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Ijc2009 Prelim 1 Paper 2
Ijc2009 Prelim 1 Paper 2
Ijc2009 Prelim 1 Paper 2
1 When aqueous sodium thiosulfate, Na2S2O3 is mixed with hydrochloric acid, HCl, a fine
suspension of solid sulfur is form.
If a beaker containing the reaction mixture is placed over a marker, the sulfur slowly hides
the marker from view. If the depth of solution is constant, the writing will always disappear
when the same amount of sulfur has been formed.
You are given 0.500 moldm-3 solution of Na2S2O3 and 0.500 moldm-3 solution of HCl to study
the rate of the reaction. You are required to determine the order of reaction with respect to
Na2S2O3.
(a) Suggest and explain the quantities of each reagent you will use in your experiments.
In order to find order of reaction with respect to Na2S2O3, volume of aqueous Na2S2O3 varies
[ 1 m], volume of HCl keep constant [ 1 m].
2 2
For the first set of experiment: 50.0cm3 of aqueous Na2S2O3 and 5.0 cm3 of HCl.
For the second set of experiment: 25.0cm3 of aqueous Na2S2O3, 25.0cm3 of water and 5.0
cm3 of HCl.
Allow a third or fourth set of experiment.
Also some students describe how to find the order of HCl as well which is not
necessary.
(b) Based on the quantities suggested in (a), write a plan consisting of a series of experiments to
determine the order of reaction with respect to aqueous Na2S2O3. This can be done by
studying the time taken for the writing to disappear with different amounts of aqueous
Na2S2O3. You may use the reagents and apparatus normally found in a school or college
laboratory.
Use a 50 cm3 measuring cylinder to place 50.0cm3 of aqueous Na2S2O3 into a 250 cm3
beaker. [ 1 m] mark for process
2
Place the beaker over the writing. [ 1 m]
2
Measure 5.0 cm of HCl using a 10 cm3 measuring cylinder. [ 1 m] mark for process
3
2
Pour the HCl into the beaker, swirl the beaker to mix the solutions [ 1 m] and at the
2
same time start the stop-watch [ 1 m]
2
When the writing is no longer visible, record the time. [ 1 m] This is T1.
2
For the second set of experiment, use a 50 cm3 measuring cylinder to place 25.0cm3 of
aqueous Na2S2O3 into a 250 cm3 beaker. Place the beaker over the writing.
Measure 25.0 cm3 of water using a 50 cm3 of measuring cylinder. Pour the water into the
beaker.
Measure 5.0 cm3 of HCl using a 10 cm3 measuring cylinder. [ 1 m] mark for process
2
(water before HCl)
Pour the HCl into the beaker, swirl the beaker to mix the solutions and at the same time
start the stop-watch.
When the writing is no longer visible, record the time. This is T2[ 1 m]
2
Common mistake: Most students just say repeat the experiment for another time by
adding varying amount of reagents and WATER!
Most students did not have the two underlined points (bold in red).
(c) Explain how you will analyse the experimental results and determine the order of reaction
with respect to aqueous Na2S2O3.
Inspection Method:
Expt Vol of Vol of water Vol of Time/s (1/time)/s-1
aqueous /cm3 aqueous
Na2S2O3 HCl/cm3
/cm3
1 50.0 0.0 5.0
2 25.0 25.0 5.0
Allow more than 2 sets of experiments and other volumes (as long as total volume is
constant)
Table with Headers (Expt, Vol of aqueous Na2S2O3, Vol of water, Vol of aqueous HCl, Time)
[ 1 m]
2
Unit of (1/time) which is s-1 [ 1 m] and vol of aqueous Na2S2O3 which is cm3, [ 1 m] reflected
2 2
on the graph
(d) Explain why the following concentrations of aqueous Na2S2O3 are not suitable for this
reaction.
50.0 mol dm-3: The concentration is too large [ 1 m] as compared to the concentration of
2
HCl and the order of aqueous Na2S2O3 cannot be determined as it is pseudo zero order.
[ 1 m]
2
Common mistake: Students only say large volume of HCl required.
