2012 G.C.E.

‘A’ Level H2 Chemistry

Paper 2

1(a) H2O2 + 2H+ + 2I– → 2H2O + I2

(b) It is a buffer solution hence the pH of the mixture would be maintained fairly constant
throughout the reaction so [H+] is constant.

(c) Prepare a new solution B with concentration of H2O2 > 1.5 mol dm-3 since time taken
is to be less than 20 seconds. E.g. A concentration of about 3 mol dm-3 solution of H2O2
could be prepared by using a measuring cylinder to add 100 cm 3 of the stock 7.5 mol
dm-3 H2O2 and make up to 250cm3 using a standard flask. The mixture must be shaken
to ensure a homogeneous solution

Procedure for experiment

1. Prepare solution B as described above.

2. Using a 100 cm3 measuring cylinder, measure out 50 cm3 of solution A and pour into a 250
cm3 beaker.

3. Use another 100 cm3 measuring cylinder to measure out 50 cm3 of solution B. Pour
solution B into the beaker containing A and start the stop watch at the same time. Swirl
the mixture.

4. Stop the stop watch when the mixture changes from colourless to dark blue.

5. Repeat with different volumes of A, B and water as indicated in the table below. The water
is measured with another measuring cylinder.

Expt Solution A /cm3 Water Solution B /cm3 Time 1/Time

/cm3

1 50 0 50

2 50 10 40

3 50 20 30

4 50 30 20

5 50 40 10
6. Plot a graph of 1/time vs Vol of Solution B. Graph should include the origin. If the graph is
a horizontal line, it is zero order wrt H2O2. If it is a straight line passing through the origin,
it is first order wrt to H2O2. If it is a parabola/curve, it is second order (or higher) wrt to
H2O2.

(d) H2O2 and ethanoic acid are corrosive chemicals, so gloves should be worn during the
experiment to minimise contact with the skin.

2 Fossil fuels which are 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?

(ii) Briefly explain how NO is formed in an internal combustion engine.

(iii) Suggest which class of compound, originally present in the living matter that
produced the fossil fuel, contained the sulfur that produces SO 2 on
combustion.

(i) alkanes or hydrocarbons

(ii) The nitrogen gas in the air reacts with the oxygen in the engine to form NO.

(iii) Proteins containing cysteine amino acid residue.

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.

SO2(g) + ½O2(g) ⇌ SO3(g) reaction 1

(b) (i) At 298K, ΔHfo(SO2) = −297 kJ mol‒1 and ΔHfo(SO3) = −396 kJ mol‒1.

Use these data to calculate ΔHo for reaction 1.

State the units.

(ii) For reaction 1, ΔSo = −93.5 JK‒1mol‒1 at 298 K.

Use this value and your answer to (i) to calculate ΔGo for reaction 1 at 298K.
State the units.

(i) ΔHo = (−396) – (−297 + 0) = −99.0 kJ mol‒1

(ii) ΔGo = −99.0 – (298)( −93.5 × 10−3) = −71.1 kJ mol‒1

 For any reaction, ΔGo and the equilibrium constant, Kc, are related according to the
equation ΔGo = −2.303RTlog Kc.

(c) (i) Use this equation to calculate a value of Kc for the oxidation of SO2 at
298 K.

(ii) Suggest what is the significance of the magnitude of your answer in (i).

(iii) Suggest why SO2 and not SO3 is formed when sulfur is heated in air.

(iv) Use your answer to (iii) to suggest why a catalyst is used industrially in the
Contact process. Explain your answer.

(i) −71.1 × 103 = −2.303(8.31)(298)log Kc

Kc = 2.97 × 1012

(ii) As Kc is very large, this indicated that the reaction is effectively complete.

(iii) The activation energy for the conversion to SO3 is very high.

(iv) A catalyst is required to provide an alternative reaction pathway with a lower activation
energy such that the fraction of molecules having energy greater or equal to the
activation energy is higher and thus leading to a faster rate of reaction.
3 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) Write an expression for Ksp of PbCl2, stating the units.

(ii) The solubility of PbCl2 is 4.7 g dm‒3.

Calculate the solubility product of PbCl2.
Give your answer to two significant figures.

(i) Ksp = [Pb2+][Cl–]2 mol3 dm‒9

(ii) [PbCl2] = 4.7 ÷ 278 = 0.0169 mol dm‒3

Ksp = (0.0169) × (2 × 0.0169)2 = 1.9 × 10−5 mol3 dm‒9

When 2.0 mol dm‒3 hydrochloric acid is added to separate samples of aqueous silver
nitrate and aqueous lead(II) nitrate, AgCl and PbCl2 are precipitated.

