1996 Paper I

Section A
Question 1
a)
12
i) Write down the number of neutrons, protons and electrons in one atom of carbon-12, C , and in
13
one atom of carbon-13, C .
12
ii) The isotopic mass of C is 12.000 atomic mass unit (a.m.u.). Calculate the mass, in kg, of 1 mol
12
of C atoms.
Given:
1 a.m.u. = 1.6605x10-27 kg
Avogadro constant, L = 6.0221x1023 mol-1
iii) The following data were obtained from the mass spectrum of a carbon-containing compound:

Ion Mass/a.m.u. Relative intensity

12
C+ 12.000 100.00
13 +
C 13.003 1.12

Using the above data, calculate the relative atomic mass of carbon.
(5 marks)

14
b) Carbon-14, C , is radioactive, emitting β-particles.
14
i) Write an equation for the decay of C .
14 12
ii) A charcoal sample from the ruins of an ancient settlement was found to have a C / C ratio 0.60
times that found in living organisms.
14 12
1) Explain why the C / C ratio in the charcoal sample is smaller than that in living organisms.
14
2) Given that the half-life for the decay of C is 5730 years, calculate the age of the charcoal sample.
(Note: The integrated form of the rate expression for radioactive decay can be represented by the
following equation:

N0 0.301
log10 ( ) = t
Nt t 1/2

where
N0 is the initial number of radioactive nuclei;
Nt is the number of radioactive nuclei at time t;
t1/2 is the half-life for the decay.)
iii) All radioactive decay has zero activation energy. Comment on the effect of temperature upon the
rate of decay.
(5 marks)

c) Explain why
i) the first ionization energy of oxygen is greater than that of sulphur;
ii) the first ionization energy of oxygen is smaller than that of fluorine.
(2 marks)

d) Sketch the pictorial representation of a p orbital and indicate the location of the nucleus in your
diagram.
(1 mark)
e) At 298 K, 50 cm3 of a solution of I2 in CCl4 were mixed and shaken with 200 cm3 of distilled water
in a separating funnel until equilibrium was attained. The two layers were then separated. 20.0 cm3
of the CCl4 layer required 12.15 cm3 of 0.105 M S2O32-(aq) for titration, whereas 50.0 cm3 of the
aqueous layer required 8.25 cm3 of 0.0050 M S2O32-(aq).
i) Calculate the distribution coefficient of I2 between water and CCl4, at 298 K.
ii) If the 200 cm3 of distilled water contain some dissolved KI, will this affect the value of the
distribution coefficient? Briefly explain.
(3 marks)

f) SO2(g) and O2(g) were mixed in the mole ratio of 3: 1 at 1000 K in the presence of a catalyst.
When equilibrium was attained at 373 kPa pressure, one half of the SO2(g) had been converted into
SO3(g).
i) Write an expression for Kp for the reaction of SO2(g) and O2(g) to give SO3(g).
ii) Calculate Kp for the above reaction under the given conditions.
iii) If the above reaction takes place in the absence of the catalyst, but other conditions remain
unchanged, will the value of Kp increase, decrease or remain the same?
(4 marks)

Question 2
a) State the method by which sodium hydroxide is produced industrially. Give two other products
obtained by this industrial process.
(2 marks)

b) For each of the following chemical species, draw a three-dimensional structure showing the bond
electron pairs and lone electron pair(s) of the central atom underlined. State the shape of the
species in each case.
i) ClO3-
ii) NOF
(3 marks)

c) What is the oxidation state of the central atom in each of the following compounds?
HClO3 HClO4 HMnO4 H2CrO4
(2 marks)

d)
i) Explain why among the four compounds in c), only HClO3 can undergo disproportionation.
ii) Write a balanced equation for the disproportionation of HClO3 to give HClO4 and ClO2.
(2 marks)

e) Which is the stronger acid in each of the following pairs of substances? Briefly explain your choice.
i) [Fe(H2O)6]2+(aq) and [Fe(H2O)613+(aq)
ii) HClO3(aq) and HClO4(aq)
iii) HMnO4(aq) and H2CrO4(aq)
(6
marks)

f) The complex ion [Co(H2NCH2CH2NH2)2Cl2]+ has three isomers. These isomers belong to two types
of isomerism.
i) Draw a three-dimensional structure for each isomer.
ii) What are the two types of isomerism?
iii) State one difference in the properties of the pair of isomers in each type of isomerism.
(5 marks)

Question 3
a) Arrange the following carbocations in the order of increasing stability. Explain your arrangement.
+
CH3 CH3 CH2+
+

