C
C
D
B
C
11
12
13
14
15
D
C
B
A
C
21
22
23
24
25
D
B
B
D
C
31
32
33
34
35
B
D
A
B
B
6
7
8
9
10
A
D
C
A
D
16
17
18
19
20
D
D
C
C
C
26
27
28
29
30
A
C
B
B
A
36
37
38
39
40
B
D
A
B
B
In the body, cellular respiration produces energy from the oxidation of glucose.
The diagram shows the structure of glucose.
CH2OH
O
H
OH
OH
OH
OH
A new artificial sweetener has been produced by replacing all of the hydroxyl groups attached
directly to the ring carbon atoms in glucose with chlorine atoms.
What is the empirical formula of this chlorinate glucose?
A
CHClO
CH2Cl
C3H4Cl2O
C6H7Cl5O
Ans :C
Keyword: only replaced all hydroxyl groups attached directly to the ring carbon atoms
CH2OH
O
H
Cl
Cl
Cl
Cl
moles of Fe3+(aq)
Which one of the following does not contain either an unpaired s electron or an unpaired p
electron?
Cr
Ge
Sc
Ans: D
Cr: [Ar]3d54s1
Ge: [Ar]3d10 4s2 4p2
S : [Ne]3s23p5
Sc: [Ar]3d1 4s2
Thus, Sc does not contain either an unpaired s electron or an unpaired p electron.
The graph shows the first thirteen ionisation energies for element X.
It is a d-block element.
Ans: B
Element has 2 valence electrons (required the least amount of energy to remove), because
2 electrons removed from outermost shell. Hence it is a Group II element, not Group III.
After removing 2 valence electrons, the inner shell contains 8 electrons, and not 18 electrons.
Thus element is not d-block element. [thus option A is out]
Element has more than 2 occupied quantum shells, hence, not in the second period. [thus,
option D is out]
The boiling point of water (100 C) is greater than that of HF (20 C).
Which statement is a correct explanation of this?
Each hydrogen bond formed between water molecules is stronger than that formed
between HF molecules.
There are more atoms in a water molecule than there are in an HF molecule, so van
der Waals forces are stronger in water.
There are, on average, more hydrogen bonds between water molecules than there
are between HF molecules.
The water molecule has a greater permanent dipole than the HF molecule.
Ans: C
Both water and HF have intermolecular hydrogen bonding.
Each Water molecule has 2 Hydrogen atoms & 2 lone pair of electrons on the oxygen atom, so
on average water molecule can form 2 hydrogen bonds.
Each HF molecule has 1 hydrogen atom & 3 lone pair of electrons on the fluorine atom, so on
average HF molecule can only form 1 hydrogen bond.
Thus, more energy needed to overcome greater number of hydrogen bonds in water that in HF.
One suggestion for the reduction of greenhouse gas emissions from coal-fired power
stations is to separate the CO2 from the flue gases and pump it into the sea bed, where it
will dissolve in water under pressure.
CO2(g) + nH2O(l)
CO2(aq)
During this process, hydrogen bonds are formed between CO2 and H2O molecules.
What will be the signs of H and S for this equilibrium for the forward reaction?
H
Ans: A
Since hydrogen bonds are formed, there is energy released & H is negative.
From the equation, it can be seen that there is a decrease in number of gas particles from
reactants to products. Thus, S is negative.
Two separate electrolyses were performed as follows, under the same conditions of
temperature and pressure.
1
When molten copper(II) chloride was electrolysed for five minutes, 100 cm3 of
If current used in electrolysis 1 was I, what was the current used in electrolysis 2?
A
0.5I
2I
4I
Ans: D
2Cl- Cl2 + 2e
2H2O O2 + 4H+ + 4e
Q = It = ne F
I=
ne F
t
Thus, I
ne
2.0
+ CO(g)
1.0
CH3OH(g)
0
A
B
C
H2(g)
CO(g)
CH3OH(g)
1
2.0 x
2
1
2.0 x
2
1.0 x
1
x
2
2.0 x
2.0 x
1.0 2x
1
1.0 x
2
1.0 x
1
x
2
1
x
2
Ans : C
2H2(g)
+ CO(g)
CH3OH(g)
Initial moles
2.0
1.0
Change in mole
-x
-1/2 x
-1/2 x
Eqm moles
2.0 x
1
1.0 x
2
1
x
2
Pyruvic acid is a weak acid that is an important intermediate in many biochemical processes.
CH3COCO2H
Pyruvic acid
Which graph best represents the change in pH that occurs when a sample of pyruvic acid is
titrated with NaOH(aq)?
A
Answer: D
HA is a weak acid which dissociates partially into H+ and A-.
HA
Ini conc
Eqm conc
H2 Chemistry 9647 2012
c
cx
H+ + A0
0
x
x
A 1 dm3 solution was made by mixing 0.0040 mol of HCl(aq) and 0.0025 mol of NaOH(aq).
What was the pH of the resulting solution?
A
B
C
D
2.19
2.40
2.60
2.82
Answer: D
HCl
+ NaOH NaCl + H2O
0.0040
0.0025
0.0015 mol of HCl is in excess.
Concentration of H+ after neutralization = 0.0015 mol dm-3
pH = - log 0.0015
= 2.82
12
Lead is the final product formed by a series of changes in which the rate-determining step is
the radioactive decay of uranium 238. This radioactive decay is a first order reaction with a
half-life of 4.5 x 109 years.
How long would it take for a rock sample, originally lead-free, to contain a molar proportion of
uranium to lead of 1 : 3
A
B
C
D
Answer: C
Number of half - life
Uranium
1
1/2
1/4
4.5 x 109
4.5 x 109
Lead
1/2
3/4
13
5%
10%
19%
20%
Since decomposition is a first order process, the half-life of H2O2 at the same temperature
remains constant.
n x t1/2 = 5 mins
0.09 1
=
0.1 2
x 1
=
0.2 2
0.09
x
=
0.1 0.2
Answer: A
Catalyst will lower the activation energy by providing an alternative pathway. However, it
does not alter the initial and final states of the system and hence do not affect H of the
reaction. In the catalyzed reaction, the reaction pathway undergoes two steps hence there
should be two humps for the reaction.
15
Adding concentrated HCl(aq) to CuSO4(aq) causes the colour of the solution to change from
blue to green.
Which row best explains this observation?
A
B
C
D
number of d-electrons
around copper
changes
changes
remains the same
remains the same
Answer: C
Adding concentrated HCl to CuSO4 causes ligand exchange reaction to occur.The identity of
the green solution is CuCl42-.
There is no change in the oxidation number of Cu hence there should be no change in the
number of d electrons around copper.
