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2015 C2 H2 Chemistry Preliminary Examination

Paper 3 Teaching Solutions


1 (a) (i) Heterogeneous catalysis [1]

A fair number of students spelt heterogeneous wrongly. Effort must be put in to ensure
that key words should be spelt correctly. This was an easy mark that should not be
wasted.

(ii) Optical isomerism [1]

[1]

Note that the question asked for the type of isomerism. Hence writing optical isomer
is not answering the question as that refers to the molecule and not to the phenomena.

Also too many students wrote stereoisomerism instead of optical isomerism.


Stereoisomerism is the umbrella term for isomerism occurring via different spatial
arrangements of atoms in molecules with identical molecular formulae. It includes
geometrical (or cis-trans) isomerism and optical isomerism.
Some students read the question wrongly and identified the type of isomerism for the
reactant alkene instead of the product.

A fair number of students are unable to draw the mirror images correctly. More practice
is in order. Note that the positions of the filled and dashed wedge must be drawn as
shown in the diagram above. They are next to one another and are not to be split by the
line representing the CH bond as too many were wont to do. The wedges depict the
spatial arrangements of the groups, filled wedge sticking out of the plane of the paper
and dashed wedge sticking into the plane of the paper, while the line bonds indicate
the bonds lying on the plane of the paper.

These were two easy marks that were lost by too many careless or unprepared
students.

(iii) The addition of H2 to one side (bottom face) of the planar alkene molecule creates a
chiral alkane molecule. [1]

When the opposite side (top face) of the alkene is now adsorbed to the surface of the Ni
catalyst, the addition of H2 produces a chiral alkane molecule which is the non-
superimposable mirror image of the product formed at the bottom face. [1]

As there is 50% chance for each side (face) of the alkene to bind to the surface of the
catalyst, the two enantiomers are produced in a 1:1 ratio resulting in a racemic mixture.
Hence the product mixture does not rotate the plane of plane-polarised light. [1]

=================================================================

If a diagram is used, it will substitute the 1 st two marks:


Show opposite faces adsorbed to the catalyst surface [1]
Indicate which carbon forms the chiral alkane and the corresponding enantiomer. [1]

1
The marks are given if the following concepts are indicated:
1) The addition of H2 only on one face of the alkene produces an enantiomer.
2) It is the addition on the opposite face that generates the other enantiomer.
3) The alkene has 50% probability of being adsorbed on either face which leads to 1:1
ratio of the two enantiomers which gives a racemic mixture and hence the product
mixture does not rotate plane-polarised light.

Note that the addition of H2 to this alkene produces only one chiral carbon in the
resulting alkane i.e. on carbon C1 in the above diagram.

Note that catalytic hydrogenation of alkenes does not go through the electrophilic
addition mechanism. Please make sure that this misconception is properly tackled in
revision. The mechanism of addition was described in the question and it does not
resemble electrophilic addition at all.

Also it should be written that the alkene molecule may adsorbed on either face on the
catalyst surface and not that the catalyst binds to either face. Writing that the catalyst
binds to either face implies that the catalyst is like a molecule and will move about and
randomly bind to either face of the alkene. This does not happen. It is the alkene
molecule that moves freely in the liquid state (vegetable oil) that randomly binds either
face to the catalyst surface.

(b) (i) Hreaction = (B.E. of Bonds Broken) (B.E. of Bonds Formed)


= [B.E (C = C) + B.E. (H H)] [B.E (C C) + B.E. (C H) x 2]
= (610 + 436) (350 + 410 x 2)
= 124 kJ mol1

Correct bond energies used [1]


Correct equation and answer [1]

This question was unusually badly done. It is a very straightforward calculation of a very
simple reaction which does not involve the breaking and forming of many chemical
bonds.

Common mistakes include missing out the HH, CC or CH bond energies or inverting
the order of operation for bonds formed and bonds broken. More practice is in order.

(ii) Hreaction is exothermic.


Sreaction is negative as there is a decrease in the number of moles of gas in the
reaction. [1]

Given that Greaction = Hreaction TSreaction


Greaction is expected to be negative only at low temperatures and so the reaction would
be spontaneous only at low temperatures. [1]

2
This is also a very straightforward question. The question requires a student to predict
the conditions under which the reaction would be feasible, and using part (b)(i). Many
students did not make use of the sign of the H value in (b)(i) in their answer, assuming
that the examiner could read their minds, and an equally large number failed to
associate a spontaneous reaction with G < 0, assuming the examiner would make the
link. Please write everything down explicitly. The question had no reference to any of
the thermodynamic terms hence the relationship between the reaction and these terms
must be clearly spelt out in your answer. Note also the feasibility of a reaction or its
spontaneity must always be discussed in the light of the Gibbs free energy (G). Some
students merely used the enthalpy change of reaction (H) to discuss the feasibility
which is incorrect.

Note that it is the entropy that is decreasing (in this case) and not the disorderliness
(what does that mean?!). And it is the entropy change (S) that is negative and not the
entropy is negative. Entropy is a form of energy, hence it can never take on a negative
value.

