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TEST CODE
FORM TP 2016166 %. MAY/JUNE 20I6

CARIBBEAN EXAMINATIONS COUNCIL

CARIBBEAN ADVANCED PROFICIENCY EXAMINATION@

CHEMISTRY

UNIT I -Paper02

2 hours 30 minutes

READ THE FOLLOWING INSTRUCTIONS CAREFULLY.

I This paper consists of SIX questions in TWO sections. Answer ALL questions.

2. Write your answers in the spaces provided in this booklet.

J. Do NOT write in the margins.

4. Where appropriate, ALL WORKING MUST BE SHOWN in this booklet.

5. A data booklet is provided.

6. You may use a silent, non-programmable calculator to answer questions.

7. If you need to rewrite any answer and there is not enough space to do so on the
original page, you must use the extra lined page(s) provided at the back ofthis booklet.
Remember to draw a line through your original answer.

8 If you write the question number clearly in the

use the extra page(s) you MUST
box provided at the top of the extra page(s) and, where relevant, include the
question part beside the answer,

DO NOT TURI\ THIS PAGE UNTIL YOU ARE TOLD TO DO SO.

Copyright O 2015 Caribbean Examinations Council

All rights reserved.

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SECTION A

AnswerALL questions.

MODULE 1

FUNDAMENTALS IN CHEMISTRY

1. (a) John Dalton proposed the atomic theory in 1803.

(i) State THREE postulates of Dalton's atomic theory.

John Dalton's postulates are as follows:

1. All matter is made of atoms, which are indivisible.
2.All atoms of a given element are identical in mass
and properties.
3.Compounds are combinations of two or more different
types of atoms.

[2 marks]

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5

(ii) Later developments in science led to the modification of the atomic theory. Explain
the modification of ONE of the postulates.

The indivisibility of an atom was proven wrong,

for, an atom can be further subdivided into
protons, neutrons and electrons.

[2 marks]

(b) The dichromate(Vl) ion reacts in an acidic medium according to the following half-equation:

CrrO,2 (aq) + l4 H* (aq) + 6e- --------------> 2 Ct'.(aq) + 7 H,O(l)

(i) Identify the ion responsible for the green colour.

Cr3+

I mark]

(ii) Given that the sulfate(lV) ion, SO.2-, is converted to the sulfate(Vl) ion, SOo2 , in
the presence of wateg deduce the balanced equation for the redox reaction between
CrrOr2 (aq) and SOr'-.

SO32-(aq) +H2O(l) ---------> SO42-(aq) + 2H+(aq) +2e- --- eqn 2 x3

add both Cr2O72- (aq) + l4 H+ (aq) + 6e- --------------> 2 Cr3+(aq) + 7 H2O(l) --- eqn 1
equations +
3SO32-(aq) + 3H2O(l) ---------> 3SO42-(aq) + 6H+(aq) + 6e- ---- eqn 3
__________________________________________________
Cr2O72-(aq)+l4H+(aq)+3SO32-(aq)+3H2O(l)---->2Cr3+(aq)+7H2O(l)+3SO42-(aq)+6H+(aq)
Cr2O72-(aq)+8H+(aq)+3SO32-(aq)---->2Cr3+(aq)+4H2O(l)+3SO42-(aq)

[4 marksl

(iii) Identify the oxidizing agent in (b) (ii).

dichromate(VI) ion
[1 mark]

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(c) The results of two tests are to be recorded in Table l. Complete the table by inserting the
missing observations or inferences.

TABLE 1: RESULTS OFTESTS

Test Observation Inference

(i) Chlorine water is added a Red-brown solution. Br- oxidized to Br,

to potassium bromide formed
solution followed by
aqueous silver nitrate.
. silver chloride
White precipitate formed a
wasformed

no change no reaction
(ii) Bromine water is added o a

to potassium chloride
in colour
solution followed by
aqueous silver nitrate.

. White precipitate formed a silver chloride

on addition of AgNOr(aO) was formed

[5 marks]

Total 15 marks

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MODULE 2

KINETICS AND EQUILIBRIA

2. (a) Define EACH of the following terms:

(i) Weak acid

A weak acid is one which is partially dissociated when it

is disolved in water.

