Hess's law states that the total enthalpy change in the chemical reaction is independent

of the route by which the chemical reaction takes place as long as the initial and final

conditions are the same.

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(i) State the type of enthalpy changes represented by ∆H1, ∆H2, ∆H3 and ∆H4 in Figure
1.
Enthalpy of Atomization of K or Enthalpy of Sublimation for K.
∆H1 ........................................................................................................................
Enthalpy of Atomization of F or Bond Dissociation Energy for F.
∆H2 ........................................................................................................................
Enthalpy of First Ionization Energy of K.
∆H3 ........................................................................................................................
Enthalpy of Electron Affinity of F.
∆H4 ........................................................................................................................
[4 marks]

(ii) Calculate the lattice energy of potassium fluoride, given the following information:

∆H1 = +89.6 kJ mol–1 ∆H2 = +419.0 kJ mol–1

∆H3 = +79.1 kJ mol–1 ∆H4 = –332.6 kJ mol–1

^H6 = ^H1 + ^H2 + ^H3 + ^H4 + ^H5

^H6 is Enthalpy of Formation & ^H5 is the lattice energy

^H5 = ^H6 - (^H1 + ^H2 + ^H3 + ^H4)

= - 562.6 - (+ 89.6 + 419.0 + 79.1 + (- 332.6))

= - 817.7 KJ mol-1

[4 marks]

(iii) Comment on the nature of the bonding in potassium fluoride based on the theoretical
lattice energy value of –801.35 kJ mol–1, compared with the experimental value
obtained in (b) (ii).
There is close agreement between the theoretical lattice energy value and the
.................................................................................................................................
experimental value suggesting an ionic lattice with ionic bonding. There is ionic
.................................................................................................................................
bonding between potassium and fluorine due to the large difference in electronegativity
.................................................................................................................................
between the ions. This bonding results in an ionic lattice structure for potassium fluoride.
.................................................................................................................................
[2 marks]

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(c) A student is asked to write the steps to be followed in determining the enthalpy of
neutralization of 50 cm3 of 1.0 M hydrochloric acid and 50 cm3 of 1.0 M of potassium
hydroxide. Outline the experimental steps (including calculations) required in the
determination.

[Assume that the densities of the solutions of acid and base, and their heat capacities are
1 g cm–3 and 4.18 J g–1 °C–1 respectively.]
1. Using a pipette, exactly 50 cm3 of 1.0 M KOH is added to a Styrofoam cup.
..............................................................................................................................................
2. The temperature of the KOH solution in the cup is noted.
..............................................................................................................................................
3. Separately, the temperature of the HCl is noted.
..............................................................................................................................................
4. Using a burette, 5 cm3 aliquots of 1.0 M HCl is added to the Styrofoam cup.
..............................................................................................................................................
5. The mixture is stirred and the temperature is noted upon the addition of each 5 5cm3 aliquot until
..............................................................................................................................................
the 50 cm3 of acid is added.
..............................................................................................................................................
6. Using T1 a (KOH temp + HCl temp) / 2 and T2 as highest temperature recorded. T = T2 - T1
..............................................................................................................................................

7. Calculate the heat generated by using q = mc T where m = 100 g and c is 4.18 Jg-1 C-1. Note
..............................................................................................................................................
q will be -q since the reaction is exothermic.
..............................................................................................................................................
8. Find the number of moles of HCl or NaOH used since there is a 1 : 1 mole ratio of HCl : NaOH : H2O.
..............................................................................................................................................
No. of moles of HCl = (vol x conc) / 1000 = (50 x 1) / 1000 = 0.05 mols
..............................................................................................................................................

9. ^H neutralization (KJ / mol) = -q / 0.05

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................
[4 marks]

Total 15 marks

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MODULE 2: KINETICS AND EQUILIBRIA

2. (a) State TWO factors which affect the rate of a reaction.

Surface area, Concentration of reagents, Temperature of reactants,
..............................................................................................................................................
Catalysts, Light.
..............................................................................................................................................
[2 marks]

(b) The data in Table 1 were obtained for the reaction between hydrogen and nitrogen oxide
at 800 °C.