5.0 x 10-3 mol dm-3: The concentration is too small [ 1 m] as compared to the concentration
2
of HCl and since rate is proportional to the concentration of aqueous Na2S2O3, the reaction
may be too slow. [ 1 m]
2
(e)
Based on the procedures or limitations of apparatus used, state one significant source of
error in this experiment.
The temperature throughout the reaction may not be kept constant [1m] and hence will affect
the accuracy of the time taken and the rate of reaction calculated. OR Burette can be used to
measure Na2S2O3 as it is more precise. [1m]
Common mistake: Students ten to give (i) human error in starting and stopping
stopwatch (ii) subjective in determining the end point of reaction.
[Total: 12]
2 (a) Suggest why the relative atomic mass stated in the periodic table for Cu is 63.5 but not a whole
number.
[1]
Cu exists as isotopes [ 1 m] and atomic mass is the weighted average [ 1 m] of the mass of
2 2
the isotopes
(Most students only mentioned the presence of isotopes, but did not mention how the
relative atomic mass is calculated)
(b) When separate beams of 63Cu2+ and 127I are passed through an electric field as shown below,
they behave differently.
(i) Given that the angle of deflection of the beam of 63Cu2+ ions is 7.0o, calculate the angle of
deflection of the beam of 127I ions, correct to 1 decimal place.
(Marks deducted when beam deviates before entering the electric field)
(ii) Sketch on the diagram in (b), the paths taken by beams of 63Cu2+ and 127I ions in the
presence of the electric field.
Each correct direction [ 1 m] x 2; each correct angle of deflection. [ 1 m] x 2
2 2
Total : [2m]
[3]
(c) Copper and iodine are both shiny crystalline solids. The crystal structures of copper and iodine
are both face-centred cubic. The diagram shows the arrangement of the particles in this type of
crystal lattice.
(i) What type of particles is present in the copper crystal? State the interactions within the
crystal.
(ii) What type of particles is present in the iodine crystal? State the interactions between the
particles.
(i) When dilute aqueous ammonia is added gradually to a solution containing copper (II)
ions,
Observation: A pale blue precipitate [ 1 m] of Cu(OH)2 [ 1 m] is formed.
2 2
Equation: NH3 + H2O NH4+ + OH- [ 1 m]
2
Cu(H2O)6]2+ (aq) + 2OH- (aq) Cu(OH)2 (s) + 6H2O(l) [ 1 m] OR
2
2+ - 1
Also accept: : Cu (aq) + 2OH (aq) Cu(OH)2 (s) [ m]
2
(ii) When excess ammonia is added,
Observation: Pale-blue precipitate [ 1 m] of Cu(OH)2 dissolves to form a deep blue
2
solution [ 1 m]
2
Equation: Cu(OH)2 (s) + 4NH3 (g) + 2H2O(l) [Cu(NH3)4(H2O)2]2+ (aq) + 2OH-(aq)
[1m]
I. Hess Law states that the enthalpy change in a chemical reaction is the same regardless
of the reaction pathway taken provided the initial states of the reactants and final states of
the products are the same. [1m]
Use the data in the table above to construct an energy cycle to calculate the standard
enthalpy change of the following reaction:
Ca2+(aq) + SO42-(aq) CaSO4(s)
[ 1 m] for each correct path, Total [4 x [ 1 m]]
2 2
H = + 907 347 1435
= 875 kJmol-1 [1m]
[4]
[Total: 14]
3 When carbon dioxide gas dissolves in water, carbonic acid (a diprotic acid) with Ka1 value of 4.3 x
107 mol dm3 is formed.
H2CO3 (aq) H+ (aq) + HCO3- (aq) Ka1 = 4.3 x 10-7 mol dm-3
HCO3- (aq) H+ (aq) + CO32- (aq)
(a) A student was instructed to titrate 25.0 cm3 of 0.100 mol dm3 carbonic acid, H2CO3, with
0.0625 mol dm3 barium hydroxide, Ba(OH)2.
(ii) Write an equation for the reaction between aqueous barium hydroxide and carbonic acid.