Finally, the entropy decreases because there are fewer number of moles of gas left
after the reaction (loss of H2 gas), not only because there are fewer number of
molecules. The loss of gas is much more significant in this case.

It is also quite clear that the starting alkene is an oil (liquid) while H 2 is a gas and
resulting alkane is a solid margarine maybe considered a solid. Some students
mistake all molecules as being in the gaseous state. It is quite clear that these students
have very little real world experience with vegetable oil or margarine such that they are
not aware of the physical states of these common foods.

It is quite clear from the chemical equation given that the reaction goes to completion
and it is not an equilibrium. Hence all mention of Le Chateliers Principle and the
condition of high pressure are not relevant.

(iii) Although the reaction is energetically feasible, the activation energy is very high.
Or as the low temperatures are necessary for the reaction to be feasible, the rate of
reaction may be very slow. [1]

Hence the catalyst provides an alternative pathway with a lower activation energy and
the reaction speeds up. [1]

The gist of the question is really dependent on the answer in part (c)(ii). There are two
ways to answer this question. The easiest is to recognize that although the reaction may
be feasible, the fact that a catalyst has to be used points to a high activation energy.
The other way is to look at the conditions where the reaction is only feasible at low
temperatures and hence the rate of reaction would probably be very slow and a catalyst
is required to speed things up to some appreciable rate.

Finally, the second mark goes to explaining how the catalyst helps the reaction to
proceed. Many students identified the catalyst as lowering the activation energy of the
reaction. This patently wrong. The activation energy is only dependent on the reaction
mechanism/pathway taken. Adding a catalyst will change the reaction pathway such
that this new pathway has lower activation energy than the uncatalysed reaction. The
catalyst cannot directly lower the activation energy of a reaction. No credit was given to
students who wrote statements that implied the above.

(d) (i) A homogeneous catalyst acts in the same phase as the reactants. [1]

Phase is not the same as state or physical state. The term phase is a larger term
that encompasses the three physical states as well as other possibilities like solutions.
For any solute dissolved in water, we would say that the solute in now in the aqueous
3
phase (not state) and the solution is in the liquid state. Hence physical state cannot
describe a solution adequately and the term phase is used to describe it more
accurately. Another example would be of a solute dissolved in an organic solvent; the
solute would be described as being in the organic phase.

(ii) Oxidation number of Rh in compound 2: +3 [1]


x + (-1) + [(-1) x 2] = 0
x = +3 (working is not required)

Students who did not get marks here clearly need revision as to how to calculate the
oxidation number of the central metal ion or atom in a transition metal complex. Note
that hydride ligands are H.

(iii) The coordination number indicates the number of dative bonds about the central atom
or ion. [1]

Wilkinsons catalyst: coordination number = 4


Compound 3: coordination number = 6

[] for each correct coordination number

Note that the coordination number refers to the number of dative bonds that are
connected to the central metal ion or atom and not the number of ligands or lone pairs.
For example, edta (refer to transition metal notes) can form 6 dative bonds with the
central metal ion or atom. Hence a metal complex with edta has a coordination number
of 6 and not 1.

(iv) Rh is able to exhibit variable oxidation states. [1]


The proposed mechanism requires the addition of H 2 to Rh in the form of two hydride
ligands, which causes the oxidation state of Rh to increase from +1 to +3. [1]

Rh is able to form complexes of variable coordination numbers. [1]


The proposed mechanism requires the alkene and H2 to bind to Rh as ligands before
the addition reaction occurs. Or coordination number changes from 4 to 6 from
Wilkinsons catalyst to Compound 3. [1]

The question asks for illustration of the property stated and not an explanation of how
the catalyst works or how the property comes about. Hence stating the changes in the
oxidation number would suffice. Explanation of how the variable oxidation states are
possible is not required.

Note that the transition metals have partially vacant d subshell, not vacant d
subshell/orbitals. The difference is significant. d 1 to d9 are considered partially vacant d
subshell whereas vacant d subshell can only mean d0. Vacant d orbitals on the other
hand would only refer to d 1 to d4 configurations. Partially vacant d subshell is not a
property that is responsible for the behavior that is seen in the reaction pathway for
Wilkinsons catalyst. What the pathway shows is the alkene and H2 molecule becoming
ligands on the Rh and this must mean that the Rh centre must be able to exhibit variable
coordination numbers. If the Rh in Wilkinsons catalyst fails to exhibit variable
coordination numbers, then the catalysis will fail. Not all transition metal complexes
readily exhibit variable coordination numbers.

Note also that the transformations shown in the pathway are not ligand exchanges. A
ligand exchange would mean a substitution of a ligand already attached to the Rh with
an external ligand without a change in coordination number, which does not happen
here. Complexes that do not show variable coordination numbers would tend to undergo
ligand exchange since the number of dative bonds it can form is fixed.

