1997 Paper I

Section A
Question 1
a) At room temperature, iron has a body-centred cubic structure.
i) Draw the unit cell representation of iron.
ii) Deduce the number of atoms in one unit cell of iron.
(2 marks)

b) In a nickel-plating experiment, after passing a current of 5.0 A through an electroplating bath

containing a nickel compound for 5.5 minutes, 0.50 g of metallic nickel was deposited at the
cathode. Assuming that the current efficiency is 100 %, deduce the oxidation state of nickel in the
compound.
(3 marks)

c) Arrange, with explanation, the following chemical species in the order of decreasing size.
F O O-
(3 marks)

d) Explain why
i) the boiling point of HF is higher than that of HCl;
ii) the boiling point of HI is higher than that of HBr.
(2 marks)

Question 2
a) Consider the following dissociation reaction:
PCl5(g) PCl3(g) + Cl2(g)

At 400 K and 101 kPa pressure, the percentage dissociation of PCl5(g) is 86 %

i) Calculate Kp for the reaction at 400 K.
ii) State the effect of an increase in pressure
I) on Kp, and
II) on the percentage dissociation of PCl5(g).
(4 marks)

b) Account for the difference in Ka values given in the following equilibrium reactions:
H2SO4(aq) + H2O(l) H3O+(aq) + HSO4-(aq) Ka = 7.94x102 moldm-3
HSO4-(aq) + H2O(l) H3O+(aq) + SO42-(aq) Ka = 0.10 moldm-3

c) Consider the standard reduction potentials listed below:

Eo/V
[FeF6]3- + e- [FeF6]4-(aq) +0.40
I2(aq) + 2e- 2I-(aq) +0.54
Fe3+(aq) + e- Fe2+(aq) +0.76

Explain the following observations, giving a balanced equation in each case.

i) When Fe(NO3)3(aq) is added to KI(aq), a brown solution is formed.
ii) When concentrated KF(aq) is added to the resulting solution in i) above, the brown colour fades.
 (4 marks)

Question 3
0For each of the following materials, identify one inorganic compound which is an active ingredient:
i) photographic film
ii) gun powder
iii) bleaching powder
iv) antacid
(3 marks)

1For each of the following sulphur-containing chemical species, state its shape and the oxidation state
of sulphur.
i) H2S
ii) SO2
iii) SO42-
(3 marks)

2The effluent from an electroplating factory contains toxic Cr2O72-(aq). Suggest, with balanced
equations, how all chromium-containing species can be removed from the effluent before discharge.
(4 marks)

Question 4
a) The formula
HO2CCH=CHCO2H

can represent two compounds.

i) Draw a structure for each compound, clearly showing the difference between them.
ii) One of the compounds reacts with P2O5(s) to give compound A. Give the structure of A.
(2 marks)

b)
i) Draw all possible isomeric structures of dimethylbenzene.
ii) Upon oxidation, one of the isomers of dimethylbenzene produces a compound with the formula
C8H6O4. This compound on condensation with ethane-1,2-diol gives a useful textile material B.
Give the structure of B.
(3 marks)

0
0Give the hybridization state of the carbon atoms and the bond angles in ethene.
1Outline a free radical mechanism for the conversion of ethene to poly(ethene). Your answer should
include appropriate arrows to show how the new bonds are made.
(3 marks)

1Suggest, with explanation, a chemical reaction which would enable 4-methylbenzoic acid and 4-
methylphenol to be distinguished from each other.
(2 marks)

Question 5
a) Give a structure for each of the compounds D, E, F, G and H:
 LiAlH4
i) CH3CH2CONH2 H2 O D

ii) CH3CH2CONH2 Br2/NaOH(aq) E

SOCl2
iii) CH3CH2CO2H F

O3
iv) C8H16 Zn/CH CO H butanal only
3 2

v) C4H8O I2/NaOH(aq) triiodomethane + sodium salt of a carboxylic acid

H
(5 marks)

b) Consider the following reactions:

conc. H2SO4
J HBr K
heat

CH3CH2COCl
CH3CH2CH2OH L

NHNH2
NO2

M N
Na2Cr2O7
NO2
H3O+

(a red precipitate)

Give structures for J, K, L, M and N.