H2CO3 (aq) + Ba(OH)2 (aq) BaCO3 (aq) + 2H2O (l) [1m]
Not marking for state symbols
Some students thought CO2 was one of the products
(iii) Calculate the volume of Ba(OH)2 needed to completely react with 25.0 cm3 of 0.100 mol
dm3 H2CO3.
H2CO3 + Ba(OH)2 BaCO3 + 2H2O
(iv) Calculate the pH of a solution which contains both H2CO3 and HCO3 in equal
concentrations.
[HCO 3 ][H + ]
Ka1 = pH = pKa1 [ 1 2 m] = 6.37 [ 1 2 m]
[H 2 CO 3 ]
Again, those who cannot do it is because they forgot the simple formula
(v) Using your answers from (a)(i) to (a)(iii), sketch the shape of the pH curve during the
titration in the space below.
General shape:
pH Curve shows 2 equivalence pt [ 1 m]
2
3
6.37 Full equivalence pt at 40cm of Ba(OH)2 [ 1 m]
2
3.68
Volume of Ba(OH)2/cm3
0 10 unable
Majority were 20 to draw40 this graph correctly, not knowing there were two equivalence
points, and not able to label the pKa correctly.
[7]
(b) Three experiments were performed where different masses of ethanoic acid were expanded into
a vessel of volume 15 dm3 at different pressures and at a temperature of 100 oC.
It is also known that ethanoic acid undergoes dimerisation via the following equation:
2CH3COOH(g) (CH3COOH)2(g)
(i) Assuming ideal behaviour, calculate the relative molecular mass of ethanoic acid, for
experiment C.
(ii) Using Le Chateliers Principle, explain the trend in relative molecular mass of ethanoic
acid with increasing pressure.
Ethanoic acid will form dimer via:
2 CH3COOH (g) (CH3COOH)2 (g)
When pressure increases, the equilibrium shifts to the right [1m] so as to decrease the
pressure by forming lesser gaseous molecules [ 1 m]. Thus, the mixture will contain
2
more dimer (CH3COOH)2 molecules [ 1 m] and therefore the Mr increases.
2
Many did not explain more dimmers will be formed
(iii) When experiment B was repeated at 200 oC, keeping all other conditions constant, the
relative molecular mass of ethanoic acid calculated decreased. Explain this phenomenon.
2 CH3COOH (g) (CH3COOH)2 (g) H = exothermic
The formation of dimer is exothermic as hydrogen bonds are formed. As temperature
increases, the equilibrium shifts to the left [1m] so as to absorb additional heat to
decrease the temperature [ 1 m]. Thus, the mixture will contain more of the
2
monomers CH3COOH / less of the dimers [ 1 m] and therefore the Mr decreases.
2
Many did not explain that heat was absorbed to counteract the change
[5]
[Total: 12]
4 (a) By using the relevant E values from the Data Booklet and writing equations when
necessary, explain the following observations.
(i) When iron(III) sulfate is added to aqueous KI, the solution turns brown. [2]
Markers comments
A number of candidates were not precise in their answers and left out keywords such
as reduced to iron(II) and oxidised to iodine.
(ii) When iron(III) sulfate is added to aqueous KCN, an orange-red solution is formed.
[2]
(b) The standard electrode potential of the Fe3+(aq)/Fe2+(aq) half-cell relative to the standard
hydrogen electrode is + 0.77 V. Predict, with reasons, how the EFe3+ / Fe2+ and Ecell of
reaction will change if distilled water is added to the Fe3+(aq)/Fe2+(aq) half-cell.
Addition of pure water will decrease [Fe3+] and [Fe2+] to the same extent [ 1 m]
2
Hence the equilibrium will not shift [ 1 m] and E Fe3+ / Fe2+ will not change [ 1 m]
2 2
Thus the Ecell will not change. [ 1 m]
2
Markers comments
A large number of candidates did not state clearly that the concentrations would decrease
to same extent. A few candidates did not read the question properly to state clearly that
BOTH the EFe3+ / Fe2+ and the Ecell will not change.
OH
H3C
OH
Draw the structures of the products formed when Compound X is separately reacted with
each of the following reagents.