However, the colour of the solution is due to the magnitude of the energy gap between the d
orbitals. Since there is a colour change, this shows that the magnitude of the energy gap
differs, resulting in the absorbance of a different wavelength from the visible light spectrum.
Examiners Comment:
The most common incorrect response to Question 15 was A, showing that candidates
thought that the number of copper d orbital electrons changed in the reaction.
16
Which reaction will not take place readily under the conditions specified by the state
symbols?
[Note: H2O(g) = steam]
A
B
C
D
Answer: D
Mg(s) has slow or no reaction with cold water, does not produce Mg(OH)2(aq).
H2 Chemistry 9647 2012
CaO(s) dissolves in water to give a white precipitate (of calcium hydroxide) is formed,
together with an alkaline solution (also of calcium hydroxide calcium hydroxide is slightly
soluble).
17
group I
group II
group VII
Ans: D
Thinking process:
There is no drastic increase from the 1st to the 3rd ionisation energies.
A high melting point indicates the element has a giant structure.
The element has a high density.
Hence, the element is most likely to be the transition element.
18
When chlorine reacts with hot aqueous sodium hydroxide, the reaction below occurs.
chlorine + sodium hydroxide
What is compound X?
A
sodium chlorate(I)
sodium chlorate(III)
sodium chlorate(V)
sodium chlorate(VII)
Ans: C
Thinking process:
Under hot aqueous NaOH, chlorine undergoes disproportionation to form NaCl and NaClO3.
3Cl2(g) + 6NaOH(aq)
19
Covalent bonds are formed by orbital overlap. The shape of unsaturated hydrocarbon
molecules can be explained in terms of hybridisation of orbitals.
Which bond is not present in HCCCH2CH=CH2?
A
Ans: C
Thinking process:
Between C1 and C2, and between C4 and C5, there are bonds formed by a 2p2p overlap.
A bond is formed between 1s of H and 2sp of C1.
A bond is formed between 2sp2 of C4 and 2sp3 of C3.
20
When heated with chlorine, the hydrocarbon 2,2-dimethylbutane undergoes free radical
substitution. In a propagation step, the free radical X is formed by the loss of one hydrogen
atom.
Ans: C
Thinking process:
21
PGE2 and PGF2 are two prostaglandins, both with pharmacological activity.
PGF2
PGE2
Which reagent will convert PGE2 into PGF2 efficiently?
H2 / Ni
H2O / H+
H2 / Pt
NaBH4
Ans: D
Thinking process:
H2/ Ni and H2/Pt will reduce both C=C bond in alkenes and C=O bond in carbonyl compounds.
H2O / H+ is the reagent and condition for hydration.
NaBH4 is a specific reducing agent for reduction of carbonyl group.
22
cholesterol
Cholesterol reacts with cold, dilute acidified KMnO4.
Four students made claims about this reaction.
W
X
Y
Z
W and Y
X and Y
W and Z
X and Z
Ans: B
Thinking process:
H3C
CH3
CH3
*
*
HO
OH
OH
23
The diagram represents the transition state of an SN2 reaction in which N is an anionic
nucleophile and L the leaving group, but without any indication of the location of positive
or negative charges.
charge on L
Ans: B
Thinking process:
Both N and L are . It is the carbon atom that is +.
24
Chlorofluorocarbons (CFCs) have been widely used in aerosol sprays, refrigerators and in
making foamed plastics, but are now known to destroy ozone in the upper atmosphere.
What will not destroy ozone, and therefore can be used as a replacement for CFCs?
A
CHBr3
CCl3CBr3
CHClFCCl2F2
CH3CH2CH2CH3
Ans: D
Thinking process:
A safe replacement for CFCs is to use compounds that do not contain CX bond where X is a
halogen.
Note: repeated question from N2007/P1/23
25
Rosmaric acid occurs in culinary herbs such as rosemary, sage and thyme.
OH
O
O
O
HO
OH
rosmaric acid
H2 Chemistry 9647 2012
OH
OH
How many moles of NaOH(aq) will react with one mole of rosmaric acid when the acid is
heated under reflux with an excess of NaOH(aq)?
A
Thinking process:
5 moles of NaOH is required to react with acidic functional groups like RCOOH and phenol, via
acid-base reaction.
1 mole of NaOH is required to react with the carboxylic acid functional group formed after the
alkaline hydrolysis of the ester functional group.
Answer: C
26
Thinking process:
Option B: Prolonged heating with acidified concentrated KMnO4 will form (CH3)2C=O and
HO2CCH2CH2COCH3
Option C: Methanolic solution of NaBH4 only reduces carbonyl compounds. Hence the product
will be (CH3)2C=CHCH2CH2CH(OH)CH3. Molecular formula is C8H16O.
Option D: Warming with alkaline aqueous iodine produces (CH3)2C=CHCH2CH2COO- and
CHI3.
Answer: A
27
Thinking process:
Answer: C
28
After the reduction of nitrobenzene to phenylamine using tin and concentrated hydrochloric
acid, an excess of sodium hydroxide is used.
What is the purpose of the sodium hydroxide?
A
Thinking process:
Recall: Tin, conc HCl, heat with reflux, followed by aqueous NaOH, room temperature
Addition of NaOH in step 2 is to react with the acidic ammonium salt, and liberate phenylamine.
Answer: B
29
Amides form a zwitterion in which the nitrogen atom carries a positive charge.
Amides have resonance structure involving the movement of a pair of electrons from
the nitrogen atom to the oxygen atom.
Electrons on the nitrogen atom move on to the C-N bond giving it some double bond
character so that it is more difficult to break.
The amide carbonyl group withdraws electrons from the NH2 group to make the
hydrogen atoms acidic.
Thinking process:
Option A: Amino acids, not amides, form zwitterions
Option B: In amides, the lone pair of electrons on N atom is delocalised over the C=O bond.
The presence of the highly electronegative O atoms decreases the electron density on N,
further making the lone pair of electrons less available to accept H+.
Option C: This is a correct conclusion but it does not explain the concept of basicity
D
Answer: B
30
2-methylphenylamine
NH2
C
Br
D
Br
Br
Thinking process:
This is the typical reaction in which phenylamine react with aqueous Br2 under r.t.p conditions.
The type of reaction is electrophilic substitution.
Answer: A
Section B
31
Thinking process:
H2 Chemistry 9647 2012
In graphite, each carbon atom is sp2 hybridised (each C has 1 unhybridised 2p orbital). Hence,
out of the 4 valence electrons that C has, the 4th electron is not used in bonding but is
delocalised parallel to the layer of graphite. Hence option A is correct.