4
2 (a) Chlorine is a greenish yellow gas. Bromine is a reddish-brown liquid. Iodine is a black solid.
[1]

Down the group, the volatility decreases as the number of electrons in the halogen
molecule increases. The size of the electron cloud increases, making the electron cloud
more polarizable and hence giving rise to stronger dispersion forces. Thus more energy is
required to overcome the stronger dispersion forces between the molecules for them to
vaporize. [2]

Students need to remember the appearance of the halogens. It is fluorine, not chlorine,
which appears as a pale yellow gas. Iodine appears violet only as a gas. At room
temperature, it exists as a solid which is (shiny) black.

In explaining the volatility trend, dispersion forces or instantaneous-dipole induced dipole


interactions should be specified, instead of simply van der Waals or intermolecular
forces. Care must be taken when referring to atoms or molecules. In this question, it is
important to show that it is the number of electrons in the molecules and size of electron
cloud of the molecules that matter.

(b) Add a few drops of aqueous AgNO3 to the sample solution, followed by dilute aqueous
ammonia.

If a white ppt forms which dissolves in dilute aqueous ammonia, the sample contains Cl
ion.
Ag+(aq) + Cl (aq) AgCl (s) --- white ppt
AgCl (s) + 2NH3 (aq) Ag(NH3)2+ (aq) + Cl aq)

If a cream ppt forms which is insoluble in dilute aqueous ammonia, the sample contains Br

ion.
Ag+(aq) + Br (aq) AgBr (s) --- cream ppt
{AgBr (s) + 2NH3 (aq) Ag(NH3)2+ (aq) + Br (aq)} this reaction occurs as well but
does not decrease the [Ag+] sufficiently to make AgBr dissolve completely since Ksp(AgBr)
is lower than Ksp(AgCl).

[1] for correct reagents


[1] for equation for AgX precipitation and colours of ppt
[1] for equation with ammonia and correct observation of solubility

OR

Add a few drops of Cl2(aq) into the sample solution.

If the solution turns from colorless to yellow-orange, the sample contains Br ion.
Cl2(aq) + 2Br (aq) Br2(aq) + 2Cl (aq)

If the solution does not turn yellow-orange (OR remains colourless), the sample contains
Cl ion.

[1] for correct reagents


[1] for correct observations for both ions
[1] for redox equation

Most students remembered to use silver nitrate to precipitate the silver halides. Fewer
followed up with dilute aqueous ammonia to test for solubility. Note that the colors of the
silver halides are not that easily distinguishable in practice, especially if they are not placed
side-by-side. Hence to confirm the ion, the solubility test should be used.

Oxidizing reagents such as KMnO4 or K2Cr2O7 are not accepted as the expected color

5
change could be easily obscured by excess reagent. Concentrated H2SO4 is suitable only if
the halides were in solid states e.g. solid NaX. When added to aqueous solution of halides,
no HX fumes will be released, and H+(aq) and X(aq) ions in solution are obtained instead.
The conc. H2SO4 will also be diluted and non-oxidizing. Fluorine gas is not appropriate as it
is highly toxic and oxidizes water readily.

Some students added an immiscible organic solvent e.g. hexane, together with Cl2(aq), in
which case the Br2 formed will dissolve in the organic solvent to give an orange/red layer,
whereas the unreacted Cl2 will give a colorless/pale green organic layer.

All equations must be balanced, with the correct products and state symbols. The equation
illustrating the formation of AgCl and AgBr precipitate must be single arrow and not a
reversible arrow.

(c) (i) Pyridinium tribromide is a solid and is less volatile, hence it is safer to use compared
to bromine which is a fuming liquid and gives off toxic bromine fumes. [1]
OR Pyridinium tribromide is a solid, hence it is easier to weigh and use compared to
bromine which is a fuming liquid.

Pyridinium tribromide is given as an ionic salt, hence students can deduce it is a


solid and will be less volatile compared to bromine which is fuming and toxic, and
relate its advantage to safety and ease of use.

(ii)

[1]

The structure should show all 3 lone pairs around the central Br atom, as well as the
negative charge. According to VSEPR, the 5 electron dense regions (3 lone pairs
plus 2 bond pairs) will arrange themselves in a trigonal bipyramidal manner around
the central Br atom. Since the 3 lone pairs occupy the equatorial positions, the shape
of the tribromide ion is linear.

The following dot-and-cross diagrams show the possible bonding in the tribromide
ion:

or

Corresponding structures: or are accepted.

(iii) Step 1: condensation [1]


OR nucleophilic (acyl) substitution or addition-elimination

Step 2: electrophilic substitution [1]

Step 1: The reagent used is ethanoic anhydride. Anhydrides are carboxylic acid
derivatives that can react like an acid chloride (though not as reactive). The
phenylamine acts as a nucleophile to attack the C=O carbon of the anyhydride,
forming an amide. This is similar to the formation of amide from the reaction between
an amine and an acid chloride. Note that although nucleophilic substitution was
accepted as the type of reaction in Step 1, the mechanism is not the same as that
of SN1 or SN2 of an alkyl halide.

Step 2: One of the H atoms in the benzene ring is substituted by a Br atom. Hence, it
is an electrophilic substitution.