2H2(g) + 2NO(g) → 2H2O(g) + N2(g)

TABLE 1: DATA FOR THE REACTION BETWEEN HYDROGEN AND NITROGEN OXIDE

Initial Concentration of Initial Rate of

Experiment Initial Concentration
Nitrogen Oxide/ Production of Nitrogen/
Number of Hydrogen/mol dm–3
mol dm–3 mol dm–3 s–1
1 1 × 10–3 6 × 10–3 3 × 10–3
2 2 × 10–3 6 × 10–3 6 × 10–3
3 3 × 10–3 6 × 10–3 9 × 10–3
4 6 × 10–3 1 × 10–3 0.5 × 10–3
5 6 × 10–3 2 × 10–3 2.0 × 10–3
6 6 × 10–3 3 × 10–3 4.5 × 10–3

(i) Define the ‘reaction rate’ in terms of the production of nitrogen.

Change in concentration of Nitrogen per unit time.
.................................................................................................................................
Rate = [N2 (g)] / t
.................................................................................................................................

.................................................................................................................................
[2 marks]

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(ii) From the data, determine the order of the reaction with respect to

hydrogen

Rate changes by the same factor as concentration: 1st order

[1 mark]

nitrogen oxide.

Rate changes by the square of the factor that the concetration

is changing: 2nd order

[1 mark]

(iii) Write the rate law for the reaction.

Rate = k [H2] [NO]^2
.................................................................................................................................

.................................................................................................................................
[1 mark]

(iv) Calculate the value of the rate constant, k, stating the appropriate units.

Substituting using values experiment 1 (any experiment can be used):

Rate = k [H2] [NO]^2

3 x10^-3 = k (1 x 10^-3)(6 x10^-3)^2

k = 8.33 x10^-4 mol-2 dm6 s-1

[3 marks]

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(c) (i) Suggest another experimental technique which would be suitable to investigate
the rate of reaction between hydrogen and nitrogen oxide.
Since the reacting system involves gases, you can measure the pressure of the system
.................................................................................................................................
at regular time intervals.
.................................................................................................................................
[1 mark]

(ii) The investigation of the effect of concentration on the rate of reaction between
aqueous bromine and methanoic acid (in large excess) is catalysed by acid. Outline
the experimental steps required.

Br2(aq) + HCOOH(aq) → 2Br–(aq) + 2H+(aq) + CO2(g)

> Carbon dioxide gas is produced.
.................................................................................................................................
> The volume of Carbon dioxide is measured at time intervals.
.................................................................................................................................
> The volume of CO2 is plotted against time.
.................................................................................................................................
> The tangent is drawn to the curve to determine reaction rate.
.................................................................................................................................
> The reaction rate is plotted against volume of CO2.
.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................
[4 marks]

Total 15 marks

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MODULE 3: CHEMISTRY OF THE ELEMENTS

3. Table 2 provides data on two properties of the oxides of some Group IV elements.

(a) Complete Table 2 by describing the thermal stability of the oxides. [4 marks]

TABLE 2: TWO PROPERTIES OF THE OXIDES OF SOME GROUP IV ELEMENTS

Group IV Element Group IV Element

+2 Oxidation State +4 Oxidation State
Property
CO SiO PbO CO2 SiO2 PbO2

Thermal Readily Readily Stable Stable even Stable Changes to

stability oxidized to oxidized to at high PbO on
Carbon dioxide temperatures warming.
dioxide
(+2 oxidation
state more
stable than
+4 state).

Melting point –56 1610 290

of XO2 or
dioxide/°C

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(b) Account for the type of structure and bonding of the oxides of the elements C, Si and Pb
in the +4 oxidation state described in Table 2. Use the melting point data provided in the
table to aid your response.
CO2 has a simple covalent molecular structure. The molecules are held together by
..............................................................................................................................................
weak Van der Waals Forces so that CO2 is a gas at room temperature so not much
..............................................................................................................................................
energy is required to break the bonds hence it has the lowest melting point.
..............................................................................................................................................

..............................................................................................................................................
SiO has a macromolecular structure in its solid state hence highest melting point.
..............................................................................................................................................

..............................................................................................................................................
PbO2 has a giant covalent structure with some degree of ionic character.
..............................................................................................................................................

