This paper consists of sections A, B and C.

- Answer five (5) questions including at least one question from each the section A, B and C.

- In your calculation you may use the following constant.s

C = 12, H = 1, O = 16, Cl = 35.5, P = 31, N= 14, Zn =65, Cu =64, S =32

h = 6.626 10-34J.S, RH = 1.0967  107

/m c = 3.0  108m/s R = 0.0821L atm/molK, R

=8.314J/molK, Kf of water = 1.86 o

c/m Kb of water = 0.510C/m

SECTION A

1. (a) Define the following terms:

(i) Activation energy

(ii) Molecularity

(iii) Order of reaction

(iv) Mechanism of reaction [08 marks]

(b) Show that the mechanism:

I2 K1

2 I (fast)

K-1

I + H2 K2 H2I (fast)

K-2

H2I + I K3 2HI (slow) [04marks]

Leads to the result that the rate equation for the overall reaction is r = k[H2

][I

].

(c) The initial rates of the reaction 2A + B  2C + D at various concentrations of A and B

are given below:

[A] moldm-3

[B] moldm-3

Initial rate /moldm-3

-1

0.01 0.20 0.10

0.02 0.20 0.20

0.01 0.40 0.40

(i) What is the order of reaction with respect to A and B?

(ii) What is the overall order of reaction?

(iii) What is the rate constant?

(iv) What will be the rate of the reaction if the concentrations of A and B are both

0.01 moldm-3

? [08 marks]

2. (a) Explain briefly the following terms:

(i) Common ion effect

(ii) Salt hydrolysis

(iii)Buffer solution [06 marks]

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(b) How many grams of sodium acetate, NaC2H3O2, would have to be added to 1.0 L of 0.15

M acetic acid (pKa 4.74) to make the solution a buffer for pH 4.00? [06 marks]

(c) For the titration of 75.00 mL of 0.1000 M acetic acid with 0.1000 M NaOH, calculate the

pH

(i) before the addition of any NaOH solution,

(ii) after 25.00 mL of the base has been added,

(iii)after half of the HC2H3O2 has been neutralized, and

(iv)at the equivalence point. [08 marks]

3. (a) Define the following terms

(i) Redox reaction

(ii) Reducing agent

(iii) Oxidation [06 marks]

(b) Hair bleaching solutions contain hydrogen peroxide, H2O2. The amount of hydrogen

peroxide in the

solution can be determined by making H2O2 react with an acidic solution of potassium

dichromate.

The unbalanced equation for the reaction is H2O2(aq) + Cr2O7

2-
(aq) + H

(aq) → O2(g) +

Cr3+

(aq) + H2O

A 30.00g sample of the bleach solution needed 75.8 mL of 0.388 M K2Cr2O7 to react

completely with

the bleach. Assuming no other compounds that react with K2Cr2O7 are in the solution,

what is the

mass percent of H2O2 in the bleach? [07 marks]

(d) A 1.00g sample of a mixture of Na2Co3 (anhydrous) and NaHCO3 was dissolved in water.

With phenolphthalein as indicator, 17.05cm3

of 0.200M hydrochloric acid were

required to neutralize the solution. Calculate the percentage by mass composition of the

mixture.

[07 marks]

4. (a) Define the following terms:

(i) Cathode

(ii) standard reduction potential [04 marks]

(b) Describe the function of a salt bridge in an electro chemical cell. Explain what happen

when the salt bridge is removed from the system and why? [03 marks]
(c) What is the difference between electrochemical cell (such as Daniel cell) and electrolytic

cell? [03 marks]

(d) The magnitude (but not the signs) of the standard electrode potential of two metals x and

y are

X 2e X

2

  E 0.25V

Y 2e Y

2

  E 0.34V

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Where the notation denotes that only the magnitude (but not the sign) of the E0

values

is shown. When the half-cell of X and Y are connected, electrons flow from X to Y. When X

connected to standard hydrogen electrode (SHE), electrons flow from X to SHE.

(i) Are E0
values of the half-reactions positive or negative?

(ii) What is the standard emf of a cell made up of x and y. [05 marks]

(e) Calculate the potential in the following cell when 99.9% of the copper ions (Cu2+) have

been consumed. [05 marks]

Zn / Zn (1.00M)//Cu (1.00M)Cu.

2 2

Given

(s)

2 Zn  2e  Zn  

= -0.76V

(s)

2 Cu  2e  Cu  

= +0.34V.

SECTION B

5. (a) (i) The formation of the complex ion [Cu(H2O)6]

2+ is described as a Lewis acid–base

reaction. Explain.

(ii) What are the formulas of the Lewis acid and the Lewis base in this reaction?

(iii) What is the formula of the ligand?

(iv) What is the name of the species that provides the donor atom?

(v) What atom is the donor atom, and why is it so designated?

(vi) What is the name of the species that is the acceptor? [08 marks]

(b) Analysis of a coordination compound gives these results: 22.0% Co, 31.4% N, 6.78%

H, and 39.8% Cl. One mole of the compound dissociates in water to form 4 mol ions.