Note: The unhybridised 2p orbitals of the C atom overlaps to form a delocalised -electron cloud. The electrons act
as mobile charge carriers to conduct electricity along the plane.
Answer: B
32
A 1 mol dm-3 aqueous copper(II) salt is electrolysed between copper electrodes, using a
constant current for 60 s.
What affects the mass of copper deposited on the cathode?
1
Thinking process:
33
After the closure of a chemical plant in Switzerland, the reaction between 1-bromobutane and
hydrogen sulfide ions (HS-) was found to be taking place in the ground.
The following results were obtained.
Initial concentration of 1bromobutane /mol dm-3
0.1
0.2
0.3
0.1
0.1
Initial concentration of
hydrogen sulphide ions /mol
dm -3
0.1
0.1
0.1
0.2
0.3
Both 1-bromobutane and hydrogen sulfide ions are involved in the rate-determining
step.
The rate constant is 1.5 x 10-3 mol-1 dm3 s-1.
Thinking process:
H2 Chemistry 9647 2012
34
The number of moles of chlorine that react with 1 mol of X is twice the number of moles of
chlorine that react with 1 mol of Y.
Which of these pairs could be X and Y?
X
Mg(s)
Na(s)
H2(g)
KBr(aq)
Cold NaOH(aq)
Hot NaOH(aq)
Thinking process:
Mg(s) + Cl2(g) MgCl2(s)
Na(s) + Cl2(g) NaCl(s)
Ratio of Cl2 needed = 1 : = 2 : 1 (Option 1 is correct)
H2(g) + Cl2(g) 2 HCl(g)
KBr(aq) + Cl2(g) KCl(aq) + Br2(aq)
Ratio of Cl2 needed = 1 : = 2 : 1 (Option 2 is correct)
2 NaOH(aq) (cold) + Cl2(g) NaCl(aq) + NaClO(aq) + H2O(l)
NaOH(aq) (cold) + Cl2(g) NaCl(aq) + NaClO(aq) + H2O(l)
6 NaOH(aq) (hot) + 3Cl2(g) 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
NaOH(aq) (hot) + Cl2(g) 5/6 NaCl(aq) + 1/6 NaClO3(aq) + H2O(l)
Ratio of Cl2 needed = : = 1 : 1 (Option 3 is wrong)
Answer : B
35
Hydrogen + chlorine
Thinking process:
Which properties of transition elements are not shown by s-block elements such as calcium?
1
They have variable oxidation states.
2
Thinking process:
s-block elements do not have variable oxidation states.
s-block elements have only one oxidation number. Eg. +1 for Group I elements; +2 for Group II
elements (Option 1 is correct)
The ions of s-block elements cannot act as oxidising agents in aqueous solution.
The ions of s-block elements do not undergo reduction in aqueous solutions due to very
negative Eored. Eg. Na+ Na (Eored = -2.71V; not feasible) (Option 2 is correct)
The ionic radii of s-block elements are less than their atomic radii.
The ions has one less occupied shell as compared to their atoms. (Option 3 is wrong)
Answer : B
Examiners comments:
The majority of candidates gave D, rather than B, thinking that calcium ions can act as
oxidising agents in aqueous solution.
37
During the preparation of many organic compounds by-products are formed. This usually
occurs because the reagents can react in more than one way depending on the conditions
used or because the products formed may react with the reactants.
Propan-1-ol is produced by the reaction between 1-bromopropane and aqueous sodium
hydroxide.
CH3CH2CH2Br + NaOH CH3CH2CH2OH + NaBr
What could be a by-product of this reaction?
1
CH3CH=CH2
2
CH3CH2CH2ONa
CH3CH(OH)CH3
Thinking process:
** It is important that students read the question carefully especially on the part the products
formed may react with the reactants
Although aqueous sodium hydroxide is used ie. the predominant reaction is nucleophilic
substitution, a possible competing reaction ie. elimination could still occur. Thus, alkene could be a
by-product. (Option 1 is correct)
The product, CH3CH2CH2OH formed, does not react with NaOH. (Option 2 is wrong)
H2 Chemistry 9647 2012
38 The mould Phytophthora damages many plants, destroying agricultural crops such as potatoes.
A hormone-like compound called alpha 1 regulates the reproduction of all species of
Phytophthora. The structure of alpha 1 is now known, giving scientists a key to the possible
future eradication of the mould.
SOCl2
H2 / Pt
Thinking process:
Identify the functional groups present in alpha 1 :alcohol, ketone
Cl2(g) / light reacts with alkane chain via FRS
SOCl2 reacts with the alcohol via nucleophilic substitution
H2 / Pt reacts with ketone to form secondary alcohol via reduction
Answer : A
39
whereas
3-bromopropene,
The presence of the bond prevents free rotation of the C-Br bond thus decreasing the
reactivity.
Thinking process:
3
In CH2=CHBr, the p orbital of the Br can overlap with the bond, causing the electrons of the
Br atom to delocalise into the bond. This decreases the partial positive charge on the carbon.
Hence, the carbon is less susceptible for nucleophilic attack. Also, the overlapping of the p
orbital of the Br atom causes the C-Br bond to have double bond character, making the bond
stronger. (Option 1 is correct)
The electrons of the C=C bond are electron rich and it repels the attacking nucleophiles are
nucleophiles are also electron rich. (Option 2 is correct)
The presence of bond which prevents free rotation does not affect the reactivity. (Option 3 is
wrong)
Answer : B
Examiners comments:
Unfamiliar with the reaction mechanism details
40
CH3CH2CH2CH2CH2CH2CH3
CH3
+ 4H2
Under similar conditions, which of the C8H18 isomers could give 1,4-dimethylbenzene?
Thinking process:
To form methylbenzene, six carbons (CH3CH2CH2CH2CH2CH2-) are linked up to form the
benzene ring.
For Option 1:
(correct)
For Option 2:
(correct)
For Option 3,
(wrong)
Answer : B
Examiners comments:
Not confident in deducing the organic reactant
Paper 2
Please use the table format for our internal exams for keying in the 2012 questions.
Formatting wise, not so strict, just try your best =)
You can use this table for a start.
Please type in your relevant question and answer, and assign marks or ticks whenever
you can. We can refine it when the examiners report is out.
Please also insert a border around the solution, for ease of reading/finding the
answer.
Please also leave a row of one line spacing between the answer and the next question.
Thank you!
1
contains starch (0.20 g), potassium iodine (50.00 g), sodium ethanoate
(4.10 g) and sodium thiosulfate (9.40 g) in 1.0 dm3 water.