I mark]

(ii) Ku

The acid dissociation constant is the equilibrium constant

of the dissociation reaction of an acid and is a
quantitative measure of the strength of an acid in a
solution.

[2 marks]

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(b) In aqueous solution, carbonic acid forms a weak acidic solution containing the hydrogen
carbonate ion.

(i) Write an equation to represent the dissociation of carbonic acid in aqueous solution

H2CO3(aq) H+(aq) + HCO3-(aq)

[2 marks]

(ii) Write the K, expression for the reaction in (b) (i)

Ka = [H +(aq)][HCO -(aq)]
_________________
3

[H2CO3(aq)]

I mark]

(iii) Calculate the pH of a 0.100 mol dm-3 aqueous solution of carbonic acid.
(K":4.5 x l0-7 mol dm-3 at25 "C.)
[H+(aq)] = ([H2CO3(aq)]Ka)
= (0.100 x 4.5 x 10-7)

= (4.5 x 10-8) mol dm-3

= 0.000212 mol dm-3

pH = -log [H+(aq)]
= -log 0.000212
= 3.67
[4 marks]

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(c) A student was given a particular brand of club soda (carbonated beverage) to determine
the carbonic acid content. Outline the experimental steps required for the investigation if
the student is given 200 cm3 of 0.100 moldm-3 sodium hydroxide solution.
1. Use a pipette to transfer 25 cm3 portions of the club soda to a
conical flask.
2.Add 2 to 3 drops of phenolphthalein to the flask.
3.Titrate the mixture with the sodium hydroxide from the burette until
a permanent faint pink end point is seen.
4.Repeat the titration at least two more times for concordant results.
5.Record the intial and final burette readings for each titration.

[5 marks]

Total 15 marks

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MODULE 3

CHEMISTRY OF THE ELEMENTS

3. Figure I shows the melting points of the elements in Period 3

2000

I
E
1500

c 1000
EL
o0
E
o 500

0
NaMgAlSiPSCl Ar

Figure 1. Melting points of elements in Period 3

(a) Explain, in terms of structure and bonding, why

(i) aluminium has a higher melting point than sodium

The higher melting point of aluminum compared to sodium can be attributed
to its stronger metallic bonding, which arises from the presence of
multiple (three) valence electrons and the stronger nuclear attraction.
Additionally, the more compact face-centered cubic crystal structure of
aluminum further reinforces its higher melting point.

[2 marksl

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(ii) silicon has the highest melting point in the period

silicon has the highest melting point in its period due to
the presence of a three-dimensional covalent network
structure. The strong covalent bonds between silicon atoms,
resulting from the sharing of four valence electrons,
contribute to the high melting point. The dense and rigid
lattice arrangement further reinforces the overall strength
of the structure, making silicon resistant to melting at
high temperatures.

[2 marksl

(iii) sulfur melts at a higher temperature than phosphorous.

The difference in melting points between sulfur and phosphorus
arises primarily from the strength of their intermolecular forces.
In the case of sulfur, the intermolecular forces are weak van der
Waals forces. These forces are the result of temporary
fluctuations in electron distribution and induce weak attractions
between neighboring S8 molecules. These van der Waals forces are
relatively easy to overcome, leading to a lower melting point for
sulfur.

In contrast, white phosphorus has a higher melting point compared

to sulfur due to the presence of stronger covalent bonds within P4
molecules. The phosphorus atoms within each P4 molecule are held
together by relatively strong covalent bonds, making it more
difficult to break the molecular structure and transition into a
liquid state.

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(b) The reactions ofthe oxides of magnesium and phosphorous with waterare to be summarized
in Table 2.

TABLE 2: REACTION OF OXIDES WITH WATER

Oxide Reaction with Water pH of Resulting Liquid

9
sparingly soluble
weakly alkaline
Mgo forms
magnesium hydroxide

forms
phosporous acid
3
Poo,o
acidic

(i) Complete Table 2 by describing the reaction of EACH oxide with water and
suggesting a pH value for the resulting liquid. [2 marks]

(ii) Write the equation which represents the reaction of water with PoO,o.

[2 marksl

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(c) Write equations to show what happens when EACH of the following chlorides reacts with
water.