6
(iv) In Route 2, the Br2 reacts with phenylamine. The lone pair on NH2 delocalises into
the benzene ring and increases electron density in the ring. The ring is highly
activated towards electrophilic attack, hence it is able to undergo further
brominations to give multi-brominated products. [1]

In Route 1, the anilide is not as activated as phenylamine as the NHCOR group is


less electron-donating due to the delocalization of the nitrogen lone pair into the
C=O group as well. [1]

This question is about the activating effect of substituents on the benzene ring. In
both phenylamine and anilide, the lone pair of electrons on N is delocalized into the
benzene ring, hence both NH2 and NHCOR activates the benzene ring towards
electrophilic attack, though to different extents. In anilide, the lone pair on N is also
delocalized into the C=O group, so its delocalization into the benzene ring is
reduced, hence NHCOR donates less electron density into the ring.

Note that the effect of C=O group is more due to the delocalization of the lone pair
of N into C=O than the inductive effect from the highly electronegative O atom.

The NHCOR group is not deactivating (or electron-withdrawing) because anilide


can still be brominated with reagents like aqueous bromine, unlike benzene. [This is
in contrast to the CONHR group, which is deactivating (and electron-withdrawing) --
- note which atom is attached directly to the benzene ring, though both groups are
amides.]

(v) The bulky NHCOR group sterically hinders the approach of the electrophile towards
the 2nd carbon. Hence substitution occurs mainly on the 4 th position. [1]

Note that NHCOR group is 2,4-directing (just like NH2 group) and not 3-directing.
Steric hindrance describes the crowding of large substituents which may affect how
well a reaction would go (e.g. reactivity of aldehydes vs ketones, approach of an
electrophile or nucleophile etc.)

Answers about electronegative O or N atoms and lone pairs of electrons are not
relevant here. Steric hindrance can come from a large hydrocarbon group without
any need for electronegative atoms or lone pairs.

(vi) Phenylamine is the most basic of the three, followed by bromophenylamine and then
bromoanilide. [1]

Bromoanilide is the least basic. In the amide group, the lone pair on N is delocalized
into the C=O group (as well as into the benzene ring) and least (or not) available for
protonation.

In bromophenylamine and phenylamine, the lone pair on N delocalizes into the


benzene ring. However, bromophenylamine is less basic because its Br substituent
is electron-withdrawing and decreases the electron density on the benzene ring.
Hence the lone pair on N delocalizes into the benzene ring to a greater extent and is
less available for protonation, compared to phenylamine. [1]

Many students lost marks through careless errors or inaccurate use of terms in this
standard question on relative basicity. First students must recognize that one of the 3
compounds is an amide, and the reason why amides are neutral is due to the
delocalization of lone pair of electrons on N over the C=O bond, rather than the
inductive effect of the electronegative O atom. Simply writing electron-withdrawing
C=O group also does not convey the idea of the delocalisation.

7
The other 2 compounds are both phenylamines, the difference being one having that
extra Br substituent. Note that the Br substituent is electron-withdrawing overall.
The inductive electron-withdrawing effect of Br on benzene is much more significant
than the resonance effect (even though lone pairs on Br can delocalize into the
benzene ring to give partial double bond character to CBr which we use to explain
the unreactivity of bromobenzene vs alkyl bromide].

Please draw the correct compounds in your answer or label them A, B and C for
easy reference.

(d) (i) amount of Br2 = 16.0 x 103 / (79.9 x 2) = 1.00 x 104 mol

[Br2] = 1.00 x 104 / (150/1000) = 6.67 x 104 mol dm3 [1]

The value of KC >1 shows that the equilibrium is product favoured. The concentration
of Br is 0.5/6.67 x 104 = 750 times more than that of Br2. The large excess of Br
will push the equilibrium position very much to the right, such that the reaction is
almost complete. [1]

The molecular mass of Br2 = 79.9 x 2. Many students forgot to multiply by 2.

After calculating the initial concentration of Br 2, students should compare it with the
initial concentration of Br and realize that Br is present in large excess. By only
saying a low concentration of Br2 or high concentration of Br is used does not
convey the great disparate in relative amounts of the reactants. The use of one
reactant as a limiting reagent or simply having more Br 2 than Br is also not a
sufficient reason for the equilibrium to lie so much towards completion.

(ii) Assuming the reaction is complete,


[Br3] at eqm = 6.67 x 104 mol dm3
[Br ] at eqm = 0.5 6.67 x 104 = 0.499 mol dm3 [1]

Since the reaction is virtually complete, we can assume [Br 3]eqm [Br2]initial i.e. all the
Br2 reacted since Br is in such large excess.

Br however cannot be all reacted since there is not much Br 2 to react with it.
Assuming all Br2 reacted, and reaction is a 1:1 ratio:
[Br]eqm = [Br]initial - [Br2]reacted.
In fact, Br is in such large excess that we can also assume that [Br]initial [Br]eqm,
i.e. concentration remains largely constant at 0.500 mol dm 3

Alternatively, students can use the KC expression to calculate the answers. For
example, 100 = (x) / (6.67 x 10 4 x) (0.500 x) and assume x << 0.500 to solve for
x. [Note that the assumption x << 6.67 x 104 is not valid here because the amount
of Br2 reacted is going to be significant compared to the initial amount of Br 2.]