(3 marks)

b) Arrange the following compounds in the order of increasing basic strength. Explain your
arrangement.
NH2

NH2 NH3

(3 marks)

c) Consider the following structure:

i) Give the hybridization states of the carbon atoms a, b and c.

ii) Suggest expected values for the bond angles α, β and γ.
(3 marks)

d) Give the structure of the major organic product(s) in each of the following reactions:
O
C
i) O + H
NaOH(aq)
CH3 C CH3 warm

O O
ii) HO C CH CH2 C OH
2 heat

CH3

iii) C CHO conc. NaOH

CH3 heat

(4 marks)

e) The structures for compounds A and B are shown below:

 OH OH

Outline a laboratory method, based on a difference in their chemical properties, to separate a mixture of
A and B.
(3 marks)

f)
i) Give the structures of compounds D and E in the following organic synthesis:
O
C
H D E
H3O+
HCN
heat

ii) Outline a reaction mechanism for the formation of D. (Movement of electron pairs should be
indicated by curly arrows.)
(4 marks)

Section B
Question 4
a) BaO is a basic oxide, while CO2 is an acidic oxide.
i) State all observations when dilute HCl(aq) is added to BaO(s).
ii) State all observations when CO2 is bubbled, until in excess, into the following solutions.
1) dilute HCl(aq)
2) Ca(OH)2(aq)
(4 marks)

b) Describe the experimental procedures of a chemical test that you would employ in order to
demonstrate that a liquid sample is an aromatic primary amine. State the observation of your test.
(4 marks)

c) In a titration experiment, a H2O2 solution was diluted 25 times. 25.0 cm3 of the diluted H2O2
solution, in the presence of excess dilute H2SO4, required 26.45 cm3 of 0.00995 M KMnO4 solution
for titration.
i) Describe, with experimental details, how you would dilute the H2O2 solution.
ii) Write a balanced equation for the reaction involved in the titration.
iii) Describe the colour change at the end point of the titration.
iv) Calculate the molarity of the diluted H2O2 solution.
v) What reagent would you use to standardize the KMnO4 solution in this experiment?
(8 marks)

d) In an experiment to determine the concentration of H2O2 contained in a rainwater sample, 5.0 cm3
of the sample were mixed with an excess of a certain transition metal complex solution, giving a
coloured mixture. The absorbance of the mixture was measured by a colorimeter and was found to
be 0.0273. When 5.0 cm3 of 1.46x10-6 M H2O2 (instead of the rainwater sample) were treated in the
same way, an absorbance of 0.0398 was recorded.
i) Calculate the concentration of H2O2 in the rainwater sample assuming that concentration is directly
proportional to absorbance.
ii) Why is the method of titration not suitable for the determination of the concentration of H 2O2 in the
rainwater sample?
iii) Why is it not suitable to collect the rainwater sample for this experiment in an iron container?
(4 marks)

Section C
Question 5
Write an essay on the structures of different types of solid, and the relationship between structure and
physical properties of solids.
(20 marks)

Question 6
Write an essay on the group of elements carbon to lead, covering the trends in their physical properties
as well as the trends in properties of their hydrides and oxides.
(20 marks)

Question 7
Write an essay on amino acids, polypeptides and proteins.
Your essay should include the properties of amino acids in aqueous solutions and a method of
separation for a mixture of amino acids, as well as the constitution of polypeptides and proteins and
their hydrolysis.
(20 marks)

1996 Paper II

Section A
Question 1
a) For the hydrogenation of buta-1,3-diene,
H2C=CHCH=CH2(g) + 2H2(g) CH3CH2CH2CH3(g)

The experimental molar enthalpy change is -239 kJmol-1.

i) Estimate the molar enthalpy change for the above hydrogenation using the bond energy terms
below:

Bond Bond energy term/kJmol-1

H-H 436
C-H 413
C-C 346
C=C 611

ii) Explain why the estimated value differs from the experimental value.
(4 marks)

b)
i) Draw the Maxwell-Boltzmann curves for the distribution of molecular speeds at two different
temperatures for an ideal gas.
ii) Use your curves in i) to explain why, for a fixed mass of an ideal gas at constant volume, the
 pressure increases as the temperature is raised.
(4 marks)

c)
i) At 298 K, the pH of 0.050 M CH3CH2COOH is 3.10. Calculate the Ka of CH3CH2COOH at 298 K.
ii) Calculate the pH at 298 K of a solution which is 0.050 M with respect to CH 3CH2COOH and to
CH3CH2COONa.
iii) 5.0x10-4 mol of solid NaOH were added separately to
1) 100 cm3 of 0.050 M CH3CH2COOH, and
2) 100 cm3 of the solution in ii) above.
Assuming that the change in volume upon the addition of NaOH is negligible, calculate the pH at
298 K of the solution in each case. Comment on the difference in the pH change of the two
solutions.
(9 marks)

Question 2
a)
i) The graph below shows the variation of pressure with volume at 298 K for 1 mol each of an ideal
gas and a real gas.