..............................................................................................................................................
[3 marks]

(c) Explain the relative stabilities of the oxides of the Group IV elements carbon, silicon and
lead, of oxidation states +2 and +4.
The stability of the +4 state increases as we move from PbO2 to CO2. CO2 posses
..............................................................................................................................................
the lowest oxidizing power. Bonding in PbO is ionic and PbO is more stable due to the
..............................................................................................................................................
inert pair effect (unreactive s electrons) which is not present in carbon in CO. The
..............................................................................................................................................
stability of the +2 state decreases on moving from PbO to CO.
..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................
[4 marks]

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(d) Describe the expected observations when

(i) concentrated hydrochloric acid is added to solid lead(IV) oxide

Solid dissolves. A white ppt is produced. Yellow-green gas evolved.
.................................................................................................................................

.................................................................................................................................

.................................................................................................................................
[2 marks]

(ii) concentrated sodium hydroxide solution is added to solid lead(IV) oxide

Solid dissolves. Colourless Solution forms.
.................................................................................................................................

.................................................................................................................................

.................................................................................................................................
[1 mark]

(iii) an aqueous solution of Fe2+ ions is added to solid lead(IV) oxide.

.................................................................................................................................
Pale green solution changes to a pale-yellow solution or reddish-brown solution.

.................................................................................................................................

.................................................................................................................................
[1 mark]

Total 15 marks

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SECTION B

Answer ALL questions.

MODULE 1: FUNDAMENTALS IN CHEMISTRY

4. (a) State FOUR basic assumptions of the kinetic theory, with reference to an ideal gas.
> Particles are in a constant random motion.
..............................................................................................................................................
> Volume of the particles are negligible compared to the volume of the gas.
..............................................................................................................................................
> There exist no intermolecular forces of attraction.
..............................................................................................................................................
> Collisions between particles are perfectly elastic. (no loss of energy)
..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................
[4 marks]

(b) (i) Real gases deviate from ideal gas behaviour under certain conditions of temperature
and pressure. Outline TWO assumptions of the kinetic theory of gases which DO
NOT hold under these conditions of temperature and pressure.
Real gases deviated from ideal behaviour at high pressures and low temperatures.
.................................................................................................................................
Under these conditions there now exist intermolecular forces of attraction since particles
.................................................................................................................................
are closer together and the volume of the particles are no longer negligible when
.................................................................................................................................
compared to the overall volume of the gas.
.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................
[3 marks]

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(ii) Sketch a graph of PV against P to illustrate the deviation of ONE real gas from
ideal gas behaviour.

CO CH4
H2

He

Ideal gas

pV

p [3 marks]

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(c) (i) Describe the nature of the liquid state in terms of the motion and arrangement of
particles.
Particles in the liquid state move less randomly than those in a gaseous state and are
.................................................................................................................................
arranged closer together in clusters where they can slip and slide over each other.
.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................
[2 marks]

(ii) A gas syringe contains 18.4 cm3 of air at 57 °C. When 0.187 g of a volatile liquid
is injected into the syringe, the volume of gas in the syringe increases to 54.6 cm3
at 57 °C and 1.01 × 105 Pa. Calculate the molar mass of the liquid.

p = 1.10 x 10^5 Pa

V = (54.6 - 18.4) = 36.2 cm3 = 36.2 x 10-6 m3

n = mass / molar mass

R = 8.31 JK-1mol-1

T = (57 + 273) = 330 K

m = 0.187

pv = nRT

pv = (mass / molar mass) RT

molar mass = (mass / pv) RT

(0.187 g / (1.01 x 10^5 Pa)(36.2 x 10-6 m3)) x 8.31 x 330 [3 marks]

Molar mass = 140.26 g/mol Total 15 marks

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MODULE 2: KINETICS AND EQUILIBRIA

5. (a) (i) Define the term ‘standard electrode potential of a half-cell’.

The potential of that half cell relative a standard hydrogen electrode under
.................................................................................................................................
standard conditions.
.................................................................................................................................

.................................................................................................................................
[2 marks]

(ii) Draw a labelled diagram to illustrate how the standard electrode potential of the
Fe3+(aq)/Fe2+(aq) half-cell can be measured.

H2 (g)
1 atm
Salt bridge

Pt
298 K
Pt

H+ (aq)
Fe3+ (aq) 1 mol dm-3
1 mol dm-3
Fe2+ (aq) 1 mol dm-3

Fe2+ / Fe3+ (aq) 1 mol dm-3

[4 marks]

(iii) State TWO uses of standard electrode potentials.

> Predict the feasibility of the reaction.
.................................................................................................................................
> Determine the direction of electron flow in a cell.
.................................................................................................................................
> Calculate standard cell potential. [2 marks]
> Indicate the oxidizing / reducing ability of species.