(b) (i) When the HCl(aq) is added to AgNO3(aq), what will be seen in the
container
immediately,
after one hour in daylight?

(ii) How would you 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.

(iii) When concentrated hydrochloric acid is added to the precipitate of PbCl2,

the precipitate dissolves.
Suggest, with an ionic equation, an explanation for this observation.

(i) immediately: a white precipitate of AgCl

after one hour in daylight: a grey precipitate of Ag

(ii) Addition of aqueous NH3.

The dissolving of the white precipitate to give a colourless solution would confirm the
identity of the white precipitate to be AgCl.

AgCl(s) + 2NH3(aq)  [Ag(NH3)2]+(aq) + Cl–(aq)

(iii) PbCl2 (s) ⇌ Pb2+ (aq) + 2Cl– (aq) ---- (1)

Pb2+ (aq) + 4Cl–(aq)  [Pb(Cl)4]2−(aq)

When concentrated hydrochloric acid is added the white precipitate of PbCl2 would
dissolve due to the formation of the [Pb(Cl)4]2− complex ion. The concentration of
Pb2+ drops which results in equilibrium (1) shifting to the right until I.P. is smaller
than Ksp.
 or

PbCl2 (s) + 2Cl–(aq)  [Pb(Cl)4]2−(aq)

When concentrated hydrochloric acid is added the white precipitate of PbCl2 would
dissolve due to the formation of the [Pb(Cl)4]2− complex ion which is soluble in
water.

(c) When concentrated hydrochloric acid is added to aqueous copper(II) chloride,

the solution eventually becomes yellow. When water is added to this yellow
solution, it becomes blue.
Suggest by means of ionic equations, an explanation for these observations.

Aqueous copper(II) chloride is a light blue solution due to the [Cu(H2O)6]2+ complex ion.

When concentrated hydrochloric acid is added, ligand exchange occurs to form the complex
ion, [CuCl4]2−, which is yellow.

[Cu(H2O)6]2+(aq) + 4Cl−(aq) ⇌ [CuCl4]2−(aq) + 6H2O(l)

As water is added the concentrated hydrochloric acid is diluted, and [Cu(H2O)6]2+(aq) which
is light blue in colour is formed.

[CuCl4]2− + 6H2O(l) ⇌ [Cu(H2O)6]2+(aq) + 4Cl−(aq)

Selective precipitation of sulfides may be used to separate the cations present in a

solution containing Cu2+, Ni2+ and Zn2+.
The reagent used is hydrogen sulfide which behaves as a dibasic (diprotic) weak acid
when in aqueous solution.
H2S(g) + aq ⇌ H+(aq) + HS‒(aq) Ka = 9.1 x 10‒8 mol dm‒3
and HS−(aq) ⇌ H+(aq) + S2‒(aq) Ka = 1.0 x 10‒15 mol dm‒3

Metal sulfides are precipitated by the following reaction.

M2+(aq) + S2‒(aq)  MS(s)

Relevant Ksp values are given in the table.

salt Ksp / mol dm‒3

CuS 6.3 x 10‒36

NiS 4.0 x 10‒21

ZnS 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.
 M2+ H2S passed through H2S passed through
H2S passed through a
being an acidic solution of an alkaline solution of
neutral solution of M2+
tested M2+ M2+
black precipitate ofblack precipitate of black precipitate of
Cu2+
CuS CuS CuS
black precipitate of
Ni2+ no precipitate no precipitate
NiS
2+ white precipitate of white precipitate of
Zn no precipitate
ZnS ZnS
(d) Use the data to give an explanation for each of the following questions. You
should give equations where appropriate. You are not expected to do any
calculations.

(i) Why is CuS the only sulfide of these three precipitated in acid solution?

(ii) Why is NiS precipitated in alkaline solution and not in neutral or acidic
solution?

(iii) Why is ZnS precipitated in both neutral and alkaline solution?

(i) H2S(g) + aq ⇌ H+(aq) + HS‒(aq) ------- (1)

HS−(aq) ⇌ H+(aq) + S2‒(aq) ------- (2)

CuS has the lowest Ksp of the three sulfides hence the least soluble in water.
In an acidic solution, there’s an increase in [H+] and the equilibrium position in (2) will
shift to the left to reduce the [H+]. Hence [S2‒] decreases.
With the decreased [S2‒], the ionic product is still greater than Ksp(CuS) and hence
CuS will precipitate out from the acid solution.

(ii) NiS has the highest Ksp of the three sulfides most soluble in water.
In an alkaline solution, there’s an increase in [OH−] which will react with H+ in the
solution and decrease [H+] and the equilibrium position in (2) will shift to the right to
increase the [H+]. Hence [S2−] increases.
With the increased [S2−], reaction ionic product will be greater than Ksp (NiS) and hence
NiS will precipitate out from the alkaline solution.
In neutral or acidic solutions, [S2−] is not high enough such that ionic product is less
than the Ksp(NiS) hence no precipitation occurs.