The A Level exam will not require you to solve quadratic equations so knowing when
to make appropriate assumptions will be useful.

(iii) KC = [Br3] / [Br2][Br ]


100 = 6.67 x 104 / [Br2] (0.499)
[Br2] = 1.34 x 105 mol dm3 [1]

From the answers in (ii), students can substitute the values directly into the KC
expression to obtain the concentration of Br 2. The concentration of Br2 is close to
zero (since reaction is virtually complete) but not zero (remember that this reaction
is still an equilibrium).

8
3 (a) (i) No. of moles of sulfoxide recovered = 91.3% of theoretical no. of moles
no of moles of thioanisole used
= theoretical no of moles of sulfoxide
= (9.82/(124.1 + 16.0))/(91.3/100)
= (9.82/140.1)/(91.3/100)
= 0.07677 mol
[1] correct substitution of Mr and % yield

mass of thioanisole used = 0.07677 x 124.1 = 9.53 g (must be 3 s.f.) [1]

Too many students still do not present their working properly, and were penalised for
some of the following:
- No statements
- No units
- Missing working
- Rounding too early, resulting in inaccurate answers
- Showing way too many significant figures in intermediate steps or in the final
answer

(ii) Since IO4 and thioanisole react in a 1:1 ratio,


no of moles of IO4 required = 0.07677 mol (from (i))
volume of sodium iodate solution required
= 0.07677/0.500 x 1000
= 154 cm3 [1]
(allow ecf from no of moles of thioanisole in (i))

As the questions explicitly requires a volume in cm3, answers in dm3 were rejected.

(iii) Oxidation state of iodine in IO4 = +7


change in oxidation state of iodine = (+5) (+7) = 2

By observing the structure of thioether and sulfoxide product, the sulfur [1]
atom changes its oxidation state by +2 (due to new double-bond formation
with the more electronegative oxygen atom)

As such, IO4 and thioanisole should react in a 1:1 ratio.

Students should be careful not to mix up electron gain and loss. Iodine is getting
reduced, which means it is gaining electrons, while sulfur is getting oxidised, so it is
losing electrons in the process.
Simply saying that the no. of electrons lost and gained is the same is not sufficient to
score here as that statement is always true, regardless of the reacting mole ratio. More
importantly, students should notice that each iodine atom in IO 4 changes oxidation state
by 2 units, while each sulfur atom in thioanisole also changes by 2 units. This is why they
should react in a 1:1 ratio.

(b) (i) Electrophilic addition [1]

The word electrophilic should be mentioned, and spelt correctly.

It is possible to deduce that it is an addition reaction from the fact that all atoms in the 2
initial reactants can be accounted for in the product.

9
(ii)

[2]

Note: not necessary to show all 3 lone pairs on S atom in 2nd step (only 1 is necessary)

Based on the product formed, it is possible to deduce that it is the S-H bond in CH3SH
that is broken in the first step (as opposed to the S-C bond, which would give a different
product). This means that the H atom is added first to form a carbocation intermediate.

Marks were deducted for omissions or errors, such as: no charge separation on S-H
bond, no indication of rate determining step, arrow starting from negative sign rather than
lone pair in 2nd step.

Other nonsensical mechanisms, such as arrows pointing in the wrong direction, etc. were
not awarded any marks.

(iii) Isopropyl methyl sulfide

= [1]
(accept other unambiguous ways of drawing the structure)

To get this answer, candidates must deduce the structure of the more stable carbocation
intermediate (the secondary carbocation, rather that the primary one).

(c)

[2] (1 mark for each correct structure)

Step 1: conc. HNO3, conc. H2SO4, >55 C [1] (since SO3H is deactivating)
Step 2: Sn, excess conc. HCl, heat [1] (no need to follow with NaOH since we add it in
the next step anyway)
Step 3: heat with NaOH(aq) [1]
OR Inverse Steps 2 and 3, then G will be as follows (all others remain unchanged):

10
Students must show understanding of directing effects of substituents (i.e. nitration
should be done first), otherwise the reaction scheme would depend on the formation of
minor products, which is not ideal.

Students who form the phenol in step 1 encounter two issues:


1. The OH group on phenol is 2,4-directing, which means the desired 3-substituted
product to be formed in the subsequent step will not be formed in significant quantities.
2. The OH group is activating, so the student will have to reflect their understanding of
this by using dilute HNO3 alone to form the nitro product.

Students should also show understanding of acidic and basic media on the OH and
NH2 substituent groups by giving the formula of the ion as appropriate. The only
exception comes in the formation of the final product, as that contains both an acidic and
a basic group so either medium is accepted.

Pay attention to the following reaction:

The heating occurs in the first step!! Students who mix up these steps show poor
understanding of what each step actually does. The addition of NaOH(aq) here is simply
to recover the phenylamine from the phenylammonium salt formed in the acidic medium
of step 1.

