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CATHOLIC JUNIOR COLLEGE

JC2 Mock Examination 2010


Higher 2

CANDIDATE
NAME
CLASS 2 T

CHEMISTRY 9647/02
Paper 2 Structured 08 October 2010

Candidates answer on the Question paper 2 hr


Additional Materials: Data Booklet

READ THESE INSTRUCTIONS CAREFULLY


Write your name and class in the spaces provided above.
Write in dark blue or black pen.
You may use a soft pencil for any diagrams, graphs or rough working.
Do not use staples, paper clips, highlighters, glue or correction fluid.

You are reminded of the need for good English and clear presentation in your answers.
The number of marks is given in brackets [ ] at the end of each question or part
question.

Answer all questions.


A Data Booklet is provided.

For Examiner’s Use


Q1
Q2
Q3
Q4
Q5
Q6

72

This document consists of 12 printed pages and 0 blank page.


CJC Chemistry Department

© CJC 2010
1 Planning (P)

Some iron tablets, containing iron (II) sulfate, were left on the shelf for too long such that
some of the iron (II) sulfate was oxidised into iron (III) sulfate.

You are to carry out a titrimetric analysis to determine the percentage by mass of Fe3+ ions
present in the sample of oxidised iron tablets.

The following reagents are provided to enable the experiment to be carried out:
• Sample of oxidised iron tablets
• 1.00 mol dm-3 sulfuric acid, H2SO4
• 0.0110 mol dm-3 potassium dichromate (VI), K2Cr2O7
• N-phenylanthranilic acid as indicator
(1 cm3 of indicator produces a violet colour change at end-point)
• Zinc powder

(a) The oxidised iron tablets must first be dissolved in water to liberate the Fe2+ and Fe3+
ions. A suitable quantity of sulfuric acid is then added to the solution.

Suggest a reason why sulfuric acid is used in the preparation of the mixture of Fe 2+
and Fe3+ solution.

Fe2+ is stabilised in an acidic medium


OR
To prevent oxidation of Fe2+ to Fe3+

[1]

(b) Write the ionic equation for the reaction between Fe2+ ions and potassium
dichromate (VI) solution.

6Fe2+ + Cr2O72- + 14H+  6Fe3+ + 2Cr3+ + 7H2O


[1]

(c)An unoxidised sample of iron tablet was dissolved and made up to 250 cm3. 25.0 cm3
of the Fe2+ ions solution required 15.00 cm3 of potassium dichromate (VI) to reach an
end-point in a titration.
Calculate the mass of FeSO4 in the unoxidised sample of iron tablet that was used.
15.00
0.0110 ×
No. of mol of Cr2O 7
2-
used = 1000
= 1.65 × 10-4 mol
6Fe2+ ≡ Cr2O72-

No. of mol of Fe2+ present in 25.0 cm3 = 6 × 1.65 × 10-4


= 9.91 × 10-4 mol [1, c.a.o.]

250
9.91×10 −4 ×
No. of mol of Fe2+ present in 250 cm3 = 25
= 9.91 × 10-3 mol

Mass of iron tablet (which contains FeSO4) = 9.91 × 10-3 × (55.8+32.1+4(16.0))


= 1.51 g [1, e.c.f.]
[2]

CJC H2 JC2 Mock Examination 2010 2


(d) A sample of oxidised iron tablet is equally divided and dissolved to give two portions
of 250 cm3 acidified Fe2+ and Fe3+ ions solutions for analysis.

Procedure 1

To one portion, the Fe3+ (aq) should be converted into Fe2+ (aq) first using excess zinc
metal, before titration against potassium dichromate (VI) solution.

Procedure 2

To the other portion, the Fe2+ (aq) can be directly titrated against potassium
dichromate (VI) solution.

Outline in order, the steps you would carry out for Procedure 1. In your description,
you should include details of the apparatus and chemicals used and measure(s) taken
to ensure reliability of results.

1) Add Zn powder to the beaker containing the 250 cm3 solution of Fe2+/Fe3+ ions with
stirring until no more Zn dissolves.
2) Filter the mixture using a filter funnel and collect the filtrate containing Fe2+ ions.
3) Pipette 25.0 cm3 of the Fe2+ solution (filtrate) into a conical flask and to it, add 1 cm 3 of
N-phenylanthranilic acid using a 10 cm3 measuring cylinder / graduated dropper.
4) Fill a burette with the given standard K2Cr2O7 solution and note the initial reading on the
burette.
5) Titrate the Fe2+ solution in the conical flask until the solution turns (from pale green to
yellow to) violet; note the final reading on the burette.
6) Repeat the titration (steps 3 – 5) for consistent results (ie. titre values are within ± 0.10
cm3 of each other).