(i) sicl4

::Ii+
NH
i-Ei
.-E{
---.r\:
]E
-:.El
.-'.E'
:I{
---.*r-.

,rf,l
[2 marksl

(ii) Alct3

AlCl3(s) + 6H2O(l)--->[Al(H2O)6]3+(aq) + 3Cl-(aq)

[2 marksl

Total 15 marks

r]$
,.._.+

..$.
rl*l
:i(:
'-'---
'.--'--s-

,-:E
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02112020/0APE 2016
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SECTION B

AnswerALL questions.

MODULE 1

FUNDAMENTALS IN CHEMISTRY

4. (a) (i) Describe how the bonds are formed in EACH of the solids, potassium chloride
and iodine.
the valence electrons of potassium are lost to the valence
shell of the chlorine atom. There is now an electrostatic
attraction between the potassium and chloride ions to form
an ionic bond.
Iodine molecules consist of strong covalent bonds which are due
to the overlapping of orbitals in the valence shells of the
iodine atoms. The iodine molecules are held together by weak
intermolecular forces called van der Waals forces.

[4 marksl

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good conductor does not conduct

soluble slightly soluble

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(b) Account for EACH of the following statements: .*-.

.rii.
.*i
(i) The boiling point of HrO is higher than that of HrS
it*.
:-ea-'.
.'Jr1--
,:ts:
it.iil
Water molecules are capable of forming hydrogen bonds with each ikr
:\--
other. Hydrogen bonding is a strong intermolecular force that occurs ..I+-
-hi-
between the δ+ hydrogen atom of one water molecule and the δ- oxygen :tiiij
,:*::
atom of a neighboring water molecule. These hydrogen bonds result in rB---
significant cohesion between water molecules, leading to a higher !fui:
boiling point. In contrast, hydrogen sulfide molecules do not form j€ii
hydrogen bonds with each other. Instead, they experience weaker
iE
.si
London dispersion forces, which are less effective at holding the .a;
molecules together, resulting in a lower boiling point compared to

[3 marks]

(ii) The molecules of aluminium fluoride in the presence of ammonia forms a white
solid of formula NH3AlF3. (lnclude an appropriate equation in your account.)
Aluminium fluoride is a Lewis acid due to the vacant orbital on it+rl
the Aluminium atom. Ammonia is a Lewis base due to the lone pair i'G-i
of electrons on the nitrogen atom.As a result of this the lone ,R'l
iol
pair on the nitrogen in ammonia is shared with the vacant orbital is:
on the Al atom forming a cordinate bond. The resulting substance
is aluminium trifluoride ammonia adduct.
H F
H F
H N Al F
H N: Al F
H F
H F
a Lewis a Lewis
base acid
:.t
..Ei-
::,Sf
..H.
:-}t+-
i:le-

..t*i.
-.4-
--\t.
[3 marks] l..a
...9
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(c) Explain the difference between the shapes of NH, and NHn*

Ammonia is trigonal pyramidal because the central atom - N has 3

bond pairs and 1 lone pair of electrons.The 1 lone pair repels the
3 bond pairs into a pyramidal shape with a bond angle of 107o.
The ammonium ion, by contrast, has a tetrahedral shape because of the 4
bond pairs around the N atom. This results in bond angles of 109.5o.

[3 marks]

Total 15 marks

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02112020/CAPE 20r6

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MODULE 2

KINETICS AND EQUILIBRIA

5. The following equation represents the reaction between hydrogen and iodine.

H,(g) + I,(g) + 2 HI(g), AH: -10 kJ mol-l

The reaction is said to be in a state of equilibrium at a particular temperature and pressure.

(a) (i) State FOUR characteristics of a reaction in'dynamic equilibrium'.

1. both the reactants and the products are always present

2. the equilibrium can be approached from either side

3. the reaction is dynamic - it is moving forwards and

backwards

4. the concentrations of reactants and products remain

constant

[4 marks]

(ii) Write the expression for the equilibrium constant in terms of partial pressures, Ko,
for the reaction shown by the equation above.

(pHI)2
______
Kp = p x p
H2 I2
[2 marksl

(iii) State TWO factors which would NOT affect the equilibrium of the reaction shown
by the equation above.

1. change in pressure since number of molecules is the same on

either side of equation.