Attention to details should be shown:


- temperature used for nitration should be above 55 C since SO3H is deactivating
(question says it behaves like NO2)
- relevant salts formed in acidic/basic media
- timing of addition of NaOH/HCl to recover salts seems to be a bit clumsy for
some, who add it twice in a row when it is unnecessary to do so

(d) 14

pH 7

0
NaCl MgCl2 AlCl3 SiCl4 PCl5
chlorides

Formula of each chloride must be correctly written [1]

Trend must be correct: [1]


- pH 7 must be clearly indicated on axis (if not, this mark is lost)
- trend in pH must be correct (neutral for NaCl, slightly below neutral for MgCl2 (accept 6-
6.5), lower for AlCl3, and lowest for SiCl4 and PCl5 (accept if PCl5 is at lower pH than
SiCl4)

11
Students should learn to read the requirements of the question properly:
- All chlorides should be in their highest oxidation state possible, ie, PCl5 and not
PCl3.
- The chlorides of sulfur and chlorine (!!) are not asked and should not be included.
- Trendline should be drawn.

(e) (i) J contains NaAl(OH)4 or Al(OH)4 [1]

(ii) Al2O3 is amphoteric, and so it is dissolves in NaOH(aq) []

Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2NaAl(OH)4(aq) [1] with correct state symbols


Accept: ionic equation (without Na+ spectator ion)

TiO2 is basic in nature, and does not dissolve in NaOH, hence it remains as a solid and
can be separated from the solution (filtered out) []

Students must learn to give complete and convincing answers addressing how each
component is separated. Simply saying that one reacts while the other does not is not
sufficient to prove that they can be separated.

(iii) Fe(OH)3 OR Fe2O3 [1]


Accept: iron(III) hydroxide OR iron(III) oxide (oxidation state of iron must be stated)

The red colour was the giveaway here. Students were supposed to link the colour to their
knowledge of the colour of iron(III) compounds.

As the question asks for the identity of a compound, answers referring to Fe 3+ ions only
were not credited.

(iv) Step A requires heating to decompose the hydroxide.


2Al(OH)3 Al2O3 + 3H2O [1]

The question says that NaOH and the white solid are formed as the only products of
cooling solution J. As such, the white solid must be Al(OH)3 for the process to be
balanced: NaAl(OH)4 Al(OH)3 + NaOH

Answers that give the correct equation but a nonsensical or contradictory set of
conditions were not accepted.

4 (a) (i) 2SO2 (g) + O2 (g) 2SO3 (g)


Initial P / atm x4 x2 0 (from doubling of volume) [1]
Change 1.8 0.9 +1.8 (from 90% conversion of SO 2)
At eqm / atm 0.2 0.1 1.8

I. Total P = 0.2 + 0.1 + 1.8 = 2.1 atm [1]


0.1
II. x(O2) = 2.1 = 0.0476 [1]
(2.1 1.01 105 ) (60 103 )
III. n= = 2.12 mol [1]
8.31 (450+273)

Many students solved this problem by using the ideal gas equation to calculate n for
each gas, and then re-converting the total no of mol at equilibrium back to pressure.
While there is no penalty if you obtain the correct answers, this is a much longer method.
You could apply the fact that P n (T, V constant), and solve the problem using partial
pressures as shown above. This is often the case when the given data is in terms of
pressure.

12
On combining the two cylinders, the total volume is doubled (now 60 dm 3) and the
respective partial pressures are halved (an application of Boyles Law). In addition, the
gases react with 90% conversion, so an I-C-E table helps to determine the equilibrium
partial pressures of each gas.

I. The total pressure is equal to sum of partial pressures - an application of Daltons


Law.
II. For gases at the same temperature and pressure, mole fraction is equal to the
ratio of partial pressure to total pressure.
III. The no of moles is calculated from the ideal gas equation. You must apply the
correct conversions to and from SI units: e.g. 1 atm = 1.01 10 5 Pa.

(ii) The actual total pressure will be smaller than in (a)(i) because the gases (are not ideal,
and) have non-negligible intermolecular forces which reduce the pressure on the
container. [1]

The specific intermolecular forces are permanent-dipole permanent-dipole interactions


for SO2 (polar), and dispersion forces for O2 and SO3 (non-polar).

(b) (i) The F atom in H2F+ has two lone pairs and two bond pairs, hence, bent / V-shaped [1]
Accept a diagram leading to a statement of bent / V-shaped.

When the question says use VSEPR theory to predict , it means you must deduce the
shape from a statement of the number and distribution of electron pairs around the
central F atom. You could have lost marks for not doing so.

(ii) Brnsted acid: HF [] and Brnsted base: HF []

In the first step of the reaction, one molecule of HF acts as the proton donor (Brnsted
acid) and forms F, while another molecule of HF is the proton acceptor (Brnsted base)
and forms H2F+.
HF + HF H2F + F
Note the coefficient of HF is 2 in the overall equation, and SbF 5 is not involved in this
step because it neither accepts nor donate a proton.

(iii) Lewis acid: SbF5 [] and Lewis base: F []

In the second step, SbF5 (Lewis acid) accepts a lone pair from the F ion (Lewis base,
from the first step) to form SbF6.
SbF5 + F SbF6
The reaction of SbF5 with F is analogous to
the catalyst (halogen-carrier) AlCl3 acting as a Lewis acid to accept a lone pair from Cl
(Lewis base) to form the intermediate AlCl4 during the electrophilic substitution of
benzene by halogens.