Marking points
Procedure should include appropriate apparatus commonly found in a college laboratory:
• Addition of excess Zn powder into Fe2+/Fe3+ solution until no more Zn dissolves
• Filtration and collection of filtrate
• Proper preparation of aliquot
• Use of correct volume of indicator added
• Titration of aliquot against standard K2Cr2O7 with end-point colour change to violet
noted
• Initial and final burette readings noted with repeat of titration for consistent results

[5]

CJC H2 JC2 Mock Examination 2010 3


(e)Using the following information, calculate the percentage by mass of Fe3+ ions in the
oxidised iron tablet sample.

No. of mol of Fe2+ (in 250 cm3) from Procedure 1 = p


No. of mol of Fe2+ (in 250 cm3) from Procedure 2 = q
Ar: O, 16.0; S, 32.1; Fe, 55.8

No. of mol of Fe3+ present in 250 cm3 = p - q

No. of mol of Fe3+ present in sample = 2 × (p – q)

Mass of Fe3+ in actual sample = 2(p – q) × 55.8 [1]

Mass of oxidised iron tablet (containing FeSO4 + Fe2(SO4)3)


= (2q × 151.9) + [½ × 2(p – q) × 399.9]
= 399.9p – 96.1q

111.6(p - q)
×100%
Percentage by mass of iron(III) in sample = 399.9 p - 96.1 q
116.1(p - q)
%
= 4.2p - q [1]

[2]

(f) By modifying Procedure 1, suggest another means by which the amount of Fe3+ in an
oxidised iron tablet sample can be determined.

Add a known mass of excess Zn powder to the solution containing Fe2+/Fe3+ ions.

Filter the resultant solution, recover and dry the residue containing the unreacted Zn
powder.

The difference in mass of Zn can be used to calculate the no. of mol of Fe3+ present.

Alternative test: Iodometric titration (Fe3+ / I-)

[1]

[Total: 12]

CJC H2 JC2 Mock Examination 2010 4


2 (a) The melting points of the chlorides of the Period 3 elements magnesium to
phosphorous, are given below.

Magnesium Aluminium Phosphorous


Compound
chloride chloride pentachloride

(i) Account for the


difference in the Melting point / oC 714 178 162
melting points of
magnesium chloride and aluminium chloride, in terms of structure and bonding.

MgCl2 has a giant ionic lattice structure held by strong electrostatic forces of
attraction between the oppositely charged Mg2+ and Cl- ions. A large amount of
energy is required to overcome the strong electrostatic forces of attraction,
hence the melting point is high.

Aluminium chloride has a simple molecular structure.


The molecules are non-polar and held by which can be easily broken during
melting weak induced dipole-induced dipole attractions/ Van der Waal’s forces of
attraction. A small amount of energy is required to overcome the weaker forces
of attraction between the molecules, hence the melting point is low.
[1: Correct structures, 1: Correct bonding, 1: relative energy mentioned]

(ii) Explain the difference in the pH values when AlCl3 and PCl5 are separately dissolved in water.
Write equations to support your answer.

Al2Cl6 undergoes both hydration and hydrolysis when dissolved in water. The
high charge density of hydrated Al3+ ion enables it to attract electrons away from
one of its surrounding water molecules, thereby polarising and weakening the O-
H bond to a greater extent which results in the release of a proton. pH = 3.0

AlCl3 + 6H2O  [Al(H2O)6]3+ + 3Cl-

[Al(H2O)6]3+ [Al(H2O)5(OH)]2+ + H+

PCl5 undergoes complete hydrolysis to form a strongly acidic solution with


pH=1.0/2.0

PCl5 + 4 H2O  H3PO4 + 5 HCl


[1: Correct description for Aluminium, 1: Correct pH, 1: Correct Equations]

[6]

CJC H2 JC2 Mock Examination 2010 5


(b) Elements K, L, M and N are four consecutive Period 3 elements. The table below
shows the first four ionisation energies of elements K, L, M and N.
Element First I.E Second I.E Third I.E Fourth I.E
K 577 1820 2740 11600
L 786 1580 3230 4360
M 1060 1900 2920 4960
N 1000 2260 3390 4540

(i) For element K, briefly explain why the energy difference between the removal of
the 2nd and 3rd electrons is smaller than that between the removal of the 3rd and
4th electrons.