Solution B
is a mixture of 500 cm3 of 1.5 mol dm-3 hydrogen peroxide and 500 cm3 of
1.0 mol dm-3 ethanoic acid.
She mixes 50 cm3 of solution A with 50 cm3 of solution B and, after about 20 seconds, the
mixture suddenly turns dark blue.
(a)
In acidic solutions, hydrogen peroxide and potassium iodide react to produce iodine.
Write an ionic equation for this reaction.
[1]
H2O2 + 2H+ + 2I- I2 + H2O [1m]
(b)
Suggest why the reaction mixture contains both ethanoic acid and sodium ethanoate.
[1]
To form a buffer solution that keeps the [H+] relatively constant. [1m]
(c)
1
to represent the reaction rate.
time
[9]
Dilution required to dilute 7.5 mol dm-3 hydrogen peroxide solution to 1.5 mol dm-3
From 7.5 mol dm-3 hydrogen peroxide solution to 1.5 mol dm -3 , its dilution by 5 times
So using a 250 cm3 volumetric flask, burette out 50 cm3 of 7.5 mol dm -3 hydrogen
peroxide solution to do dilution by 5 times.
Preparation of 1.5 mol dm-3 stock solution
1
Transfer this H2O2 solution & its washings into a 250 cm3 volumetric
flask.
Experiment
Keeping total volume of mixture at 100 cm3 (because Question say so above: She mixes
50 cm3 of solution A with 50 cm3 of solution B and, after about 20 seconds, the mixture
suddenly turns dark blue)
vol of solution A at 50 cm3 & volume of CH3COOH at 25 cm3, max vol of H2O2 in mixture =
25 cm3.
1
Stop the stop watch when the colourless mixture suddenly turns dark
blue.
Reaction
mixture
Vol
of Vol of Vol
of Vol of Time
take
solution H2O2/ CH3COOH water solution to
A/ cm3
cm3
/ cm3
/ cm3
dark blue /s
1
2
3
4
5
50
50
50
50
50
25
20
15
10
5
25
25
25
25
25
for Reaction
turn rate, 1/t
(s-1)
0
5
10
15
20
Check the graph against table 2 to obtain the order wrt H2O2.
Zero order
s-1
Rate /mol dm-3 s-1
1st order
2nd order
-1
3 1
s dm
s
Rate/ mol
Rate / mol
s-1dm3 s1
k
Rate = constant
slope = k
3
Vol [A]
H2 O
2/ cm
mol
dm-3
(d)
[A] /3mol
Vol H2O2/Cm
dm3
3
3
mol
dm
Vol[A]
H/2O
2/ cm
Identify one potential safety hazard in this experiment and state how you would
Fossil fuels which re found in deposits beneath the ground have been formed from plants
and animals that lived up to 300 million years ago.
When fossil fuels are burned in internal combustion engines, CO2 and H2O are the main
products, with NO and SO2 also being formed.
(a)
(i)
Which class of compound, present in fossil fuels, produces CO2 and H2O on
combustion?
Hydrocarbons [1]
Examiners Comment:
This was generally well answered with the majority of candidates referring to
alkanes or hydrocarbons.
(ii)
(iii)
Suggest which class of compound, originally present in the living matter that
produced the fossil fuel, contained the sulfur that produces SO2 on combustion.
Protein / Amino acid [1]
Disulfide linkages R group
Examiners Comment:
This part was less well answered with relatively few candidates correctly stating
that the sulfur comes from proteins or amino acids that are present in the
hydrocarbon fuel.
[3]
Most of the sulfur present in fossil fuels is removed at oil refineries. It is used to produce SO2
which is converted, in the Contact process, into SO3 which is used for the manufacture of
sulfuric acid.
The Contact process involves the oxidation of SO2 using a vanadium (V) oxide catalyst.
H2 Chemistry 9647 2012
(b)
(i)
SO2(g) + O2(g)
SO3(g)
reaction 1
At 298K, Hf(SO2) = -297 kJ mol-1 and Hf(SO3) = -396 kJ mol-1.
Use these data to calculate H for reaction 1.
State the units.
Weak in hess law and practice
Burn in O2 combustion
Memorise formula without understanding
BE of O2
More eyes to look through tutorial
Hr =
n H
(products)
m H
(reactants)
H = -396 (-297)
= -99.0 [1]
Units : kJ mol-1 [1]
Examiners Report:
This was generally well answered. The most common incorrect answer included
the bond energy of the O2 molecule in the calculation.
(ii)
For any reaction, G and the equilibrium constant Kc, are related according to the equation
G = -2.303 RT log Kc.
(c)
(i)
Use this equation to calculate a value of Kc for the oxidation of SO2 at 298K.
G = -2.303 RT log Kc
(-71.1 x103 ) = -2.303 (8.31) (298) log Kc
log Kc = 12.4669
Kc = 2.93 x 1012 [1]
Examiners Comment:
This was less well answered than the previous calculation.
(ii)
Suggest why SO2 and not SO3 is formed when sulfur is heated in air.
The activation energy for the conversion of SO2 to SO3 is high.[1]
Examiners Comment:
Answers to this part question were often confused. Incorrect answers included
reference to the difference in oxidation number of sulfur in SO2 and SO3, the
effect of temperature on the value of Kc, and the relative rates of the forward and
backward reactions. Candidates needed to concentrate on the focus of the
question; why SO2 and not SO3 is formed when sulfur is burned in air. Although
the answers to part (iv) demonstrated that candidates knew that the Contact
Process requires a catalyst, they did not apply this knowledge to suggest that the
activation energy for the formation of SO3 is very high.
(iv)
Use your answer to (iii) to suggest why a catalyst is used industrially in the
Contact process. Explain your answer.
A catalyst increases the rate of reaction[1] by providing an alternative pathway of
lower activation energy[1], allowing the equilibrium to be established faster[1].
Examiners Comment:
This part was more successfully answered by many candidates, who knew that
catalysts speed up reactions. Most of them were able to explain that catalysts
provide a reaction with a lower activation energy.
Fifty years ago, students of A-level chemistry carried out qualitative inorganic analysis in
their practical sessions. This method included precipitating cations as chlorides, sulfides,
etc., and used the concept of solubility product, Ksp.
(a)
(i)
(ii)
[1m]
units: mol3dm-9
[1m]
Solubility of PbCl2 =
4.7
= 0.169 mol dm-3 [1m]
207.0 + 2(35.5)
(i)
When the HCl(aq) is added to AgNO3(aq), what will be seen in the container
immediately: white precipitate [1m]
Examiners Comments:
This part was well-answered.
How would your confirm that the original precipitate was AgCl by adding a
single reagent to it?