(i) Determine the formula of the compound.

(ii) Write the equation for its dissociation in water. [06 marks]

(c) Write the name corresponding to each of these formulas.

(i) [MnCl4]

2-

(ii) K3[Fe(C2O4)3]

(iii) [Pt(NH3)2(CN)2] (iv) [Fe(H2O)5(OH)]2+ [06 marks]

6. Iron is extracted from the oxide Fe2O3 by reduction with carbon and carbon monoxide

in a Blast Furnace.

(a) In the Blast Furnace, carbon monoxide is produced from carbon in a two-

stage process. Write equations to show these two stages.

(b) Write an equation for the reduction of Fe2O3 by carbon and an equation for

the reduction of Fe2O3 by carbon monoxide.

(c) Limestone is added to the Blast Furnace to remove impurities present in the

iron ore. Identify the main impurity removed by limestone. Write an

equation or equations to show how limestone acts to remove this impurity

(d) Indentify a gas which is released from the Blast Furnace which leads to

environmental problems. State the environmental problem.

(e) Identify another gas which leads to environmental problems when sulphide

ores are used in the extraction of metals other than iron. State the

environmental problem.

Page 25 of 30

[20 marks]

7. (a) (i) State the trend in electronegativity of the elements down Group VII.

Explain this trend.

(ii) State the trend in reducing ability of the halide ions down Group VII.

(iii) Give an example of a reagent which could be used to show that the

reducing ability of bromide ions is different from that of chloride

[06 marks]

(b) The addition of silver nitrate solution followed by dilute aqueous ammonia can

be used as a test to distinguish between chloride and bromide ions. For each
ion, state what you would observe if an aqueous solution containing the ion was

tested in this way.[4.5 marks]

(c) Write an equation for the reaction between chlorine gas and dilute aqueous

sodium hydroxide. Name the two chlorine-containing products of this reaction

and give the oxidation state of chlorine in each of these products. [4.5 marks]

(d) A mixture of two precipitates, P and Q, was formed by adding aqueous silver

nitrate to a solution containing two different halide ions. Precipitate P dissolved

on addition of an excess of dilute aqueous ammonia. The remaining precipitate,

Q, was filtered off.

(i) Identify the halide ion in P.

(ii) Precipitate Q was soluble in concentrated aqueous ammonia. Identify the

halide ion in Q. [05 marks]

SECTION C:

8 A substance A (C4H6O2) rapidly decolorized a solution of potassium permanganate in the cold.

On treatment trioxygen and hydrolysis of the products, A gave a neutral substance B (C2H4O)

and acidic substance C (C2H2O3), both of which give a silver mirrors with ammoniacal silver

solutions, and orange precipitates with 2,4-dinitrophenylhydrazine in aqueous methanol

(DNPH). B, on oxidation, gave an acid D, whose calcium salt, on heating, gave E, C3H6O,

which gave an orange precipitate with DNPH, but did not react with the ammoniacal silver

solution. Oxidation of C gave an acid F, which decolorized acidified potassium permanganate

on warming, and which, on heating with concentrated sulfuric acid gave off some gas. This

gas was passed through lime water, which turned cloudy, and the effluent gas was formed to

burn in air. Deduce the structures of A, B, C, D, E, and F, and outline the course of the above
reactions. [20 marks]

9. (a) Each of the following compound names represents an impossible structure. In each case,

explain why.

(i) Methanone (ii) 1-Chlorobutanal

(iii) 3-Methyl-3-pentanone (iv) Cyclohexanal [06 marks]

(b) Show how you would convert benzaldehyde into each of the following. You may use any

other needed reagents, and more than one step may be required.

(i) Benzyl alcohol (ii) Benzophenone

(iii) Benzoyl chloride (iv) 1-Phenylethanol [08 marks]

(c) Draw the structures formulae of the organic products that would result from treating

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(CH3)2CHCH2OH as follows:

(i) Warm with metallic sodium.

(ii) Heat under reflux with potassium dichromate (VI) in dilute sulphuric acid.

(iii) Heat under reflux with SOCl2.

(iv) Heat strongly with an excess of concentrated sulphuric acid. [08 marks]

10. (a) Assign an IUPAC name to each of the four isomeric amines that have the molecular

formula C3H9N. [06 marks]

(b) The repeating units of two polymers, P and Q, are shown below.

(i) Draw the structure of the monomer used to form polymer P. Name the type

of polymerisation involved.
(ii) Draw the structures of two compounds which react together to form

polymer Q. Name these two compounds and name the type of

polymerisation involved.

(iii) Identify a compound which, in aqueous solution, will break down polymer Q

but not polymer P. [08 marks]

(c) Propylamine, CH3CH2CH2NH2, can be formed either by nucleophilic substitution

or by reduction.

(i) Draw the structure of a compound which can undergo nucleophilic

substitution to form propylamine.

(ii) Draw the structure of the nitrile which can be reduced to form propylamine.

CH3