(5 marks)

Question 6
a)
i) Vegetable oils (e.g. peanut oil) can undergo the following chemical reactions to give useful solid
products P and Q.
excess H2/Pt
P

Vegetable oil
NaOH(aq)
Q
heat

Give one use each for P and Q. Suggest a possible structure for P.
ii) What is meant by the ‘iodine value’ of a fat/oil?
(3 marks)

b) Consider the reaction:

 R
C12H22O11 C6H12O6

disaccharide S glucose only

i) Give a chemical reagent R for the reaction.

ii) Draw a possible structure for S, clearly showing the linkage between the monosaccharide units.
(2 marks)

c)
0Explain, with the help of chemical equations, why ozone in the stratosphere is important to life on
earth.
1Show, with the help of chemical equations, how the presence of chlorofluorocarbons (CFCs) can
influence the amount of ozone in the stratosphere.
2What have CFCs been widely used for in the past? Suggest a more environmentally acceptable
chemical to replace CFCs.
(5 marks)

Section B
Question 7
a) Briefly describe how a sample of dry chlorine gas can be prepared in the laboratory. Draw a
labeled diagram of the laboratory set-up and state the safety precaution(s) that is/are required.
(6 marks)

b) An aqueous solution contained 0.40 g of a complex salt Cr(NH3)5Cl3. The free chloride ions
present in the solution required 21.90 cm3 of 0.150 M silver nitrate(V) solution for complete
precipitation. Deduce the structural formula of the complex ion present in the salt.
(4 marks)

Question 8
a)
i) Give the reaction conditions and the necessary chemicals/reagents required for the formation of
benzenediazonium ion from phenylamine.
ii) Benzenediazonium ion reacts with naphthalen-2-ol to give compound T. Give the structure of T.
(3 marks)

b) You are provided with a mixture of two liquids, hexan-l-amine (U) and ethyl ethanoate (W).
Outline an experimental procedure, based on a solvent extraction process, to enable U to be
separated from W.
(3 marks)

c) For each of the following groups of compounds, suggest a chemical test which would enable each
compound to be distinguished from the other(s). In your answer also give the changes that you
would expect to observe for each compound.
i) CH3CH2CH2OH, (CH3)2CHOHand (CH3)3COH
ii) C6H5CH2I and C6H5CH2Cl
(4 marks)

Section C
Question 9
Write an essay on the variation in properties of the Group II elements and their compounds.
(20 marks)

Question 10
Write an essay on the chemistry of amines.
(20 marks)

1997 Paper II

Section A
Question 1
a)
i) Explain the terms ‘dipole’ and ‘dipole moment’, using HBr as an example.
ii) Explain why the dipole moment of HF is greater than that of HI.
iii) State the effect of an electric field on molecules of the following compounds and explain the effect
in terms of dipole moment.
Cl
Cl
Cl

Cl

(7 marks)

b) At 360 K and 101 kPa pressure, the vapour produced by 0.226 g of a volatile liquid occupies 85.0
cm3. Assuming that the vapour behaves ideally, calculate the molar mass of the liquid.
(1 kPa = 1x103 Nm-2)
(3 marks)

c) Three types of boiling point-composition curves for two miscible liquids A and B at one
atmospheric pressure are shown below.

Account for the characteristics of these curves.

(7 marks)

Question 2
a) Describe and account for the characteristics of the emission spectrum of atomic hydrogen.
(7 marks)

b)
i) What is an electron shell in an atom?
ii) For each of the electron shells with principal quantum numbers 1,2 and 3, list the subshells.
iii) Deduce the maximum number of electrons in each of the electron shells in ii).
(6 marks)

c) Given the following thermochemical data at 298 K:

Standard enthalpy change of formation of CO2(g) = -393.5 kJmol-1
Standard enthalpy change of formation of H2O(l) = -285.8 kJmol-1
Standard enthalpy change of combustion of CH3CH2OH(l) = -1336.9 kJmol-1

Calculate the standard enthalpy change of formation of CH3CH2OH(l) at 298 K.

(4 marks)

Question 3
The reaction of iodine with propanone in acidic solutions can be represented by the following
equation:
I2(aq) + CH3COCH3(aq) CH2ICOCH3(aq) + H+(aq) + I-(aq)

a)
i) The progress of the reaction can be monitored by a titrimetric method. Outline the experimental
procedure.
ii) State how the initial rate of the reaction can be determined from the titrimetric results.
iii) Suggest another method to monitor the progress of the reaction.
(6 marks)

b) The following initial rates and initial concentrations were obtained in an experiment at 298 K:

Initial rate/moldm-3s-1 Initial concentration/moldm-3

[I2(aq)] [CH3COCH3(aq)] [H+(aq)]
-5
3.5x10 2.5x10-4 2.0x10-1 5.0x10-3
3.5x10-5 1.5x10-4 2.0x10-1 5.0x10-3
1.4x10-4 2.5x10-4 4.0x10-1 1.0x10-2
7.0x10-5 2.5x10-4 4.0x10-1 5.0x10-3

i) Deduce the rate equation for the reaction.

ii) Calculate the rate constant for the reaction at 298 K.
(5 marks)

c) Suppose that the reaction takes place in a buffer solution of pH 4. On the basis of your results in b),
deduce the half-life of the reaction at 298 K.
(4 marks)

d) For a given set of initial concentrations, the initial rate doubles when temperature is increased from
298 K to 308 K. Calculate the activation energy of the reaction.
(2 marks)

