Revision STPM 1

PART B
CHEMISTRY
ESSAY QUESTIONS

1. (a) The equation below shows the reaction between ammonia and a hydrogen ion.
NH3 + H+  NH4+
In terms of the electrons involved, explain how the bond between NH3 molecule and
H+ ion is formed. Name the type of bond formed in the reaction.
(3 marks)

(b) Boiling point data of three hydrides are given as below.

Hydrides Relative molecular mass Boiling point (oC)
Methane 16 -182
Ammonia 17 -33
Water 18 100
Explain why these three hydrides have very different boiling points.
(4 marks)

(c) (i) A reaction of nitrogen monoxide is shown below.

2NO(g) + O2(g)  2NO2(g)
The rate of reaction can be found by measuring the concentration of NO2 at
different times. Define the term rate of reaction. Sketch a graph to show how the
concentration of NO2 changes with time. Indicate how the initial rate of reaction
can be obtained from the graph.
(4 marks)

(ii) In the manufacture of sulphur trioxide from sulphur dioxide, nitrogen monoxide
can be used in a two-stage process to increase the rate of reaction.
2NO(g) + O2(g)  2NO2(g)
NO2(g) + SO2(g)  NO(g) + SO3(g)
Construct an overall equation for the production of sulphur trioxide from sulphur
dioxide. State the fully explain the role of NO in this process.
(4 marks)

2. (a) (i) Using a solution of ammonium chloride and ammonia as example, explain what is
meant by a buffer solution.
(5 marks)
(ii) Calculate the mass of ammonium chloride that needs to be added to 450 cm3 of
0.10 mol dm-3 ammonia to produce a solution with pH 9.0
(Kb of ammonia = 1.7 x 10-5 mol dm-3)
(4 marks)

(b) The pKa values of four carboxylic acids are shown below.
Acid Formula pKa
1 CH3CH2COOH 4.9
2 CH3CHClCO2H 2.8
3 CH3CCl2COOH 1.4
4 CH2ClCH2COOH 4.1
(i) Describe and explain the trend in acidic strength shown by acids 1, 2 and 3.
(ii) Give an explanation for the difference in pKa values for acids 2 and 4.
(iii) Calculate the pH of a 0.010 mol dm-3 solution of acid 1.
(6 marks)
3. (a) The major buffer system that is used to control the pH of blood consists of carbonic
acid, H2CO3 and sodium hydrogen carbonate, NaHCO3. Explain how the system
works in controlling blood pH.
(4 marks)

(b) 20.0 cm3 of 0.20 mol dm-3 aqueous ammonia was titrated with 0.16 mol dm-3
aqueous HCl. Sketch a graph of pH against volume of HCl(aq) added during the
titration process. Mark and explain the position of the equivalent point.
(4 marks)

(c) The activation energy, Ea of a reaction can be calculated using the Arrhenius
equation

where k = rate constant, R = gas constant, T = temperature and A = frequency factor.

Rate constant for the decomposition of acetonedicarboxylic acid are k = 4.75 x 10-4 s-
1
at 293 K and k = 1.63 x 10-3 s-1 at 303 K.
CO(CH2COOH)2 (aq)  CO(CH3)2 (aq) + 2CO2(g)

(i) Calculate the activation energy for this reaction.

(4 marks)
(ii) Write the rate equation for the reaction.
(1 mark)
(iii) What is the time taken for the concentration of CO(CH2COOH)2 to change from
2.00 mol dm-3 to 1.00 mol dm-3 at 303 K?
(2 marks)

4. (a) Hydrogen sulphide is a hydride of sulphur. The bonding in a hydrogen sulphide

molecule is a result of the overlapping of orbitals of the sulphur and hydrogen atoms.
(i) Define orbital
(ii) Draw labelled diagrams to show the shapes of all the orbitals with quantum
number n = 2 of a sulphur atom.
(iii) Draw a labelled diagram to show the overlapping of orbitals in the hydrogen
sulphide molecule.
(iv) State the shape of hydrogen sulphide molecule.
(6 marks)

(b) In acid solution, bromide ions are slowly oxidised to bromine by bromate(V) ions as
represented by the following ionic equation:
BrO3- + 6H+ + 5Br-  3Br2 + 3H2O
The following table shows the results of four experiments carried out at constant
temperature.
Experiment [BrO3-] / [Br-] / [H+] / Initial rate of
-3 -3 -3
mol dm mol dm mol dm reaction /
mol dm-3 s-1
1 0.400 0.280 0.031 1.29 x 10-3
2 0.600 0.280 0.031 1.94 x 10-3
3 0.600 0.560 0.031 3.87 x 10-3
4 0.400 0.280 0.062 5.16 x 10-3
(i) Write the two half equations for the above reaction
(ii) Determine the order of the reaction with respect to BrO3-, Br- and H+ ions
 (iii) Write the rate equation for the reaction
(iv) Find the value of the rate constant in experiment 4
(9 marks)

5. (a) State the Dalton’s law of partial pressure.

