a 2p.

(ii) Comment on the similarity and difference in the electronic configuration of K, Sc

and Zn2+ given below

K: 1s2 2s2 2p6 3s2 3p6 4s1

Sc: 1s2 2s2 2p6 3s2 3p6 3d1 4s2
Zn2+: 1s2 2s2 2p6 3s2 3p6 3d10

Similarity:
All of the elements have more than 18 electrons, and they have the same
arrangement of electrons up until the 3p orbital (1s 2 2s2 2p6 3s2 3p6). This is
sometimes represented as [Ar] followed by the rest of the electronic
configuration
Difference:
Sc and Zn both have electrons in the d orbitals, but K does not. This is
because Sc and Zn are transition metals and K is a Group 1 metal OR
K and Sc have electrons in the 4s orbital, but Zn 2+ does not. This is because
the configuration of Zn is 1s2 2s2 2p6 3s2 3p6 3d10 4s2. For Zn2+, 2 electrons
were lost from the 4s orbital first, making it 1s 2 2s2 2p6 3s2 3p6 3d10

MODULE 2: KINETICS AND EQUILIBRIA

5. A buffer consisting of H2PO4- and HPO42- helps control the pH of physiological
fluids. Many carbonated soft drinks also use this buffer system.
(a) Using the buffer system mentioned above, describe how the solution
maintains and almost constant pH even when small amounts of acid or
alkali are added to the solution [6 marks]
This buffer consists of a solution of a weak acid in the presence of one of its salts
(that is, H2PO4- and Na2HPO4).
Two reactions will be happening:
Equation 1:

H2PO4-

H+ + HPO42-

Equation 2:

Na2HPO4 2 Na+ + HPO42-

If acid (H+) is added, Equation 1 is affected. This is because this equation

also contains H+ ions. According to Le Chatelier, in Equation 1, the
equilibrium will shift to the left. This gets rid of the added H + ions and pH
returns to normal.

If alkali is added, (OH-), Equation 1 is still affected. Two things happen:

1. The added OH- ions combine with H+ to form H2O, which is neutral. The
OH- has been removed. However, in the process we have also lost some
H+ ions.
2. In order to correct this, according to Le Chatelier, in Equation 1, the
equilibrium will shift to the right. This allows the H + ions to be replaced.
The pH returns to normal.
Optionally:
Equation 2 has not yet been used. This equation produces a large amount of
HPO42- ions. In the event that a large amount of acid (H +) is added to the
solution, then the HPO42- from Equation 2 will be used to trap the added acid
(H+).

(b) Calculate the pH of a soft drink in which the major buffer ingredients are
6.5 g of NaH2PO4 and 8.0 g of Na2HPO4 per 355 cm3 of solution
[Ka (H2PO4-) = 6.4 x 10-8 moldm-3]
[Relative atomic mass: H=1, Na = 23, O = 16, P = 31]

Using the formula: [H+] = Ka [acid]

[salt]
And we know that pH = -lg [H+]
Since we are told that Ka (H2PO4-) = 6.4 x 10-8 moldm-3, if it has a Ka (acid
dissociation constant) value then this is the acid! (NaH 2PO4)
Which makes the other species the base (Na 2HPO4)

So the concentration of the acid would be:

1 mole (NaH2PO4) = (23 x 1) + (1 x 2) + (31 x 1) + (16 x 4) = 120 g
120 g = 1 mole
1g = 1/120
6.5g = 1/120 x 6.5 = 0.05417 moles

355 cm3 = 0.05417 moles

1 cm3 =

0.05417

1000cm3 =

/355

0.05417

/355 x 1000 = 0.1526 moles. Concentration: 0.1526 moldm-3

So the concentration of the salt would be:

1 mole (Na2HPO4) = (23 x 2) + (1 x 1) + (31 x 1) + (16 x 4) = 142 g
142 g = 1 mole
1g = 1/142
8g = 1/142 x 8 = 0.0563 moles

355 cm3 = 0.0563 moles

1 cm3 =

0.0563

1000cm3 =

/355

0.0563

/355 x 1000 = 0.1587 moles. Concentration: 0.1587 moldm-3

Plug values into formula:

[H+] =

(6.4 x 10-8 moldm-3) x (0.1526 moldm-3) = 6.1 x 10-8 moldm-3

(0.1587moldm-3)

Work out pH:

pH = -lg [[H+] = -lg [6.1 x 10-8 moldm-3] = 7.21

(c) Many chemical reactions occur in living systems such as the human body.
Discuss the importance of biological buffers to the maintenance of a
healthy body. (Include an example of a chemical reaction of a blood
buffer)

[4 marks]

In living things, the pH of the blood must be kept constant, or else they will die.
The normal pH of the blood is 7.4
There are two reactions of interest in the buffering system of blood:
Equation 1:

CO2 (aq) + H2O (l)