2nd and 3rd electrons occupy the same quantum shell while 3rd and 4th electrons
are removed from the different quantum shell. [1]

(ii) Explain why the first ionisation energy of element N is lower than that of element
M.

N  N+ +e
1s22s22p63s23p4 1s 2s 2p63s23p3
2 2

M  M+ +e
1s22s22p63s23p3 1s 2s 2p63s23p2
2 2

OR

Element N is Group VI and Element M is Group V.


There is inter-electron repulsion between the paired electrons in the 3p orbital of
element N.
Hence less energy is required to remove one valence 3p electron from N.
⇒ 1st ionisation energy of M > N.
[1: correct electronic configuration or group, 1: correct reason]

(iii) Element T is a Period 2 element in the same group as element M. Suggest with
reasoning why element M can form an oxo-anion of formula MO43- but element T
cannot.
M, being in Period 3, has empty and energetically accessible d orbitals to expand
the octet configuration. Hence MO43- can exist. [1]

T, being in Period 2, does not have empty and energetically accessible d orbitals
to accommodate the extra electrons and cannot expand the octet configuration.
Hence TO43- cannot exist. [1]

[5]
(c) Many interhalogen compounds are very active oxidising agents as well as strong
acids. Examples are oxoacids of chlorine, chloric(V) acid, HClO3 and chloric(VII) acid,
HClO4.

(i) With an aid of an equation, show HClO3 as a strong Bronsted-Lowry monoprotic


acid in an aqueous solution.

HClO3 + H2O → H3O+ + ClO3- [1: only full arrow accepted]

CJC H2 JC2 Mock Examination 2010 6


(ii) Explain why chloric(VII) is a stronger acid than chloric(V) acid in terms of their
structures and bonding.

ClO4- more stable as the negative charge is delocalised over a larger number of
oxygen atoms. Hence chloric(VII) is a stronger acid.
[1]

(iii) Draw the dot-cross diagram of HClO3. Using VSEPR model, predict the shape
with respect to Cl and indicate a possible O-Cl-O bond angle.

xx
x x x
H O Cl x O
xx

Shape – trigonal pyramidal ; bond angle - 1070


[1: Correct dot and cross, 1: correct shape, 1: correct angle] [5]
[Total: 16]

3 (a) Consider an equilibrium mixture,

4NH3(g) + 3O2(g) 2N2(g) + 6H2O(g) ΔH = −1267 kJmol−1

The graph below shows how the fraction of N2(g) in the equilibrium mixture varies with
temperature and pressure.

Fraction of N2
in equilibrium
mixture
P1
P2
temperature

(i) Comment on the shape of the curve.

As temperature increases, amount of N2 decreases[1]. Therefore the equilibrium


position has shifted to the left[1] since ΔH is exothermic.

(ii) On the same graph, sketch a curve to show how the fraction of N2 changes at a
higher pressure, P2 . [1]
[3]

(b) An initial 5 moles of NH3 and 3 moles of O2 are mixed in a 2 dm3 vessel. At 4500C, an
equilibrium mixture shows 80% of ammonia remains.
Calculate a value for the equilibrium constant, Kc and give its unit.

(0.5/2)2 (1.5/2)6
Kc = (4/2)4 (2.25/2)3 [1 correct equation used, correct values substituted]

= 4.88 X 10-4 mol dm-3 [1 e.c.f. with units]


[3]

CJC H2 JC2 Mock Examination 2010 7


(c) Hydrogen gas is used in the industry to convert N2 into ammonia for the use in
fertilizers. One method of preparing H2 is to pass a mixture of carbon monoxide and
steam over a Cu/Zn catalyst.

CO(g) + H2O(g) CO2(g) + H2(g) ΔH = −41 kJmol−1

(i) Use the given ΔH and bond energies values from the data booklet, construct an
energy cycle and hence calculate the bond energy in the CO molecule.

[1: energy cycle with correct values]


B.E.(CO) = –2(460) –41+ 2(740) + 436 = 955 kJmol-1 [1 e.c.f. with units]

(ii) With the aid of the Boltzman-maxwell distribution curve, explain how Cu/Zn
affects the rate of the above reaction.