Describe what you would see and give an equation with state symbols for the
reaction that occurs with the reagent you have chosen.
Add aqueous ammonia. [1m]
White precipitate dissolves in aqueous ammonia. [1m]
AgCl(s) + 2NH3(aq)
Examiners Comments:
The use of NH3 (aq) to confirm the identity of AgCl was known by about half of
the candidates, although many of their responses did not give a correct
equation for the corresponding reaction.
(iii)
[PbCl4]2(aq) [1m]
(c)
[Cu(H2O)6]2+(aq) + 4Cl(aq)
blue
H2S(g) + aq
HS(aq)
and
H+(aq) + S2(aq)
MS(s)
Ksp/ mol2dm-6
6.3 x 10-36
4.0 x 10-21
1.6 x 10-24
The results of passing hydrogen sulfide through separate solutions of Cu2+, Ni2+ and Zn2+
are shown in the table below.
M
2+
being tested
2+
Cu
2+
Ni
2+
Zn
(d)
Use the data on the opposite page to give an explanation for each of the following
questions.
You should give equations where appropriate. You are not expected to do any
calculations in this part.
(i)
Why is CuS the only sulfide of these three precipitated in acid solution?
In acid solution, [H+] is high. [S2] is low [].
Since Ksp of CuS is the lowest, the ionic product of CuS > Ksp of CuS [1m].
However, the ionic product of NiS and ZnS < Ksp of NiS and ZnS respectively
[].
Hence, only CuS precipitates.
2 [] 1m
(ii)
Why is NiS precipitated in alkaline solution and not in neutral or acidic solution?
In alkaline solution, [H+] is low. [S2] is high [].
Ksp of NiS is highest. Only in alkaline solution where the [S2] is high, the ionic
product of NiS > Ksp of NiS [1m].
In both acidic and neutral solution, [S2] is not high enough for the ionic product
of NiS to exceed Ksp of NiS [].
2 [] 1m
(iii)
chlorgenic acid
The chlorogenic acid molecule contains a saturated ring, an aromatic ring and an alkene
group.
(a)
(i)
Identify as fully as you can the other functional groups present in chlorogenic acid.
Ester [1], secondary alcohol [1], tertiary alcohol [1], phenol [1], carboxylic acid [1].
(ii)
How many chiral carbon atoms are there in a molecule of chlorogenic acid?
4 chiral carbons [1]
[6]
(b)
When chlorogenic acid is reacted under suitable conditions with NaOH(aq), followed by
acidification, two crystalline solids may be obtained, one non-aromatic and one aromatic.
Draw the displayed formula of each of these compounds in the boxes below.
[1]
non-aromatic compound
Examiners comments:
Most common mistake was to draw the sodium salts of the carboxylic acids! Question want
the structure of the cpds itself, NOT when they have reacted with NaOH!
[2]
(c)
Draw the structural formula of the compound formed with aromatic compound R you have
drawn in part (b) is added to an excess of Br2 dissolved in an organic solvent.
OR
Note the difference in drawing the alkene portion
[1] alkene group reacting
[1] phenol group reacting
Examiners comments:
Many students did not notice that the side-chain alkene can react too!
[2]
(d)
[1]
(ii)
Suggest why this product contains only one Na atom/ion although the NaHCO3 is in
excess.
NaHCO3 is a weak base can only react with stronger acids such as carboxylic
acids. [1] Phenol is a weaker acid than carboxylic acid [1] hence cannot react with
NaHCO3. 1 mole of carboxylic acid group can only react with 1 mole of NaHCO3.
Note:
Must explain in terms of difference in acid strength of phenol and carboxylic acid.
[3]
[Total: 13]
(a)
(i)
Name the reagent and conditions used and the type of reaction that occurs in step 1.
Reagent .
Conditions .
Type of reaction
Reagent : HCN [1]
Conditions : trace amount of NaOH, 10-20oC [1]
Type of reaction : nucleophilic addition [1]
Examiners comments:
Most candidates knew the relevant chemistry for the production of lactic acid.
(ii)
Describe the mechanism of this reaction. In your answer you should show all charges
and lone pairs and show the movement of electrons by curly arrows.
Name of mechanism : Nucleophilic addition
HCN
H+ +CN-
H+ + OH-
H2O
H
H3C
+
C
slow
H3C
C
CN
OProduct
CN
Partial charges &
arrow
Slow & fast
Both products
6 to 8 [2]
3 to 5 [1]
0 to 2 [0]
Examiners comments:
Some struggled to describe the mechanism.
Some answers did not gain credit because candidates omitted to check that they had
included relevant charges and lone pairs. One other common incorrect answer was
not regenerating the CN ion at the end of the reaction sequence.
[5]
Lactic acid present in milk rotates the plane of polarised light.
Lactic acid produced in a laboratory by the reactions above does not rotate the plane of
polarised light.
(b)
(i)
What feature of the lactic acid present in milk causes the rotation of the plane of
polarised light?
The presence of chiral carbon in lactic acid causes the rotation of the plane of
polarised light with only one optical isomer present [1]
Examiners comments:
Candidates performed poorly in part (i)
Very few candidates were able to explain clearly and unambiguously that lactic acid
present in milk rotates the plane of polarised light because all of the molecules
present are of the same chirality, that is, only one enantiomer is present.
(ii)
Suggest, in terms of the mechanism of step 1 in the above reaction scheme, and the
shape of the CH3CHO molecule, why synthetic lactic acid does not rotate the plane of
polarised light.
As the nucleophile CN- can attack the planar carbonyl carbon from either side of the
plane with equal chance [1] , it will result in the formation of a racemic mixture [1] of
the products. The optical activity of the 2 optical isomers cancel out, hence synthetic
lactic acid shows no optical activity [1] (ie. does not rotate the plane of polarised
light).s
[4]
The effect of plane polarised light on tartaric acid (2,3-dihydroxybutanedioic acid),
HO2CCH(OH)CH(OH)CO2H was investigated by Louis Pasteur.
explanation
Or
Paper 3
1
(a)
Aluminium oxide has a giant ionic structure with strong ionic bonds
between the Al3+ & O2- ions.
high charge density of Al3+ can polarise the electron cloud of O2- to
some extent to give rise to some covalent character.
2AlCl3(g)
H = +63 kJ mol-1
(iii)
When 1.50 g of aluminium chloride was introduced into an evacuated flask of 250 cm3
capacity and heated to 500 K, the pressure inside the flask rose to 1.16 x 105 Pa.