Question 4
a) The diagram below shows an electrochemical cell connected to a digital voltmeter. An
electromotive force of 0.83 V was recorded at 298 K.
i) Write half-equations for the reaction at the anode and at the cathode, and give their corresponding
standard electrode potentials.
ii) Write the overall equation for the electrochemical reaction.
iii) Write the cell diagram for the electrochemical cell, using the IUPAC convention.
(6 marks)

b) Discuss and write relevant equations for the electrochemical processes involved when broken
surfaces of the following are exposed to moist air.
i) galvanized iron
ii) tin-plated iron
(4 marks)

c) A solution is formed by mixing equal volumes of 0.20 M CH3CO2H(aq) and 0.20 M

CH3CO2Na(aq).
i) Identify all Bronsted acids and all Bronsted bases in the solution.
ii) Calculate the concentration of each chemical species, excluding H2O, present in the solution at 298
K.
(Ka of CH3CO2H = 1.76x10-5 moldm-3 at 298 K)
(7 marks)

Section B
Question 5
a) In an experiment, 10.0 g of butanone reacts with 5.0 g of hydrogen cyanide to give 11.0 g of 2-
hydroxy-2-methylbutanenitrile.
i) Find the limiting reactant of the reaction, showing clearly your calculation.
ii) Calculate the percentage yield of 2-hydroxy2-methylbutanenitrile.
iii) Name the type of reaction and outline the mechanism involved. (Movement of electron pairs
should be indicated by curly arrows.)
(6 marks)

b) The following equation represents the acid hydrolysis of a dipeptide D to produce compounds E
and F, one of which is a chiral compound.
H3C
O
H3O+ E+F
H2NCHC NHCH2CO2H

D
0Name all functional groups in D.
1Give one structure for E and one for F. Draw a suitable representation for the chiral product.
2Suggest a method to separate E and F from the reaction mixture.
(5 marks)

c) Briefly explain with a chemical equation how butylated hydroxytoluene (BHT) acts as an
antioxidant to retard rancidity in fats and oils.
OH
(CH3)3C C(CH3)3

CH3

BHT
(3 marks)

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

CH3 CH3
N

i)

O
ii) CH CH
3 2 C CH(CH3)CH2CH3

H CH3
C
iii) C
HO2C H

(3 marks)

Question 6
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 conversion in the laboratory and for each step, give the
reagent(s), conditions, and structure of the product.
i) (CH3)3CCH=CH2 (CH3)3CC≡CH

ii) NH2

iii) CH3CH2C≡N
(9 marks)

b) Saponification of 1 mol of fat G with NaOH(aq) produces 1 mol of a triol C3H8O3, 2 mol of
CH3(CH2)16CO2-Na+ and 1 mol of CH3(CH2)14CO2-Na+.
i) If G is optically active, suggest its structure. Explain.
ii) If G is optically inactive, suggest its structure.
iii) What is the minimum number of moles of base required for the complete saponification of 1 mol of
G?
(4 marks)
c) Compound H, C3H6O2, does not react with NaBH4 and displays the following infra-red spectrum.
Deduce all possible structures of H.

(4 marks)

Question 7
a) Suggest a chemical test to distinguish one compound from the other in each of the following pairs.
Each test should include the reagent(s), expected observation with each compound and the chemical
equation(s).
a) and
b) and
c) and
d) and
(12 marks)

b) Identify J, K, L, M and N in the following reactions.

i)
ii)
iii) + CH3OH
iv) M
v) N
(5 marks)

Question 8
a) Suggest how the following nitrogen oxides can be prepared in the laboratory. In each case, state the
reactant(s) used and the reaction conditions, and write balanced equation(s) for the reaction(s)
involved.
i) dinitrogen oxide, N2O
ii) nitrogen monoxide, NO
iii) dinitrogen tetraoxide, N2O4
(6 marks)

b) The synthesis of ammonia using the Haber Process involves the following:
N2(g) + 3H2(g) 2NH3(g) ∆Ho = -92 kJmol-1

i) State the effect of a change in temperature on the reaction at equilibrium.

ii) Name a catalyst for the process and state the effect of the catalyst on the reaction.
iii) State how ammonia is isolated from unreacted nitrogen and hydrogen in the process.
iv) Give two major uses of ammonia in industry.
(7 marks)

c) The reaction of chlorine with excess ammonia in the gas phase to give ammonium chloride and
nitrogen involves several steps.
i) Write a balanced equation for the overall reaction.
ii) Briefly explain how ammonia acts as a reducing agent and as a base in the reaction.
(4 marks)