2. Use of a catalyst since rate of forward and backward

reaction would increase by the same amount.
[2 marks]
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(b) Describe the effect of decreasing the temperature on

(i) the equilibrium of the reaction

Since the reaction is exothermic, decreasing the

temperature would favour the forward reaction,
hence the equilibrium would shift to the right.

[2 marksl

(ii) the value of K'p'

Since the reaction is exothermic, decreasing the
temperature would favour the forward reaction thus
increasing the yield of product, hence the value of Kp
would increase.

[2 marks]
(c) When 0.5 mol of hydrogen and 0.5 mol of iodine are allowed to reach equilibrium in a
I .00 dm3 flask at 500 "C and l.0l x 105 N m-2, the amount of hydrogen iodide at equilibrium
is 0.78 mol. Calculate K^ at 500 "C if the total pressure is I pa.

= 0.782
__________ = _______
0.6084 = 50.3
0.11 x 0.11 0.0121
NOTE

note mole fraction and partial pressure are

calculated using the following formulas.

pT is the given total pressure [3 marksl

nT is the total Equilibrium moles = 0.11+0.11+0.78 = 1 Total 15 marks

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02112020/CAPE 2016

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MODULE 3

CHEMISTRY OF THE ELEMENTS

6. (a) List FOUR properties of transition metals

▪ They form compounds with different oxidation states.
▪ Transition element ions form coloured compounds.
▪ Transition element ions form complex ions.
▪ Transition elements and their compounds are often good catalysts
[this is often related to the differences in oxidation states].
▪ Transition elements have very high density.
▪ Transition elements have very high melting points and boiling
points.
▪ They have typical magnetic properties

ANY 4 WILL DO

[4 marks]

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02112020/CAPE 2016

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-21
.

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(b) Titanium(Ill) chloride forms a violet solution when dissolved in water.

(i) Write the electronic configuration using the s, p and d orbitals of the titanium ion
Ti3+ = 1s22s22p63s23p63d1

[1 mark]

(ii) Explain the colour of the aqueous solution

. The formation of the hexa aqua titanium(III) complex is
responsible for the violet color observed in the solution.
. The absorption of light in the visible region occurs due to
electronic transitions within the complex. These transitions
involve the movement of electrons between different energy
levels in the ligand field around the titanium(III) ion. The
energy gap between these levels corresponds to the absorption
of light in the violet region of the spectrum, resulting in
the violet coloration of the solution.

TiCl3(s) + 6H2O(l) → [Ti(H2O)6]3+(aq) + 3Cl-(aq)

hexa aqua
titanium(III)
complex

[4 marks]

GO ON TO THE NEXT PAGE

02112020/CAPE 2016

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0211202021 I
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(c) (i) Describe what would be observed when concentrated hydrochloric acid is slowly
::]s
added to an aqueous solution of Co2*. .ICl
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ni+
rla
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When concentrated hydrochloric acid is added to a solution .F
containing hexaaquacobalt(II) ions, the solution turns from its iIIj

original pink color to a dark rich blue. iE

..I+
jH
.!ii
[1 markl jfigl

(ii) Write an ionic equation to represent the observation in (c) (i). IFi.-
,Qi
.E
:H
..-*r-
pink ,.4

[2 marksl

(iii) Using the concept of stability constant, explain the changes observed in (c) (ii).

The stability constant is a measure of the strength of the

bond between a metal ion and a ligand. When concentrated
iE
ifil
--Gr
hydrochloric acid (HCl) is slowly added to an aqueous -\
solution of cobalt(II) ions, the cobalt(II) ions react with ,!(
.'*
.t
the chloride ions in the acid to form a series of complex iH
ions. The stability constants of these complex ions .-€!
-:t
increase as more chloride ions are added. The addition of ts
HCl causes the equilibrium to shift towards the formation -.e
of these complex ions, which are more stable than the
original cobalt(II) ion in water.

:.....
::+
,f(
::R
..{d
.']'|r1
.-E
:-trt

[3 marksl
H
Total 15 marks '.'-ht
i:E
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END OF TEST ,.trl
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IF YOU FINISH BEFORE TIME IS CALLED, CHECK YOUR WORK ON THIS TEST. :G
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o2lt2020lcAPE 2016

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