(iv)
Assuming the gaseous mixture behaves ideally, use the general gas equation
to calculate the average Mr of the mixture.
pV = nRT
Average Mr = 214.9
(v)
Using the following relationships, calculate the mole fraction of Al2Cl6, x, and
the mole fraction of AlCl3, y, in the mixture.
x+y=1
Mr(average) = 267x + 133.5y
Rearrange: x = 1 y
214.9 = 267(1-y) + 133.5y
y = 0.390
x = 1 0.390 = 0.610
Hence calculate the partial pressures of Al2Cl6 and AlCl3 in the mixture.
(vi)
0.610
(1.16 105 ) = 7.08 x 104 Pa
1
Write an expression for Kp for the reaction, and calculate its value. Include units
in your answer.
[11]
(PAlCl ) = ( 4.52 10 )
=
2
Kp
PAl Cl
2
(c)
7.08 104
= 2.89 x 104 Pa
The benzene ring is then attached by the Cl+ cation in the second step.
AlCl3 reacts in a similar way with acyl chlorides, producing a carbocation that can
then attack a benzene ring.
(i)
Compound A:
Compound B:
(ii)
Suggest the reagents and conditions for a reaction that could be used to
distinguish between A and B. you should state how each of A and B react.
Draw the structures of the products of any reactions that occur.
[4]
[Total: 20]
Add I2(aq) & NaOH(aq) to A and B separately & warm.[1m]
Observation:
Compound A: yellow ppt [1m]
Compound B: no yellow ppt
(a)
[1m]
I-(aq) + I2(s)
I3-(aq)
Draw a fully labeled diagram of the electrochemical cell you would set up in order
to measure the relative oxidising powers of chlorine and iodine under standard
conditions.
Pt
Cl2(g)
Cl (aq)
Concentration
= 1 mol dm-3
Pt
Examiners Comment:
Despite the question asking for only one electrochemical cell, many
candidates chose to draw two cells, each with a standard hydrogen
electrode on one side.
Few candidates are able to describe correctly the iodine electrode (a Pt
electrode dipping into a mixture of 1 moldm-3 I(aq) and I2(s) or I3 (aq)).
Many suggested a solid electrode made of (non conducting) iodine, or
suggested passing I2(g) over a Pt electrode.
Other incorrect answers were the omission of the salt bridge, or the
inclusion of a battery in the circuit.
(ii)
Describe the measurements you would make, and explain their significance.
First measurement:
The electromotive force of the cell [] at zero current is measured.
E cell = E (reduction half cell) E (oxidation half cell)
A positive cell potential indicates that the reaction is spontaneous[].
Second measurement:
Titrate the I3- solution against S2O32- to determine the concentration of I3- [] after
some time. If the concentration of I3- falls below 1 mol dm-3, it will indicate that I2
has been reduced and I3-/ I- half cell is the cathode. []
2 [] 1 mark
Alternative:
- Using colorimeter to measure the colour intensity of I2. The increase in the
intensity of the red-brown colour indicates that I- has been oxidised to I2.
Examiners Comment:
Candidates were expected to suggest measuring the Eo of the cell, and to
explain that the more positive of the two electrodes would contain the
stronger oxidising agent.
Candidates should be aware of the difference between more positive and
larger or bigger.
(iii)
Write a balanced equation for the reaction that would take place if the electrode
of the cell were connected together by an external circuit.
Cl2(g) + 2I-(aq) 2Cl-(aq) + I2(aq) [1]
Examiners Comment:
Most candidates who answered (i) in terms of a single cell gained credit here.
[7]
(b)
When solutions of I-(aq) and Fe3+(aq) are mixed, an equilibrium is set up.
(i)
2Fe2+ + I2 [1]
Examiners Comment:
Some candidate suggested incorrectly the Ksp-like equilibrium:
3I(aq) + Fe3+(aq) FeI3(s)
Others suggested that I- could reduce Fe3+ to Fe metal.
(ii)
Use the Data Booklet to suggest how the position of equilibrium, involving I- and
Fe3+, would change in the presence of CN-(aq) ions. Explain your answer.
Fe3+ + e
[Fe(CN)6]3- + e
Fe2+
[Fe(CN)6]4-
E = +0.77 V
E = +0.36 V[]
The different reactivities of organic halogeno compounds, and of amines and alcohols,
can be exploited in successive reactions of dihalogeno compounds
Predict the outcomes of the following transformations, drawing the structures of the
intermediates C and E and the products D and F.
Both D and F are cyclic compounds.
(i)
C:
D:
[1]
[1]
Examiners Comment:
A large number of candidates correctly predicted the outcomes of these two
reactions: the CI bond is hydrolysed first, giving the chloroalcohol C, which is
then aminolysed to the aminoalcohol D. A frequent incorrect answer was the
inclusion of an NH3 group rather than an NH2 group in the aminoalcohol.
(ii)
O
H2
C
E:
F:
CH2Cl
N
H
OH
C
H2
[1]
[1]
Examiners Comment:
Fewer candidates achieved full credit for this part; often suggesting that E
was the chloroester rather than the chloroamide: they did not relate the
higher basicity of amines compared to alcohols to their higher
nucleophilicity.
Often the structure of F was given as the alkoxide anion, but better
responses gave its structure as the cyclic amide-ether.
[4]
(e)
(i)
(ii)
Predict the products of the hydrolysis of the amide groups in the following two
drugs.
Acidic hydrolysis:
Phenylbutazone
OH
[1]
OH
[1]
Phenobarbital
(a)
When heated, the carbonates of the Group II elements can lose carbon dioxide.
MCO3(s)
MO(s) + CO2(g)
Under the influence of the metal cation, the carbonate ion is thought to break up as
follows.
M2+
M2+
O2
Examiners Comments:
This part is well-answered by most candidates.
(ii)
State and explain the trend observed in the thermal stability of the Group II
nitrates.
Down the group,
radius of cation increases
charge density of cation decreases []
polarising power of cation decreases []
ease of distortion of electron cloud of NO3 decreases []
NO bond is less weakened
more energy required to break NO bond []
stability of nitrates to heat increases [1m]
4[] 1m
Examiners Comments:
The explanations of the trend were sometimes lacking steps in their logic;
mentioning the reduced charge density, and then not explaining that this
reduces the tendency for the anion to distort.
[3]
(b)
Using this information, and that provided in (a), suggest a mechanism for the
formation of N2O5 from a Group II nitrate, M(NO3)2.
Examiners Comments:
This part question required candidates to apply knowledge in an unfamiliar
context. Few candidates made full use of the information about the
decomposition of the carbonate ion in their answers. These candidates did not
appreciate that the first step in (i) would be NO3
NO2+ + O2, which
+
2NO2 + O2 [1m]
Examiners Comments:
The equation in (ii) was usually correct.