OH OH
H3C OH Br H3C Br OH
OH OR OH [1m]
(ii) hot acidified K2Cr2O7
NH3
H3C
OH [1m]
(iii) hot alkaline KMnO4
NH2
C
O
O O
H3C
OH [1m]
Markers comments
This question is very badly done even for the more able candidates. Many failed to
associate the reagents with the various functional groups present in the molecule.
(d) (i) Suggest the reagents and conditions for the following conversion.
Markers comments
Majority failed to gain credit for Step 1 as they have wrongly used KMnO4, forgetting
it will undergo side chain oxidation to benzoic acid.
CONH2
OR
Compound A: Reddish brown bromine remains/No white HBr fumes are formed.
[ 1 m]
2
Markers comments
Quite a number of candidates used bromine without any halogen carrier and the
correct conditions (HEAT, in the dark) was also not often stated. Quite a number of
candidates even wrote heat with reflux in their answers.
[Total:14]
5 (a) (i) Group II elements, magnesium and barium, react with water to give different
products. Explain the reactions by writing appropriate equations with state symbols.
(ii) Comparing calcium sulfate and barium sulfate, calcium sulfate is sparingly soluble in
water while barium sulfate is insoluble in water. Explain this phenomenon. You may
use the following information to help you but you are not required to show any
calculations in your answer.
The radius of the sulfate ion is much larger than the radius of Ba2+ and Ca2+.
[ 1 m]. Hence the sum of the ionic radii remains almost constant, and lattice energy
2
is almost constant [ 1 m]. Hence Hsol depends predominantly on Hhyd. Since
2
2+
Ba has a larger ionic size than Ca2+, charge density of Ba2+ is lower [ 1 m],
2
Hhyd is less exothermic and hence Hsol becomes less exothermic [ 1 m].
2
and barium sulfate is less soluble in water.
[4]
Markers Comments:
Many students could not do this question. For those that did, they were not precise with
their use of terms. Common errors were:
- The charge density of CaSO4 is higher than that of BaSO4.
- The Hsol of CaSO4 is more than that of BaSO4 (did not specify whether is is more
or less exo.)
(b) Coumarin is a naturally occurring organic compound with a grassy odour. A series of
reactions involving Coumarin is shown below.
Compound A coumarin
CH CHCOCl
I H2O(g)
C
Q
heat Conc. H3PO 4
OH O O 300oC
65 atm
H2SO4(aq) KMnO4(aq)
B
P D
R E
S F
T
heat
Draw the structures of organic compounds B F.
B: C: D:
OH
CH CHCOOD H
COOH COO-Na+
OH OH O-Na+
COOH
OH OH
[1m] [1m]
[Total: 9]
Markers comments:
Whole question generally badly done.
B: Many students performed Electrophilic addition at the C=C double bond instead of
reacting with acyl chloride.
For those that reacted with acyl chloride, they ignore the presence of D in D2O, using
H2O instead.
C: Most students did not realise that the ester bond will be hydrolysed in the presence of
conc H3PO4 too.
D and E: Most students did not know how to get the products
F: A handful of students oxidised phenol to get a ketone to get a double bond at the
benzene ring without realising that carbon can only form 4 bonds.
6 (a) Two common qualitative analysis tests are used to differentiate between the different
classes of alkyl halides.
Alcoholic silver nitrate test
When silver nitrate is added to an alkyl halide in ethanolic conditions, a silver halide
precipitate may form after some time:
AgNO3 + RX + C2H5OH ROC2H5 + HNO3 + AgX(s)
These two tests were performed on a series of alkyl halides and the results are tabulated
below:
(i) Due to the conditions used, alkyl halides react predominantly by SN1 mechanism in
the silver nitrate test. By considering the structure of the alkyl halides used in the
tests above, explain why 2-bromo-2-methylpropane reacts fastest in the silver nitrate
test.
Markers comments:
Many students were able to identify the presence of 3 alkyl groups, and that they
were electron-donating. But they often omit the explanation on carbocation.