Explain why
1) At low pressures, the curve for the real gas approaches that for the ideal gas;
2) At 298 K and when contained in vessels of identical volume, 1 mol of N 2 exerts a greater pressure
than 1 mol of HCl.
ii) At 298 K, 1.0 dm3 of N2 at 0.20 Pa pressure was mixed with 2.0 dm3 of O2 at 0.40 Pa in a 4.0 dm3
container. Assuming that both N2 and O2 behave ideally, calculate the pressure of the gaseous
mixture at 298 K.
(5 marks)

b) Briefly describe each of the following intermolecular forces and illustrate your answer with an
appropriate example in each case.
dipole-dipole interactions
hydrogen bonding
van der Waals’ forces
(4 marks)

c)
i) Two miscible liquids A and B form ideal solutions when mixed. At 298 K, the vapour pressures of
pure A and pure B are 32 kPa and 16 kPa respectively. For a mixture of 1 mol of A and 3 mol of B
at 298 K, calculate
1) the vapour pressure of the mixture;
2) the mole fraction of A in the vapour which is in equilibrium with the mixture.
ii) Predict whether the following pairs of liquids when mixed, would give solutions showing positive
deviation or negative deviation from Raoult's Law. Explain your prediction.
CH3

1) CH3CH2OH and

2) C2H5OC2H5 and CHCl3

(8 marks)

Question 3
a)
i) Given that at 298 K, the solubility product of Cu(OH)2 is 2.0x10-19 mo13dm-9, calculate the
concentration of Cu2+(aq) ions in a saturated solution of Cu(OH)2 in a buffer solution at pH 10.
ii) Consider the following electrochemical cell:

1) Identify, with explanation, the negative terminal of the electrochemical cell.

2) Comment on the change in concentration of Cu2+(aq) ions in beakers D and E as electrochemical
reaction occurs.
3) Using the IUPAC convention, write the cell diagram for the electrochemical cell.
(8 marks)

b) Draw a labeled diagram of a dilatometer and briefly describe how a dilatometer can be used to
follow the progress of a reaction.
(4 marks)

c) The following equation represents the decomposition of N2O5(g):

2N2O5(g) 4NO2(g) + O2(g)

The progress of the above decomposition can be followed by measuring the partial pressures of

N2O5(g), PN 2O5 , at different times, t. The table below lists the results of such an experiment:

t/minute 0 100 200 300 400 550 800 1250

PN 2O 5 /kPa 13.3 10.9 8.9 7.2 5.9 4.4 2.7 1.1

i) By plotting a suitable graph, find the order of the decomposition.

ii) Using your graph in i), determine the rate constant of the decomposition.
(5 marks)
Section B
Question 4
a) Give two reactions to illustrate the following statement:
‘Lithium compounds differ in their chemical properties from compounds of other Group I
elements.’
(4 marks)

b) For each of the following pairs of compounds, suggest a test to distinguish one compound from the
other
i) Na2CO3(s) and NaHCO3(s)
ii) KCl(s) and MgCl2(s).
(4 marks)

c) Briefly explain why magnesium sulphate(VI) is soluble in water, whereas barium sulphate(VI) is
almost insoluble.
(2 marks)

d) Describe the bonding, structure and the reactions with water of the Group IV tetrachlorides.
Explain how the thermal stability of these tetrachlorides varies on descending the group.
(7 marks)

Question 5
a) The first electron affinities of chlorine and bromine are -364 kJmol-1 and -295 kJmol-1 respectively.
i) What is the meaning of ‘electron affinity’?
ii) Explain why the first electron affinity of chlorine is more negative than that of bromine.
(4 marks)

b) What are the highest and lowest oxidation states of bromine? Give one compound in which
bromine is in its highest oxidation state and another compound in which bromine is in its lowest
oxidation state.
(3 marks)

c) Hydrogen chloride can be prepared by the action of concentrated sulphuric(VI) acid on potassium
chloride.
i) Write a balanced equation for the reaction of concentrated sulphuric(VI) acid and potassium
chloride.
ii) Briefly describe how a sample of dry hydrogen chloride can be prepared in the laboratory, using the
above reaction. Draw a labeled diagram of the laboratory set-up and state the safety precaution(s)
that is/are required.
iii) Briefly explain why hydrogen bromide cannot be prepared by the action of concentrated
sulphuric(VI) acid on potassium bromide. Write a balanced equation to represent the reaction that
occurs.
iv) Suggest how a sample of hydrogen bromide can be prepared in the laboratory.
(10 marks)

Question 6
a) Using the ‘electrons-in-boxes’ representation, write the ground state electronic structure outside the
argon core for V2+ and Cu+ respectively.
 (2 marks)

b) What do you understand by the following terms?

i) complex ion
ii) stability constant

In each case, illustrate your answer with an example involving copper(II).