(iii)
Use the information given above to draw out the full mechanism for the thermal
decomposition of N2O5. You are advised to use structural formulae for all
species, such as
for N2O5, so that it is clear which bonds
are broken and which are formed. Indicate any unpaired electrons by a dot ().
(c)
(ii)
Suggest a mechanism for this reaction, showing all charges and using curly
arrows to show the movements of electron pairs.
Electrophilic substitution
NO2+ + NO3 []
N2O5
NO2
NO2
fast
NO3 + H+
H+
HNO3 []
last step, the abstraction of the proton by NO3 to produce HNO3, was usually
missing.
[3]
The following table lists some Hf values.
Hf / kJmol-1
+33.2
+5.0
compound
NO2(g)
N2O5(g)
N2O5(g)
NO2(g) + NO3(g)
H = +92.5 kJmol-1
Hf of NO3(g)
H = Hf [NO2(g)] + Hf [NO3(g)] Hf [N2O5(g)]
+92.5 = +33.2 + Hf [NO3(g)] (+5.0) [1m]
Hf [NO3(g)] = +64.3 kJmol-1 [1m]
(ii)
H2 Chemistry 9647 2012
H for reaction 2.
2NO3(g)
2NO2(g) + O2(g)
(e) By considering the entropy and enthalpy changes during reaction 1 and reaction 2,
suggest how the standard Gibbs free energy change of the two reactions will
compare in sign and in magnitude.
Hence predict which reaction will be the more spontaneous. Explain your reasoning.
Reaction 2 would be more spontaneous. [1m]
G = H + (TS)
For both reactions, there is an increase in number of gaseous particles from reactants
to products by 1, hence S is positive [1m].
For reaction 2, G will be negative at all temperatures since H and the term
(TS) is negative [1m].
For reaction 1, G will be only be negative at higher temperatures where
magnitude of (TS) > H [1m].
Examiners Comments:
Many candidates did well in this part. Most recognised that the S of both reactions
was positive, though fewer pointed out that the G for reaction 2 would be negative at
all temperatures because of the negative H, whereas that for reaction 1 will only be
negative at higher temperatures, so reaction 2 would be the more spontaneous.
Some candidates did not give clear arguments for G values based on those for H
and S, and hence explaining the degree of spontaneity.
[4]
[Total: 20]
Beams of charged particles are deflected by an electric field. If the particles are all
travelling at the same speed, though an electric field of constant strength, the angle of
deflection is proportional to their charge/mass ratio.
In a particular experimental set-up, protons are deflected through an angle of +15o.
(a)
Assuming an identical set of experimental conditions, by what angles will the following
particles be deflected? (D is deuterium, 2H, and T is tritium, 3H)
D
T+
He2+
charge
charge
= k
mass
mass
1
1
15 = k
k = 15
All the other ions have the same k value in the same electric field.
-1
o
= 7.5
2
deflection of D = 15
[1]
+1
o
= +5.0 [1]
3
deflection of T+ = 15
+2
o
= +7.5
4
deflection of He2+ = 15
[1]
Examiners comments: The question gave the deflection angle with a + sign. This
means that the direction of deflection is important. Hence, students need to
present the deflection angle in terms of + or . Need to show working. No working
means no marks awarded.
(b)
Under identical conditions, a beam of particles, R, each having 12 times the mass of
a proton, was deflected by an angle of +5o.
(i)
x+
12
deflection of R = 15
x+
12
+5 = 15
x = 4+
[1]
Note: Sign on the charge is important, need to put + behind the number.
(For oxidation state, the + sign is in front)
(ii)
(c)
(i)
(ii)
These four elements also differ greatly in their melting points. Describe how
their melting points differ, and explain this variation.
Na has giant metallic structure [] and possess strong electrostatic forces of
attraction between cations and sea of delocalised electrons [].
o Large amount of energy is needed to overcome the strong metallic
bonds. [] Hence Na has a high melting point. []
Si has giant covalent structure [] and has strong and extensive covalent
bonds between Si atoms [].
o More amount of energy is needed to overcome the strong and
extensive covalent bonds than the metallic bond [], hence melting
point of Si is higher than Na. []
P and Cl have simple molecular structures [] with weak van der waals
forces of attraction between molecules. []
o Hence they have the lowest melting points as least amount of energy
is needed to overcome the intermolecular forces of attraction. []
However, P4 has a larger electron cloud size than Cl2 [], more easily
polarised, hence stronger van der waals forces of attraction between P4
molecules [], and more energy is needed to overcome these forces of
attraction []. Hence P4 has higher melting point than Cl2 [].
10 15 []: 3 marks
5 9 []: 2 marks
2 4 []: 1 mark
Note: Variation indicates that the anomalies/details need to be included.
Student need to know that P has molecular formula of P4.
Examiners comments:
In part (ii) several described the melting point trend correctly, then did not
explain the trend well in terms of bonding. For example, that the giant covalent
bonding in silicon was stronger than the metallic bonding in sodium. Some
suggested that metallic bonding was stronger than covalent bonding, or that
sodium was giant ionic, whereas the other three were simple covalent.
(d)
Using the tetrapeptide whose structure is given below, and taking into account
of the ionic forms that the amino acid residues exist at pH7, draw the structures
of two of these tetrapeptide chains to illustrate both of the ionic interactions
mentioned above.
)
2 3
(CH
[1] for ionic interaction between COO- and NH3+ of the C- and N-terminus
[1] for ionic interaction between COO- of aspartic acid and NH3+ of arginine.
[1] for converting COOH to COO- and NH2 to NH3+ [discuss whether the 1 mark
should go to this point or to (dii) describe in greater detail]
Note: Student should show and label the ionic interaction but the red words are for
illustration purposes during teaching, student need not draw them.
Examiners comments:
Students MUST show the ionisation of the groups at both ends of the chain and their
subsequent ionic bonding with complementary groups in another chain. Common
mistake was to label hydrogen bonding instead of ionic bonding
(ii)
Describe two further ways, other than ionic linkages, by which the tertiary
structures of proteins can be stabilised.
Any of these 2 answers can be accepted:
Examiners comments:
Most performed well on part (ii), but candidates must be specific about what
type of R-group interactions there are, instead of just saying 'R-group
interactions' in general.
[5]
(e)
The antibiotic valinomycin acts by allowing the uncontrolled movement of ions across
cell membranes. Valinomycin is a cyclic compound containing six amino acid and six
hydroxyacid residues.
(i)
Apart from the peptide group, what other functional group is present in the
valinomycin molecule?
