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2 SECTION A Answer all the questions in this section.

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1(a) Nitrogen is used in the packing of junk food to keep the food fresher for a longer period. (i) Write the electronic configuration of the nitrogen atoms. [1 mark] .

(ii) Nitrogen can form the NCl3 molecule only, but phosphorous can form both the PCl3 as well as PCl5 molecule. Draw the Lewis diagram for NCl3 and PCl5 and Predict the polarity NCl3 and PCl5. [4 marks]

(iii)

Show and label the overlapping orbital of N2H4.

[3 marks]

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The diagram below shows the four electron transitions in the hydrogen atom. (i) Base on the energy level diagram, sketch the line spectrum formed from these transition. [2 marks]

(b)

n=5 n=4 Energy n=3

n=2

n=1

Some standard electrode potentials are shown below. Half Reaction Ag+ + Cl2 + Cu2+ + 2 Fe3+ + I2 + Ag ClEo/V + 0.80

+ 1.36

Cu Fe2+ I-

+ 0.34

+ 0.77

+ 0.54

(a) The diagram below shows an incomplete cell consisting of Cu/Cu2+ and Ag/Ag+ half-cells under standard conditions.

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(i)

Complete and label the diagram to show how the cell potential of this cell could be measured. [2 marks] [1 mark] [1 mark]

(ii) On the diagram, show the direction of electron flow in the circuit. (iii) Write the cell diagram for the above set-up.

............................................................................................................... (iv) Write the overall cell reaction. [1 mark]

................................................................................................................. (v) Calculate the standard cell potential. [1 mark]

(vi) Calculate the cell potential if the solution in the right beaker is replaced with 0.10 mol dm-3 aqueous silver nitrate, other factors remaining unchanged. [ 2 marks]

(b) Chlorine will oxidise Fe2+ to Fe3+ but iodine will not. Explain why using the electrode potential data. [2 marks] ................................................................................................................................................... ................................................................................................................................................... ...................................................................................................................................................

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3(a) (i)

What do you understand by the term complex ion?

[2 marks]

(ii) 1,2-ethenediamine is a chelating ligand. Explain the term chelating ligand. [1 mark]

. (b) A series of experiments were carried out on an aqueous solution of copper(II) sulphate. Experiment Aqueous sodium hydroxide is added to copper(II) sulphate solution Aqueous ammonia is added to copper(II) sulphate solution until in excess Observation A blue precipitate is formed

The blue precipitate dissolves and a dark blue solution is obtained

(i)

Write the formula of all the complex ions in the experiments

[2 marks]

(ii) Arrange the ligands in order of increasing strength with respect to copper(II). Explain your answer. [2 marks]
..

(iii) Explain why transition element complex are often coloured , whereas compounds of other metals are usually white. [3 marks]
. .

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4(a) Aspartame is an artificial sweetener which is 180 times sweeter than sugar. The structural formula of aspartame is H2N CH - CO NH CH COO CH3 | | CH2 CH2 | | COOH Name four different functional groups in the molecule of aspartame. [4 marks]

(i)

(ii) Identify two of the functional groups which contribute to its solubility in water. Give reasons for your answer. [2 marks] (b) Aspartame can be hydrolyses into its constituent parts under certain conditions. (i) Suggest the reagent and condition for hydrolysis. [1 mark]

.... (ii) Draw the structural formulae of all organic molecules obtained by hydrolysis aspartame. [3 marks]

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7 SECTION B Answer any four questions in this section.

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5(a)

Krypton is used to fill fluorescent lights and photo graphic flash lamps. (i) Use the following data to sketch a phase diagram for krypton Pressure/atm Triple point Critical point Melting point Boiling point (ii) (iii) 0.175 54 1 1 Temperature/C -169 -63 -156.6 -152.3 [1 mark] [4 marks]

What is meant by the term triple point ?

What are the physical states of krypton under P = 5.3 atm , T = -153C and P= 65 atm , T = 250C [2 marks]

(iv)

Can a sample of gaseous krypton at room temperature be liquefied by raising its pressure? Explain why? [2 marks]

(b) At 101 kPa, the boiling points of pure ethanol and water are 78.5C and 100.0C respectively. A solution of ethanol and water forms an azeotropic mixture with a boiling point of 78.2C. The percentage by mass of ethanol in the mixture is 96.0% ethanol.The boiling point-composition curve for the ethanol-water mixture is shown below. Temperature/oC (C)
100

78.5 78.2 0% 96% 100%

composition (i) This mixture does not obey Raoult law. State the type of deviation and explain. [3 marks] (ii) Briefly explain how pure ethanol can be obtained from a 70% ethanol mixture. [3 marks]

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6(a) 1.00 g of solid potassium hydroxide was dropped into 50.0 cm3 (50.0 g) of aqueous hydrogen chloride (slightly in excess) contained in a polystyrene cup. A temperature change from 30.0oC to 40.0oC was recorded with a thermometer in the solution. (The specific heat capacity of the solution is 4.0 J K-1 g-1). (i) (ii) (iii) (iv) Define the heat of neutralization. Write a balance equation for the above equation. [2 mark] [1 mark]

From the experimental data provided, calculate H for the reaction. [3 marks] Give one important reason why it is preferable to use a polystyrene cup [1 mark] [1 mark]

instead of a glass beaker. (v) (b) Why should the solution stirred during the reaction.