(ii) However alkyl halides react predominantly by SN2 mechanism in the sodium iodide
test due to the different test conditions. By considering the structure of the alkyl
halides used in the tests above, explain why 2-bromo-2-methylpropane reacts
slowest in the sodium iodide test.
On the other hand, there is a great amount of steric hindrance [ 1 m] caused by the
2
3 R groups in 3 alkyl halides (Alt: 2-bromo-2-methylpropane is a 3 alkyl
halides) [ 1 m] OR 2-bromo-2-methylpropane has more bulky R-groups [ 1 m],
2 2
hence causing reaction via SN2 mechanism to be very slow.
[2]
Markers comments:
Most students could answer this question well.
(b) Iodoethane can be prepared from phosphorus tri-iodide, PI3. However, PI3 is not easily
available and hence it is generated in situ from red phosphorus and iodine.
Preparation of iodoethane
1. Place in a 250 cm3 round-bottomed flask 2.5 g of red phosphorus, and then 25 cm3 of
ethanol. Fit the flask with an effective reflux condenser.
2. Thoroughly powder 25g of iodine, and add it to the contents of the flask in small
quantities of about 3 - 4 g at a time, allowing about two minutes between consecutive
additions. For this purpose the reflux condenser should be removed immediately before
each addition, the iodine rapidly dropped in, and the condenser at once replaced.
3. When all the iodine has been added, allow the reaction mixture to stand for 10 minutes
and then heat on a boiling water bath for an hour.
4. After the heating time has elapsed, rearrange the apparatus for distillation. Reheat the
flask on a boiling water bath and collect the distillate which consists of iodoethane,
ethanol and usually a little free iodine.
5. When distillation ceases, transfer the distillate to a separating funnel and shake with an
equal volume of 10% sodium carbonate solution. Run off the lower layer of iodoethane,
and discard the upper aqueous layer.
6. Return the iodoethane to the separating funnel and shake it with an equal volume of
water. Run off the lower iodoethane layer into a small conical flask, and add a few
granules of anhydrous calcium chloride, swirling occasionally until the liquid is clear.
7. Filter the iodoethane into a 50 cm3 round-bottomed flask, assemble this into a distillation
apparatus with a thermometer, and distil the iodoethane using a water-bath. Collect the
fraction distilling between 68 oC and 73 oC.
(i) Why is the iodine added in portions rather than all at once in step 2?
(ii) Why is the reaction mixture allowed to stand for 10 minutes in step 3?
Alt Ans:
The first reaction is vigorous, hence there is a need for the reaction to cease and cool
down to room temperature before heating up again. [Mark for idea] [1m]
Markers comments:
Only a handful got this correct.
(iii) What is the purpose of washing the product with sodium carbonate solution in
step 5?
Anhydrous calcium chloride (also called fused calcium chloride) is a drying agent /
used to remove water [1m].
Markers comments:
The majority could deduce the reason behind this step.
This range is to ensure that only iodoethane is distilled off [1m] while the rest of
the compounds remain in the round-bottomed flask.
OR
The boiling point range has to be above that of the iodoethane, but below that of
the other reactants. [1m]
* The boiling temperature of iodoethane is 72oC, so the choice of the range will
ensure that the distillate is pure.
[5]
Markers comments:
Only a handful got this correct.
(c) Explain, with the help of balanced equations, what happens when AlCl3(s) dissolves in
water.
3+
AlCl (s) dissolves [ 1 m] in water to form [Al(H O) ] (aq) [ 1 m]
3 2 2 6 2
3+
AlCl (s) + 6H O(l) [Al(H O) ] (aq) + 3Cl (aq) OR
3 2 2 6
3+
AlCl3 (s) Al (aq) + 3 Cl-(aq)
[1] with state symbols; deduct [ 1 m] for no or wrong state symbols
2
3+
A hydrolysis reaction occurs [ 1 m] for [Al(H O) ] , making the solution acidic [ 1 m]. OR
2 2 6 2
the pH = 3[ 1 m].
2
3+ 2+ +
[Al(H O) ] (aq) + H O(l) [Al(H O) (OH)] (aq) + H O (aq)
2 6 2 2 5 3