Area under curve with


Fraction of Ecat > Euncat
particles with
energy

energy
Ecat Euncat

[1: correct diagram]


Catalyst provides an alternative pathway for the reaction with a lower activation
energy. [1].
Hence more reactants have energy greater than or equal to the activation
energy[1].
as shown by bigger area. Hence effective collisions increase and rate
increases[1].

[6]

[Total: 12]

CJC H2 JC2 Mock Examination 2010 8


4 The elements of Group VII were discovered in the 17th century by different European
scientists. Due to their high reactivity, they are found in the environment only in compounds
such as halides in minerals and halogenated organic compounds in living organisms.

(a) The plots of PV/RT against P for one mole of an ideal gas and one mole of HCl at 100
K are given below.

(i) Show clearly, on the same axes, how one mole of HF will behave at the same temperature of
100 K.
HCl (100 K)
PV/RT
HF (100 K)

1 mark
HCl (400 K)

Ideal Gas
1.0

1 mark

(ii) Explain the difference in behaviour between HF and HCl at 100 K.

HF is less ideal than HCl as HF has stronger intermolecular hydrogen


bonding whereas HCl has weaker intermolecular Van der Waals forces of
attraction. [1]

(iii) Explain what happens when the HCl gas is heated to 400 K.
Illustrate your answer clearly on the same axes in a(i).

At high temperature, there are negligible forces of attraction between the


gas particles.
Hence, HCl gas will deviate less from ideal gas behaviour. [1]

[4]

CJC H2 JC2 Mock Examination 2010 9


(b) 2-chloropropane can be made by the chlorination of propane.

(i) Outline the reaction mechanism of its formation, labelling each step in the mechanism
appropriately.

Free radical substitution [1]

Initiation stage
Ultraviolet light
Cl2 2 Cl•

Propagation stage • [1]


CH3CH2CH3 + Cl• CH3CHCH3 + HCl

CH3CHCH3 + Cl2 CH3CH(Cl)CH3 + Cl•

Termination stage
2 Cl • Cl2

CH3CHCH3 + Cl • CH3CH(Cl)CH3 [1]
• •
CH3CHCH3 + CH3CHCH3 CH3CH(CH3)CH(CH3)CH3 or C6H14

(ii) Explain why the reaction requires only a flash of ultraviolet light rather than
prolonged radiation.

Condition of heat or uv light applies only in initiation step as chlorine free


radicals are regenerated in propagation stage to keep reaction going. [1]

[4]

(c) Bromine and fluorine can react to form an interhalogen liquid compound BrF3, a
common fluorinating agent. This compound can react with silicon (IV) oxide according
to the following equation.

4BrF3 + 3SiO2  3SiF4 + 2Br2 + 3O2


The amount of bromine produced can be determined by reacting it with sodium
thiosulfate solution, Na2S2O3 (aq).

(i) Write the equation for the reaction between bromine and thiosulfate ions in acidic medium,
given S2O32- + 5H2O ⇌ 2SO42- + 10H+ + 8e-.

4Br2 + S2O32- + 5H2O → 2SO42- + 10H+ + 8Br - [1]

CJC H2 JC2 Mock Examination 2010 10


(ii) Determine the mass of SiF4 produced, to one decimal place, if 30.0 cm3 of 0.100

mol dm 3 Na2S2O3 solution was required to completely react with the bromine
liberated from the reaction between BrF3 and SiO2.

No. of moles of S2O32- = 30/1000 x 0.100


= 0.00300 mol [1]
S2O32- ≡ 4Br2 ≡ 6 SiF4
No. of moles of SiF4 = 6 x 0.003
= 0.018
Mass of SiF4 = 0.036 x (28.1 +19.0 x 4)
= 1.9 g [1]

(iii) The bromine produced could also be reacted with cold aqueous sodium hydroxide to
form a mixture of products.

State the type of reaction that it has undergone and write a balanced equation
for the reaction involved.