Octane, C8H18 is used as fuel. (i) (ii) Define the heat of combustion with related to octane . [1 mark]

Write a balance equation for the combustion of octane in excess oxygen. [1 mark]

(iii) Calculate the standard enthalpy of combustion of octane by using the following information. Hf of CO2 -394 kJ mol-1 Hf of H20 Hf of C8H18 -286 kJ mol-1 -250 kJ mol-1 [3 marks]

(iv) How is the knowledge of standard enthalpy of combustion useful to a chemist other than that of as fuel? [2 marks]

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7(a)

The table below gives the melting point for each of the Period 3 elements Na to Ar.

(i) Describe and explain the difference between the electrical conductivities of the elements aluminium, silicon and phosphorus. [4 marks] (ii) When aluminium combines with chlorine, it results in the formation of aluminium chloride. Aluminium chloride can further react with chloride ions as shown by the equation below. AlCl3 + Cl AlCl4 Explain how the bond between aluminium chloride and the chloride ion is formed. [3 marks]

(b) The table below shows the elements in group II of the periodic table. Element Beryllium Magnesium Calcium Strontium Barium (i) State and explain the differences in bonding between beryllium chloride and magnesium chloride. [3 marks] (ii) Sulphates of the Group II elements have different solubilities. State and explain the trend in solubilities. [2 marks ] (iii) A student on a field trip investigates some disused mining pools which have been flooded for some time. The presence of barium ions in the water is to be demonstrated by precipitating barium(II) sulphate. The solubility of barium(II) sulphate in water at 25oC is 1.05 x 10-5 mol dm-3. Calculate its solubility product and state one use that depends upon this insolubility. [3 marks]

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8 Ammonia is one of the best-known compounds. It is prepared industrially from nitrogen and hydrogen by the Haber process. The equation for the main reaction in the Haber process is N2(g) + 3H2(g) 2NH3(g) H = negative The table below gives information about the percentage yields of ammonia obtained in the Haber process under different conditions. Pressure/atm 10 100 200 300 400 600 Temperature/C 200 50.7 81.7 89.1 89.9 94.6 95.4 300 14.7 52.5 66.7 71.1 79.7 84.2 400 3.9 25.2 38.8 47.1 55.4 65.2 500 1.2 10.6 18.3 24.4 31.9 42.3

(a) (i) From the table, state the conditions that gives the higher yield of ammonia. [2 marks] (ii) State a suitable catalyst . [1 mark] (b) Ammonia can be oxidised by air to form nitrogen oxide. 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) H= -909kJmol-1

This reaction forms the first stage in the manufacture of nitric acid from ammonia. Using Le Chatelier s principle state and explain the change in equilibrium yield of nitrogen oxide caused by: (i) Increasing the pressure at constant temperature (ii) Increasing the temperature at constant pressure [3 marks] [3 marks]

(iii)The industrial process is operated at a temperature of about 900C. Suggest a reason for this temperature. [2 marks] (c) An aqueous solution of nickel(II) chloride reacts with aqueous ammonia to form a precipitate X. The precipitate X dissolves in excess aqueous ammonia to give a solution Y. State the colours of X and Y and also write the chemical formula of each. [4 marks]

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11

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9(a) An amount of 0.01 mole of a hydrocarbon is burnt in excess oxygen. The products of the combustion are passed through anhydrous calcium chloride and then through potassium hydroxide solution. The masses of anhydrous calcium chloride and potassium hydroxide solution increase by 0.72 g and 1.76 g respectively. (i) (ii) Determine the empirical formula of the hydrocarbon. [4 marks]

Determine the relative molecular mass of the hydrocarbon and hence its molecular formula. [4 marks]

(b)

Draw the structure of the major product of each of the following reactions. (i) Br
+ NH3

ethanol

[1 marks] [1 marks]

(ii) (CH3)2CBr2 + NaOH

(iii)

CHO

(i) CH3CH2MgBr (ii) H3O+

[1 marks]

(c)

The molecular structure of compounds T is given below. O CH3C CH2

=O

What are the organic products expected when T is reacted with each of the following reagents ? (i) H2 / Pt [1 marks] + (ii) LiAlH4 , followed by H3O [1 marks] (iii) I2 / NaOH [2 marks]

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12

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10(a) Natural rubber is cis-poly(2-methyl-1,3-butadiene). Physical properties are altered after vulcanisation process. (i) Draw a repeating unit for the above polymer. [1 mark]

(ii) What characteristic must be present in the molecule of the polymer so that the vulcanisation process can be carried out? [1 mark]
(iii)

State two changes in the physical properties of natural rubber after the vulcanisation. [2 marks]
(iv)

If an excess of the vulcanising agent is added during the vulcanisation process, what would be the change in the physical properties of the natural rubber ? [1 mark] (v) State the vulcanising agent and draw the structure of vulcanised rubber. [2 marks] (vi) Natural rubber is a type of elastomer. What would you understand by the term elastomer? [1 mark] (b) The possible mechanism for hydrolysis of 3-bromo-3-methylhexane by hydroxide ion, OH- is as follows: C3H7- C(Br)(CH3)-C2H5 + C3H7- C(CH3)-C2H5 + OHslow fast + C3H7- C(CH3)-C2H5 C3H7- C(OH)(CH3)-C2H5

(i) (ii)

Write the rate equation for the above mechanism.

[1 mark]

What will happen to the rate of reaction if OH- is replaced by CN- ? Explain your answer. [2 marks] Name the above mechanism. [1 mark]

(iii) (iv)

3-bromo-3-methylhexane shows stereoisomerism. Name the type of isomerism and draw all the structural formulae of this isomers. [3 marks]

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