(c) (i)

[1]

At pH 7, the stronger acidic group (CO2H, pKa 3.67) is expected to have completely
ionized, but the second acidic group (SH, pKa 10.31) has barely started ionizing.

SH2+ is rejected as S has about the same electronegativity as C and is therefore not
13
expected to be protonated in aqueous solution.

(ii) It is harder to remove a positively charged H+ from the negatively charged thioglycolate
anion HA due to the attraction of opposite charges compared to the loss of H + from an
uncharged thioglycolic acid molecule H2A. [1]
This results in HA being a weaker acid compared to H2A and hence larger pKa. [1]

OR The CO2H group in H2A is a stronger acid than SH group because the CO2 is
stabilized by resonance (the negative charge on the carboxylate ion is delocalized over
two highly electronegative oxygen atoms), while the S ion is not similarly stabilized.

The equations for the successive ionization of thioglycolic acid are:



1. HO2CCH2SH O2CCH2SH + H+

2. O2CCH2SH O2CCH2S + H+
The second ionization occurs less readily because of the separation of charges.

Students who used the second explanation must pay attention to the use of terms: the
CO2 is not stabilized by the electron withdrawing effect of the oxygen atoms, and the
SH group is not destabilised by the electron donating effect of alkyl group.

(iii) [ +][2 ]
Ka = OR
[]
[2 ]
[2 ]
=
pKa = pH lg []
[] [ +]
[2 ] 1010.31 [2 ]
= = 0.098 [1] 10.31 = 9.3 lg
[] 109.3 []

[2 ]
lg [] = 1.01

[2 ]
[ ]
= 0.098

The calculation is based on the Ka expression for the second ionization (pKa = 10.31).
With known [H+] and Ka values, the ratio of the conjugate pair can be determined.

(iv) Not an effective buffer because ratio of concentrations of HA and A2 is too small / not
close to 1 / the reservoir of A2 is too low compared to HA, (and therefore HA will be
used up very quickly when H+ is added). [1]

Remember for a buffer to be effective, there are two criteria: besides having the ratio of
concentration of the conjugate pair close to 1 (in other words, effective buffer pH range
= pKa 1), it is also essential that the absolute reservoirs of the conjugate pair are high.
In this question, the small difference between 9.3 and 10.311 should not be used as a
decision criterion.

(v) Not suitable because the working range of phenolphthalein is 9.3 1, but at pH 9.3,
thioglycolic acid has not reached its second equivalence point, [] which occurs only
after 10.31 [].

An important criterion for selection of indicator is: the working range of the indicator (pKa
of indicator 1) falls within / coincides with the equivalence point pH, i.e. the indicator
changes colour when the pH curve is steepest, upon addition of only one further drop of
acid / base.

In the case of thioglycolic acid, the second equivalence point is above 10.31, and
phenolphthalein would change colour before that. Many students lost marks because
they did not clearly state where is the second equivalence point, or say incorrectly that it
occurs at 10.31 (which is actually the half neutralization point.)

14
(d) (i)

[1] deduct mark if not fully displayed.

This hydrolysis reaction is analogous to the hydrolysis of a methyl ester, with SCH3
taking the place of OCH3.

(ii)

X Y

X, Y, B [3] (1 mark for each compound)


Step 1: electrophilic addition [1]
Step 2: nucleophilic substitution [1]
In Step 1, H2S adds across the C=C double bond; the absence of chiral carbon in X rules
out the Markovnikov product.
In Step 2, the SH group acts as a nucleophile for substituting I in CH3I, and loses its H
as a proton.
During the condensation in Step 3, H 2O is lost between the CO2H group and CH3SH to

form .

Step 1: Since X still contains the CO2H group (effervescence with Na 2CO3), H2S must
react with the C=C double bond. Also, X does not contain a chiral carbon, H2S adds
across the alkene in anti-Markonikov manner (the Markonikov product would contain a
chiral carbon).
Step 2: Since Y also contains the CO2H group, the SH group in X reacts like a
nucleophile (think of NH3) with the halogenoalkane CH3I, and then loses a proton, to form
Y.
Step 3: This is the reverse of hydrolysis, and it adds the second sulfur atom to the
molecule, resulting in B.

5 (a) (i) The melting point of Ru is higher than that of Sr. In Sr, only the 5s electrons are involved
in metallic bonding. In Ru, both 5s and 4d electrons are involved in metallic bonding due
to their proximities in energies [1]. More energy is required to overcome the stronger
metallic bonding in Ru compared to Sr [1].

Some candidates merely mentioned that more electrons are involved in metallic bonding
in Ru, without mentioning which electrons they are, thus not gaining credit. A few
candidates mentioned molecules in their answers which should not be the case as
there are no molecules present in the two metals being compared. A number of
candidates discussed shielding effect and effective nuclear charge, which is
applicable to explaining trends in ionisation energies rather than melting point of metals.

