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CANDIDATE
NAME
CLASS 2 T
CHEMISTRY 9647/02
Paper 2 Structured 08 October 2010
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.
72
© 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.
[1]
(b) Write the ionic equation for the reaction between Fe2+ ions and potassium
dichromate (VI) solution.
(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-
250
9.91×10 −4 ×
No. of mol of Fe2+ present in 250 cm3 = 25
= 9.91 × 10-3 mol
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]
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.
[1]
[Total: 12]
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.
(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
[Al(H2O)6]3+ [Al(H2O)5(OH)]2+ + H+
[6]
(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
(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.
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
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
(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]
(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.
(ii) With the aid of the Boltzman-maxwell distribution curve, explain how Cu/Zn
affects the rate of the above reaction.
energy
Ecat Euncat
[6]
[Total: 12]
(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
(iii) Explain what happens when the HCl gas is heated to 400 K.
Illustrate your answer clearly on the same axes in a(i).
[4]
(i) Outline the reaction mechanism of its formation, labelling each step in the mechanism
appropriately.
Initiation stage
Ultraviolet light
Cl2 2 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.
[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.
(i) Write the equation for the reaction between bromine and thiosulfate ions in acidic medium,
given S2O32- + 5H2O ⇌ 2SO42- + 10H+ + 8e-.
(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]
CH2 – C – CH3
OH
Intermediate product
O O O O
Step 1
O OH
CH 2 C CH3 CH 2 C CH3
H
OH OH
Compound R
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]
(a) Using chymotrypsin, a small peptide Y was broken down to form three different amino
acids according to the following reaction.
NH2CHCO 2H
CH 2 (CH2)3
AY 2 + 3 + 2
HN
NH
H2N
OH
Tyrosine Phenylalanine Arginine
M r = 181 Mr = 165 Mr = 174
[Peptide Y]
Explain the difference in the rate of hydrolysis at high and low concentrations of
peptide Y.
[4]
(b) The table below shows some of the amino acid residues in chymotrypsin.
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.
At low pH,
[3]
(CH 2)4NH 2
CH2CONH2
Draw the structure of the products formed when polypeptide Z is treated with
excess aqueous NaOH under prolonged heating.
NH 2CHCO 2- NH 2CHCO 2- HN
COO-
[3]
[Total: 10]