Ester [1]
When treated with a peptidase enzyme, the peptide bonds in the ring of valinomycin
are hydrolysed. Only two products are formed.
(ii)
[1]
and
[1]
Note: Ester linkage must be intact as the question used peptidase and peptide
bonds are hydrolysed. Peptide = amide linkage!
Examiners comments:
Several candidates omitted part (ii), or thought the ester bonds would also be
hydrolysed.
Common wrong products (CH3)2CHCH(OH)CO2H, (CH3)2CHCH(NH2)CO2H and
CH3CH(OH)CO2H.
[3]
[Total: 20]
Malic acid occurs in green apples and grapes. It is often added to beverages and
confectionery to confer a sour taste.
(a)
Suggest the reagents and conditions you would use in a three-step synthesis of malic
acid from bromoethanal, identifying the intermediates G and H.
[5]
Step 1: [1]
Reagent : HCN
Condition : trace amount of NaOH, 10-20oC
G:
[1]
Step 2: [1]
Reagent : ethanolic aq KCN
Condition : heat with reflux
H:
[1]
Step 3: [1]
Reagent : dilute HCl
Condition : heat with reflux
Malic acid :
Examiners comments:
Some did not state clearly the conditions for the hydrolysis of nitriles (dilute HCl or
H2SO4 and heat), and some did not write the structures of the intermediates G and H.
For the cyanohydrin, HCN + NaCN, HCN + NaOH or KCN + H+ (less than one
equivalent) were acceptable. For the nucleophilic substitution reaction, the KCN in
ethanol had to be heated under reflux. Subsequent hydrolysis with hot aqueous
H2SO4 would produce malic acid. A number of candidates did not represent the
structure of G (or H) accurately enough: CNCH2CHO is an isocyanide (isonitrile),
rather than the correct nitrile NCCH2CHO.
Some unusual reagents were suggested for use in syntheses: CH2COCl; NaOCN;
LiAlH4; Na2Cr2O7.
(b)
Malic acid can be dehydrated to give a mixture of two isomeric alkenedioic acids with
the molecular formula C4H4O4.
(i)
Draw the structures of the isomers, and state the type of isomerism they show.
(ii)
(iii)
The pKa values of the two acidic groups in one isomer, J, are 3.0 and 4.4,
whereas in the other isomer, K, they are 1.9 and 6.2.
Use the pKa values to suggest which isomer, J or K, produces the more stable
mono-anion on treatment with 1 mol of NaOH? Explain your answer.
Recall : Higher pKa values imply lower Ka values, hence less acidic.
The second pKa value of isomer K is larger than 4.4 indicates that the second
COOH group in K is less acidic.[] Hence, K produces the more stable mono-
anion.[ ]
[1] for both
Examiners comments:
There was some confusion as to what was meant by the term mono-anion,
with a number of candidates thinking that the question referred to the di-anion,
O2C-CH=CH-CO2. Some took the average of the two pKs values, and
concluded that isomer J (average 3.7), was more acidic than isomer K (average
4.05), and so its anion would be more stable. A significant number, however,
appreciated that a low first pKa, coupled with a high second pKa, indicated a
stable mono-anion, and used this reasoning to correctly identify K as the acid
producing the more stable mono-anion.
(iv) Draw the displayed formula of the mono-anion produced in (iii), and use your
formula to suggest an explanation for why it is more stable than the mono-anion
of the other isomer.
[6]
[1]
The cis-mono-anion would be the more stable, due to hydrogen bonding
between the -COO- group and the unionised -CO2H group. [1] Thus, it is more
difficult for the H in the COOH group to be hydrolysed to release H+.
Examiners comments:
Only a minority appreciated that its stability arises from the ability to form a
hydrogen bond between the COO- group with the adjacent non ionised CO2H.
Gentle heating the anhydrous crystals of one of the isomers J or K produces a neutral
compound L, C4H2O3, which does not react with sodium metal or give a precipitate with
2,4-dinitrophenylhydrazine.
Compound L reacts with ammonia to give a compound M, C4H5NO3, which gives a salt on
reaction with NaOH but not with HCl. Compound M decolourises Br2(aq).
(c)
[1]
Eqn []
Since L does not have an OH group, it does not react with Na metal.
Since the C=O group in L is not a carbonyl functional group, L does not give
a precipitate with 2,4-dinitrophenylhydrazine.
L reacts with NH3 to form M. The carbon of the C=O group in L is highly
electron deficient, and is thus susceptible for nucleophilic attack by NH3.
[1]
Eqn []
M has both an amide group and an acidic group. The lone pair of electrons
on the nitrogen atom of the amide group is delocalized into the C=O group
and hence is not able to accept H+ from the HCl.
The COOH group in M is acidic and hence reacts with NaOH to form a
salt.
Eqn []
Eqn []
8 to 11 [3]
5 to 7 [2]
2 to 4 [1]
H2 Chemistry 9647 2012
0 to 1 [0]
Examiners comments:
Many responses correctly related the observations to the functional groups
present, although only a few suggested structures for the products of the
reactions.
Some candidates did not relate their inference to the test results: they merely
stated that L does not contain an OH group or a carbonyl group. There were
very few candidates who gave equations for the reactions of M with NaOH(aq)
or with Br2(aq). Most worked out that L was maleic anhydride. Fewer drew the
correct structure for M, the half-amide of maleic acid.
When malic acid is heated with acidified K2Cr2O7, compound N is formed. Heating N in an
inert solvent for several hours produces P, C3H4O3 and a gas Q. Both N and P react with
2,4-dinitrophenylhydrazine. Compound P also gives a yellow precipitate with aqueous
alkaline iodine.
(d)
Suggest structures for N and P, and use the information given to suggest the identity
of gas Q.
[3]
[Total: 20]
Information from question
When malic acid is heated with acidified
K2Cr2O7, compound N is formed.
Both N and P react with 2,4dinitrophenylhydrazine.
Compound P also gives a yellow
precipitate with aqueous alkaline iodine.
Deduction
Malic acid undergoes oxidation.
2o alcohol oxidised to ketone.
N is ketone
Both undergo condensation.
N and P contain carbonyl group
P undergoes mild oxidation.
P contains
N:
[1]
P:
[1]
Molecular formula of Q = Molecular formula of N Molecular formula of P
= C4H4O5 - C3H4O3 = CO2
H2 Chemistry 9647 2012
Q : CO2 [1]
Examiners comments:
Where it was attempted, this part was answered better than (c). Most responses gave
the structure of N, and many also recognised P as CH3COCO2H and Q as CO2.
Most candidates deduced that gas Q was CO2, although there were some H2, H2O,
O2, CO and even HCO among the answers.