15
(ii)

Small jump from 8th


to 9th electrons

Big jump from 2nd


to 3rd electrons

[1]

The IE increases as more electrons are removed. As more electrons are removed, the
number of protons is more than the number of electrons and there are stronger
electrostatic forces of attraction on the remaining electrons [1]. More energy is needed to
remove another electron from the increasingly positively charged ion.
There is a big increase in IE between the 2nd to the 3rd electrons removed. The 3 rd
electron is removed from an inner quantum shell [].
There is a small increase in IE between the 8th and 9th electrons removed. The 9 th
electron removed is from 4s subshell which is closer to the nucleus compared to 4p
subshell [].

Some candidates were penalised for not labelling their axes. On the sketch, there needs
to be a clear distinction between a small jump and big jump. Some students tend to
wrongly use the terms orbitals, subshells and quantum shells interchangably. There was
also confusion between valence electrons and the remaining electrons after some
electrons are removed. A few candidates wrongly explained the ionisation energies of Ru
instead of Sr. A number of candidates also explained the trend in IE across a period
rather than successive IE which is required by the question.

(b) (i) The standard electrode potential of a half-cell is the potential associated with a given
half-reaction when all components are in their standard states (temperature of 298 K,
pressure of any gas at 1 atm, and concentration of any ion at 1 mol dm3), measured
relative to the standard hydrogen electrode. [1]

The standard states of temperature of 298 K, pressure of any gas at 1 atm, and
concentration of any ion at 1 mol dm3 need to be mentioned in the answers to gain full
credit.

(ii) Ecell = +0.23 (0.76) = +0.99 V > 0 [1]


2Ru3+(aq) + Zn(s) 2Ru2+(aq) + Zn2+(aq) [1]

Most candidates are able to show that the reaction is feasible by calculating the Ecell
correctly. Do remember to include the positive sign and units. Some however, did not
construct the balanced equation or failed to include state symbols or use the correct
arrow in their equations.

16
(iii) Ar of Ru = 101, Mr of orange crystal = 101/0.369 = 273.7
To balance the charges, Ru2+ : Cl is 1:2 [1]
Mr of NH3 ligands = 273.7 101 2(35.5) = 101.7
Number of NH3 ligands = 101.7/(14.0 + 3.0) 6
Formula for orange crystals: [Ru(NH3)6]Cl2 [1]

Ru3+ undergoes reduction when reacted with Zn to give Ru 2+. The orange crystals formed
(solid state) implies that the complex is neutral. Since Ru 2+ has 2+ charge, there must be
two Cl anions present in the solid in order for the overall charge to be zero. The ligands
present are NH3 and there should be six of them based on its Mr. Other forms of the
formula which are accepted are RuCl2(NH3)6 and [Ru(NH3)6]2+2Cl.

(c) (i)

[1]
for each of the 3 steps
Accept protonation using just H+ in first step and deprotonation without using A in last
step

Many candidates did not read the question carefully. Even though the name of the
mechanism was already given as nucleophilic addition, a number of candidates gave a
different name (e.g. electrophilic addition, nucleophilic substitution) when describing the
mechanism. Several candidates gave a two-step or four-step mechanism even though
the question had described a three-step mechanism. The question also specifically
asked for the reaction between benzaldehyde and methanol, so alkyl groups should not
be labeled as R1, R2 and R3. When describing the mechanism, candidates should draw
parallel with the nucleophilic addition mechanism using HCN.

(ii) Test/Observation Deduction


P reacts with acidified ethanol to P undergoes nucleophilic addition with acidified
yield compound R. ethanol to produce a hemiacetal.
P contains aldehyde/ketone functional group.

Both P and R yield a colourless P and R undergoes acid-base reaction with


gas which forms a white Na2CO3 to give CO2 gas.
precipitate with limewater when P and R contain carboxylic acid functional
warmed with aqueous sodium group [1]
carbonate.

17
With alkaline aqueous iodine, P P reacts with alkaline aqueous iodine to give
gives a yellow precipitate CHI3 ppt.
P contains CH3CH(OH)- or CH3CO- group [1]
Treating P with methanolic Carboxylic acid in P cannot be reduced by
sodium borohydride yields methanolic NaBH4.
compound Q, C9H10O3. P contains ketone group which undergoes
reduction [1]

P [1]

Q [1]

R [1]
Q reacts with aqueous sodium Q undergoes acid-base/neutralisation reaction
hydroxide yields S [1]

S [1]

[1] for each correct structure (accept 1,2 or 1,3 or 1,4 di-substituted structures)
[1] for each correct deduction, max 3 out of 4 available

For compound S, Na+ must be ionically bonded to the carboxylate group as the question
indicated that S is a compound. A few candidates gave the structure of the benzene ring
as C6H4-, which is not accepted as one cannot tell the positions of substitution. Some
candidates did not attempt to explain the chemistry and reactions involved. Please note
that marks are allocated for explanations, which will gain credit even if the structures
drawn are incorrect. Be specific when stating the functional groups. For example, acid
does not imply carboxylic acid, and having C=O does not imply the presence of carbonyl
compound (as it is also present in carboxylic acid, ester etc.).

18