(iii) ZnS has a Ksp value in between that of CuS and NiS.
In a neutral solution, [S2−] is sufficiently high enough such that ionic product is greater
than the Ksp (ZnS) hence precipitation of ZnS occurs in a neutral solution.
In an alkaline solution, there’s an increase in [OH−] which will react with H+ in the
solution and decrease [H+] and the equilibrium position in (2) will shift to the right to
increase the [H+]. Hence [S2−] increases. With the increased [S2−], ionic product will be
greater than Ksp (ZnS) and hence Zn will precipitate out from the alkaline solution.
In an acidic solution, [S2−] is not high enough such that ionic product is less than the
Ksp (ZnS) hence no precipitation occurs.
4 Chlorogenic acid occurs naturally in coffee and an edible species of bamboo.

HO
OH
O

HO O

OH
OH

OH

chlorogenic 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.

(ii) How many chiral carbon atoms are there in a molecule of chlorogenic acid?

(i) secondary alcohol, tertiary alcohol, carboxylic acid, ester and phenol

(ii) 4

(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.

non-aromatic compound aromatic compound R

 H O O
H
H
O C O H C
O
H H
C C C
C C
H H
H
H C C H
O H O
C
O H
H O O
H H
H
non-aromatic compound aromatic compound R

(c) Draw the structural formula of the compound formed when the aromatic compound
R you have drawn in part (b) is added to an excess of Br2 dissolved in an organic
solvent.

Br Br Br

Br C C COOH

H H

HO Br

OH

(d) When the aromatic compound R is reacted with an excess of NaHCO3(aq),

compound S is formed which has the molecular formula C9H7O4Na.

(i) Suggest the structural formula of S.

(ii) Suggest why this product contains only one Na atom/ion although the
NaHCO3 is in excess

(i) CH=CHCOO- Na+

HO

OH

(ii) NaHCO3 is a weak base and only carboxylic acids is strong enough to react with it.
Phenol is too weak an acid to react with NaHCO3. Since there is only one carboxylic acid
group in R, thus only one mole of NaHCO3 will react with one mole of R to give the
product containing only one Na+ ion.
5 Lactic acid (2-hydroxypropanoic acid), CH3CH(OH)CO2H, is present in milk.
Lactic acid can also be produced in the laboratory from ethanal, CH3CHO, by the
following reactions.

step 1 step 2
CH3CHO  CH3CH(OH)CN  CH3CH(OH)CO2H

(a) (i) Name the reagent and conditions used and the type of reaction that occurs
in step 1.

(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.

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?

(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 polarized light.

The effect of plane polarized light on tartaric acid (2,3-dihydroxybutanedioic acid),

HO2CCH(OH)CH(OH)CO2H was investigated by Louis Pasteur.

CO2H

H C OH

H C OH

CO2H
tartartic acid

Pasteur identified three different types of tartaric acid molecule.

molecule A rotate plane polarized light to the right

molecule B rotate plane polarized light to the left

molecule C does not rotate plane polarized light

(c) Suggest an explanation for these observations.

(a) (i) reagent: HCN, small amount of NaOH(aq) or (a small amount of NaCN(s))

conditions: cold

type of reaction: nucleophilic addition

(ii) OH− + HCN  CN− + H2O

d- O-
O
slow
H C CN
C :CN-
H d+ CH3
CH3

..
O- OH

H C CN H OH H C CN + OH-

CH3 CH3

(b) (i) The lactic acid molecules present in milk are all of the same chirality, or made
up of only enantiomer.

(ii) As the CN− can attack the trigonal planar carbonyl carbon from either side of the
plane in equal probability, it will result in the formation of an equal amount of the
two enantiomers. The rotation of the plane polarized light by each of the
enantiomers is cancelled off by one another.

(c) molecule explanation

A Molecule A has 2 chiral carbons and it does not have a plane of
symmetry (the arrangement of groups at both the chiral carbons is
such that the plane of the polarised light is rotated to the right).
B Molecule B is the enantiomer of molecule A and hence rotates the
plane polarized light in the opposite direction of molecule A.
C Molecule C has 2 chiral carbons but the molecule is symmetrical
with an internal mirror plane (the arrangement of groups at both the
chiral carbons is such that the plane of the polarised light is rotated
to the right at one chiral carbon, but rotated to the left at the other
chiral carbon.)
The extent of rotation is equal for both carbons hence the rotation
of light to the right exactly cancels that to the left).