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(b) Consider the cell represented below.

Cu(s) | Cu2+(aq) || Ag+(aq) | Ag(s)

(i) Write the equation for the reaction between copper and silver ions.
Cu (s) + 2Ag+ (aq) => Cu2+ (aq) + 2 Ag (s)
.................................................................................................................................
[1 mark]

(ii) Calculate the standard cell potential.

Cu (s) => Cu2+ (aq) + 2e - 0.34 V E cell = E RHS - E LHS

2 Ag+ (aq) + 2e => 2Ag (s) + 0.80 v = E cathode - E anode

OR
= 0.80 V - 0.34 V

Cu (s) + 2Ag+ (aq) => Cu2+ (aq) + 2 Ag (s) E = + 0.46 V

[2 marks]

(iii) Assess the feasibility of the reaction.

The positive electrode potential value of emf value indicates that the
.................................................................................................................................
reaction is feasible.
.................................................................................................................................

.................................................................................................................................
[2 marks]

(iv) Assess the effect of an increase in the concentration of silver ions on the standard
cell potential.
If the concentration [Ag+] increase, according to Le Chatelier's Principle,
.................................................................................................................................
the equilibrium will shift to the right and the cell potential will become more positive.
.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................
[2 marks]

Total 15 marks
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MODULE 3: CHEMISTRY OF THE ELEMENTS

6. Table 3 provides information on the properties of halogens.

TABLE 3: PROPERTIES OF SOME HALOGENS

Property Fluorine Chlorine Bromine Iodine

State at 20 °C Gas Gas Liquid Solid

Colour Pale yellow Pale green Red brown Black

Melting point/°C –220 –101 –7 113

Bond energy of the hydrides/

562 431 366 299
kJ per mol of bonds

EӨ/V Hal2/2Hal–(aq)/Pt +2.87 +1.36 +1.07 +0.54

(a) Explain the trend in volatility of the halogens down the group.
As the group is descended volatility decreases. This is as a result of an increase in Van der
..............................................................................................................................................
Waal forces or interactions between molecules as the atomic and molecular masses of the
..............................................................................................................................................
elements increase.
..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................
[2 marks]

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(b) Use the EӨ values and the sodium thiosulfate reagent to explain the relative reactivities of
the halogens as oxidizing agents. [Equations are not required.]

E values decrease as the group is descended i.e. values becomes less positive on
..............................................................................................................................................
moving down the group which means that the oxidizing ability of the element decreases.
..............................................................................................................................................
Based on the values; F, Cl and Br are strong oxidizing agents and can oxidize the
..............................................................................................................................................
thiosulphate ion to the sulphate ion while iodine can only oxidize the thiosulphate ion to
..............................................................................................................................................
the tetrathionate ion.
..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................

..............................................................................................................................................
[4 marks]

(c) (i) Describe the reactions of the halogens with hydrogen.

F: explosive reaction with hydrogen in the dark.
.................................................................................................................................
Cl: Slow reaction with hydrogen in the dark. Explosive when exposed to heat or flame.
.................................................................................................................................
Br: Mildly explosive when exposed to a flame. Reacts with hydrogen when heated in
.................................................................................................................................
the presence of a Pt catalyst.
.................................................................................................................................
I: reacts slowly and partially with hydrogen even if heated.
.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................

.................................................................................................................................
[4 marks]

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(ii) Explain the trend in the relative stabilities of the hydrides.
Thermal stability of hydrides decreases down the group:
.................................................................................................................................
HF > HCl > HBr > HI. HF is the most stable and HI is the least stable hydride.
.................................................................................................................................
The H-X (Hydrogen - halogen) bond length increases down the group.
.................................................................................................................................
Since longer bonds are weaker bonds and shorter bonds are stronger bonds, the H-X strength decreases down
.................................................................................................................................
the group. F forms the most polar bonds with H due to the high difference in electronegativity. This results in strong
.................................................................................................................................
intermolecular hydrogen bonding between HF molecules. The reactivity therefore of Cl, Br and I decreases with H
.................................................................................................................................
and the covalent bond strength in the halogen hydrides decreases down group.
.................................................................................................................................
[3 marks]

(iii) Write a balanced equation for the reaction of ONE halogen with hydrogen.
H2 (g) + F2 (g) => 2HF (g)
.................................................................................................................................
[2 marks]

Total 15 marks

END OF TEST

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