Disproportionation [1]
- - -
3 Br2 + 6 OH  5Br + BrO3 + 3 H2O [1]

[5]
[Total: 13]

5 The structural formula of


O a compound R is shown below.
O
O

CH2 – C – CH3
OH

(a) Compound R undergoes a 2 step reaction to produce Compound Z. Draw the


intermediate product and state the reagents and conditions used for both steps. [3]

Intermediate product
O O O O
Step 1
O OH
CH 2 C CH3 CH 2 C CH3
H
OH OH
Compound R

NaBH4 in dry ether


Step 1: ______________________________ Step 2

Excess concentrated H2SO4, 170 C o O O


Step 2: ______________________________

CH 2CHCH 2
Compound Z
CJC H2 JC2 Mock Examination 2010 11
(b) Draw the structural formula(e) of the organic product(s) formed when compound
R reacts with each of the following reagents.
[6]

Reagent Structural O
Oformula(e) of the organic product(s)

O
II
Aqueous CH2 – C – O– + CHI3
alkaline I2 OH
[2]

OH
O OH
Acidified
potassium
dichromate(VI),
reflux CH2COCH3
O [1]

O O

O
Ethanoyl II
Chloride CH2 – C – CH3
OCOCH3
[1]

O- Na+
O O- Na+
Aqueous
NaOH, reflux
CH2COCH3 [1]
OH

O O

O
II
Thionyl chloride CH2 – C – CH3
Cl

[1]

[Total: 9]

CJC H2 JC2 Mock Examination 2010 12


6 Chymotrypsin is a digestive enzyme found in the small intestines that can hydrolyze peptide
bonds within the protein. It is also used as a form of treatment for sports injuries to reduce
pain and inflammation.

(a) Using chymotrypsin, a small peptide Y was broken down to form three different amino
acids according to the following reaction.

NH2CHCO 2H

CH2 NH 2CHCO 2H NH 2CHCO2H

CH 2 (CH2)3
AY 2 + 3 + 2
HN
NH

H2N
OH
Tyrosine Phenylalanine Arginine
M r = 181 Mr = 165 Mr = 174

(i) Calculate the Mr of peptide Y.

Hydrolysis of peptide Y  gain in 1 H2O for every peptide bond broken.


No. of peptide bonds broken = 6 [1]

Mr of peptide Y = 2 x 181 + 3 x 165 + 174 x 2 - 6 x 18


= 1097 [1]

CJC H2 JC2 Mock Examination 2010 13


(ii) The graph shows the results of an investigation of the initial rate of hydrolysis of peptide Y by
the enzyme chymotrypsin. In the experiments, the initial concentration of peptide Y was varied
but that of chymotrypsin was kept constant.
Rate

[Peptide Y]
Explain the difference in the rate of hydrolysis at high and low concentrations of
peptide Y.

At low concentration of peptide Y,


 Rate of reaction increases linearly as active sites of the enzyme are
not fully occupied
 Reaction is approximately first order wrt the concentration of
peptide Y. [1]
However, at high concentration of peptide Y,
 Rate of reaction is constant
 Rate is independent of concentration of peptide Y as all active sites
occupied
 Reaction is zero order wrt the concentration of peptide Y. [1]

[4]
(b) The table below shows some of the amino acid residues in chymotrypsin.

Name of amino Formula of side chain


acid residues (R in RCH(NH2)CO2H)
Serine ―CH2OH
Histidine
NH
― CH2

N
Aspartic Acid ―CH2COOH
Valine ―CH(CH3)2
Lysine ―(CH2)4NH2
Phenylalanine ―CH2(C6H5)

(i) The amino acids which are on the outside of the chymotrypsin are hydrophilic.
Suggest, with reasoning, which two of the amino acids in chymotrypsin are likely to
have this property.

Any 2 of the following: Serine, Aspartic acid, Lysine, Histidine. [1]


This is due to the formation of hydrogen bonding between the amino acids
and water molecules. [1]

CJC H2 JC2 Mock Examination 2010 14


(ii) Explain, in terms of R group interactions, how a low pH might affect the enzymatic
activity of chymotrypsin.

At low pH,

 Excess H+ will react with basic amine group in histidine/lysine of the


chymotrypsin.
 Hence, low pH will disrupt ionic bonds and hydrogen bonds formed
between basic amine group in histidine/lysine and the acidic carboxylic
group in aspartic acid which are critical to the tertiary and quaternary
structure of the enzyme.
 This will thus lead to changes in enzyme shape and shape of active
site and hence loss of enzyme activity and denaturation. [1]

[3]

(CH 2)4NH 2

(b) Part of the chain of polypeptide Z is shown below.


CONHCHCONHCHCON CHCONH

CH2CONH2

Draw the structure of the products formed when polypeptide Z is treated with
excess aqueous NaOH under prolonged heating.

(CH 2) 4NH2 CH 2COO-

NH 2CHCO 2- NH 2CHCO 2- HN

COO-

[1 mark each, must show carboxylate ion]

[3]
[Total: 10]

CJC H2 JC2 Mock Examination 2010 15