H2CO3 (aq) (carbonic

acid)
Equation 2:

H2CO3 (aq)

H + + HCO3 -(aq)

(bicarbonate)
If a person has been running rapidly for a long time, he usually starts gasping for
breath. This means that he is struggling to inhale oxygen and exhale carbon
dioxide.
If carbon dioxide is allowed to build up in the blood, it combines with water to form
carbonic acid. This carbonic acid rapidly breaks down into H + and CO32- ions. The H+
ions can cause the blood to become acidic. This can be lethal to cells.
By exhaling carbon dioxide rapidly, there will be less reactant in Equation 1.
According to Le Chatelier, the equilibrium will shift to the left. This causes the
carbonic acid to break up into CO 2 and H2O, instead of harmful H+ ions. The CO2
produced can then be exhaled.

MODULE 3: CHEMISTRY OF THE ELEMENTS

6. (a) The atomic and ionic radii of the Group II elements gradually increase
down the group. Outline the reasons for this trend
[3 marks]
The atomic radius can be visualized as the distance between the nucleus and
the outermost shell.
As the Group is descended the atoms have an increase in the number of
electrons. Be only has 2 electrons, while Ba has 56 (optional). Since Ba has

more electrons, there will also be more shells, and so the distance between
the nucleus and the outermost shell increases.
The Group II elements lose 2 electrons to become stable, thus forming cations
with a charge of +2. Since they all lose one shell, there is still an increase in
the number of shells as the Group is descended. Hence the radius of the ion
formed also increases.

(b) Account for the variation in the melting points of the Group II elements
from magnesium to barium
[4 marks]
There is actually a decrease in melting points as the Group is descended. All
of the Group 2 elements are metals and so are held together by metallic
bonds. This is the attraction between the cation and the sea of delocalized
(lost) electrons.
It would make sense to reason out that, as the Group is descended, there are
more electrons and so there would be more metallic bonds, hence an
increase in melting points. However, this is not so for Group 2.
What happens is that since the ionic radius is becoming larger, the attraction
for the delocalized electrons becomes weaker. Thus there is a decrease in
melting points.
**I am not sure if you were supposed to know this or if CAPE wanted you to
just reason it out and go with what is expected

(c)Table 4 shows the observations when 0.1 moldm -3 solutions of the metal
ions are treated with 1 moldm-3 Na2SO4
TABLE 4: OBSERVATIONS OF REACTIONS
Solution of Group II cations

Observations with 1 moldm-3 Na2SO4

0.1 moldm-3
Mg2+

No precipitate

Ca2+

Thin, white precipitate

Sr2+

White precipitate

Ba2+

Thick, white precipitate

Account for the trend indicated in Table 4

marks]

[5

When the ions are reacted with sodium sulphate, the Group 2 sulphates are
being formed.
It is observed that as the group is descended, there is a general decrease
in solubility of the sulphates. This is seen from the observations, as BaSO 4 is
a thick white precipitate (less soluble) than MgSO 4 which is no precipitate (very
soluble)
We can explain this by considering the sulphates being dissolved in water as two
steps:
Step 1: The ions in the solid must be separated:
MgSO4 (s) Mg2+ (g) + SO42- (g)
(Remember: An ionic lattice is being broken up. The energy needed for this is the
reverse of the lattice energy -Hlatt).
Step 2: The separated ions must be hydrated (completely surrounded) by water
Mg2+ (g) + SO42- (g) + (aq) Mg2+ (aq) + SO42- (aq)
The smaller the ionic radius, the less hydration energy will be required. Hence
BeSO4 will require the least hydration energy, while BaSO 4 will require the most.
It makes sense that the greater the total energy for these processes, the less
soluble the compound will be. As the group is descended, solubility of the
sulphates decreases.

(d) Explain the variation in the thermal decomposition of the nitrates of the
Group II elements
[3 marks]
The oxide ion is smaller than the nitrate ion. It will follow that the oxide ion is
more stable than the nitrate ion. This explains why the nitrates of the Group II
elements decompose under heat to form Group II oxides.
2 X(NO3)2 (s) 2 XO (s) + 4 NO2 (g) + O2 (g)
Where X is any Group 2 element (Be, Mg, Ca, Sr or Ba)
As the Group is descended, it requires more heat to decompose the nitrates.
This is because the stability of the nitrates increases as Group II is
descended.
The more reactive an element is, when it forms a compound, that compound will
be very stable. Since reactivity increases as the Group is descended, the most
reactive Group 2 element would be Ba. Therefore Ba(NO 3)2 would be most stable

No matter how many mistakes you have made, this paper was ONLY
40%. You still have a fighting chance to get that distinction. CAPE
accepts many answers, and I have only given a few of them here. And
marks CAN be given for different things than I have suggested Keep
believing in yourself Yes, you can still do it!