(5 marks)

c) State three characteristic properties of d-block elements, apart from complex ion formation. In each
case, illustrate your answer with an example involving copper or vanadium.
(3 marks)

d) You are provided with the following standard reduction potentials:

Eo/V
Cu2+(aq) + e- Cu+(aq) +0.15
Cu2+(aq) + 2e- Cu(s) +0.34
+
Cu (aq) + e -
Cu(s) +0.52
I2(s) + 2e - -
2I (aq) +0.54
2+ -
Cu (aq) + I (aq) + e -
CuI(s) +0.92

Using the above information,

i) explain why copper(I) compounds are unstable in aqueous solutions; and
ii) predict what will be observed when a potassium iodide solution is added to a copper(II)
sulphate(VI) solution. Explain your prediction and write a balanced equation for the reaction
involved.
(5 marks)

e) In acidic conditions, VO2+(aq) can be reduced by sulphur dioxide to give VO 2+(aq). Write a
balanced equation for the reaction.
(2 marks)

Section C
Question 7
a) Two compounds F and G, with the same molecular formula C4H8O, give the following results in
four chemical tests.

Reagent F G
H2NOH No reaction No reaction
Cr2O72-/H+ Colour changes from orange to No reaction
green
Br2/CH3CCl3 Decolorization No reaction
I2/NaOH Yellow precipitate No reaction

i) Give the structure for F. Explain your answer with reference to the result of each of the chemical
tests.
ii) Suggest a structure for G and explain your suggestion.
(7 marks)
b) In an experiment, 25 g of (CH3)3COH react with 36 g of HCl to give 28 g of (CH3)3CCl.
i) Find the limiting reactant of the reaction, showing clearly your calculation.
ii) Calculate the percentage yield of (CH3)3CCl.
iii) Name the type of the reaction and outline the mechanism of the reaction. (Movement of electron
pairs should be indicated by curly arrows.)
(6 marks)

c) Suggest a chemical test to distinguish one compound from the other in each of the following pairs.
Your answer should include the reagents used and the observation expected.

O
CHO
i) and

CH2Cl CH2I
ii) and

(4 marks)

Question 8
a)
i) An acyclic compound H of molecular formula C4H8O2 has a fruity smell. It does not produce a
derivative with 2,4-dinitrophenylhydrazine nor with propanoyl chloride. Deduce the functional
group(s) of H. Draw four possible structures for H.
ii) On reduction with an excess of LiAlH4, H gives only one product, J, which reacts with ethanoic
anhydride. Deduce, giving equations, the structure for H and also the structure for J.
(8 marks)

b) The following compounds can exist in isomeric forms:

i) butenedioic acid, and
ii) 2-aminopropanoic acid.

In each case, state the type of isomerism and draw suitable representations for the isomers.
(4 marks)

c) Identify K, L, M, N and P in the following reactions:

PCl5
i) K (CH3)2CHCH2CH2Cl

+ CH3
N NCl-

ii) N
N
L HO

NO2
NO2
iii) CH3
CH3 M NO2
 OH

iv) NaOH N
CH3I

O
v) CH CH C CH3
NaHSO3 P
3 2

(5 marks)

Question 9
a) Each of the following conversions can be completed in not more than three steps. Use equations to
show how you would carry out each of these conversions in the laboratory. For each conversion,
give the reagent(s), conditions, and structure of the intermediate(s).

CH2Br CH2CH2NH2
i)

Br
O O
ii)
C(CH3)3 H C (CH2)3 C C(CH3)3

COCl NH2
iii)

OH OH
iv)
OH

(12 marks)

b) Give the structure of the major product in the following reaction and outline the mechanism of the
reaction. (Movement of electron pairs should be indicated by curly arrows.)

CH2
+ HBr

(3 marks)

c) Give a systematic name to each of the following compounds:

CH3 OH
i) CH CH CH2 CH CH3
3

CH3
CH3
ii)
CH3
O
(2 marks)