(2 marks)
3
(b) A 3.0 dm vessel contains 4.0 mole F2, 5.0 mole Cl2 and 3.0 mole O2 at 273 K.
(i) Calculate the initial partial pressures of each gas in the vessel in atm.
(ii) Then, 4.0 mole of neon gas is added into the vessel at constant pressure and
temperature. Calculate the new partial pressure of O2.
(R = 0.082 dm3 atm mol-1 K-1)
(5 marks)
(c) (i) Using the gas laws, derive the ideal gas equation.
(ii) State two important assumptions made in deriving the ideal gas equation.
(iii) For each example, give the reason of a gas that:
- behaves as an ideal gas
- deviates greatly from ideal gas
(8 marks)

6. (a) Write an equation for the dissociation of ethanoic acid in aqueous solution.
(1 mark)
(b) The dissociation constant, Ka for ethanoic acid is 1.8 x 10-5 mol dm-3 at 25oC.
(i) Calculate the pH of 0.10 mol dm-3 ethanoic acid.
(ii) Calculate the pH of a solution which contains both ethanoic acid and sodium
ethanoate in equal concentrations.
(5 marks)
(c) A solution which contains only sodium ethanoate in 0.050 mol dm-3 concentration
has a pH of about 9.
(i) Write an equation involving the ethanoate ion which explains why the pH of the
solution is above 7.
(ii) Write an equation for the base dissociation constant, Kb for ethanoate ions.
(iii) Calculate the value of Kb for ethanoate ions using the value of Ka in (b) and the
ionic product of water, Kw = [H+][OH-] given in the data booklet.
(iv) Use the value of Kb to calculate accurately the pH of 0.050 mol dm-3 sodium
ethanoate.
(7 marks)
(d) Use the pH values in (b)(i), (ii) and (c)(iv) to sketch the pH changes which occur when
20 cm3 of 0.10 mol dm-3 sodium hydroxide is gradually added to 20 cm3 of 0.10 mol
dm-3 ethanoic acid.
(2 marks)

7. (a) (i) Using the same axes, sketch the Maxwell-Boltzmann distribution curve for a
sample of gas at 25oC and 50oC.
(2 marks)
(ii) Use your sketched graph to explain the effect of temperature on the rate of
reaction.
(2 marks)
 (b) 3.00 g of antimony pentachloride is vapourised. The vapour occupies a volume of
285 cm3 at standard temperature and pressure.
(i) Calculate the relative molecular mass of antimony pentachloride in the vapour
state.
(3 marks)
(ii) Calculate the relative molecular mass of antimony pentachloride from its
molecular formula. Explain the difference between this value and the value
obtained in (b)(i).
(5 marks)
(iii) Draw the Lewis structure and state the shape of antimony pentachloride
molecule.
(2 marks)
(iv) Antimony pentaiodide does not exist. Explain why.
(1 mark)

8. (a) The following are all equilibrium processes. In each case, write a chemical equation
to show the equilibrium and use the Le Chatelier’s principle to explain the
observations described.
(i) When potassium nitrate dissolves in water, the temperature drops. If a saturated
solution of potassium nitrate at 100oC is cooled down to room temperature, a
crystals are formed.
(ii) When a small volume of concentrated solution of sodium sulphate is added to a
saturated solution of calcium sulphate, a white precipitate is formed.
(iii) When brown NO2 gas is cooled, colourless N2O4 gas is formed. A gas syringe is
filled with NO2 and the end sealed. When the gas is compressed, the brown
colour fades. Warming the syringe restores the colour.
(8 marks)
(b) The following reaction is used industrially to produce a combustible gas from coal.
H2O(g) + C(s) ↔ H2(g) + CO(g)
A mixture of powdered coal and steam at a pressure of 1 atm and a temperature of
1300oC was allowed to reach equilibrium. It was found that the total pressure had
increased to 1.9 atm but the remaining steam had a partial pressure of only 0.1 atm.
Use the data given to calculate the partial pressures of hydrogen and carbon
monoxide and hence calculate the value of Kp.
(3 marks)
(c) Hydrangeas are flowering plants which commonly have pink flowers. They produce
blue flowers in soils which contain high concentration of Mg2+(aq). The pH of well
limed soil is 9.0, whereas the pH of peat-based soil is 6.5. The numerical value of the
solubility product, Ksp of magnesium hydroxide is 1.8 x 10-12
Deduce and explain which of these types of soil favours good cultivation of blue
hydrangeas.
(4 marks)
9. (a) Krypton is used to fill fluorescent lights and photographic flash lamps.
(i) Use the following data to sketch a phase diagram for krypton.
Pressure/ atm Temperature/ oC
Triple point 0.175 -169
Critical point 54 -63
Melting point 1 -156.6
Boiling point 1 -152.3
(4 marks)
(ii) What is meant by the term triple point?
(1 mark)
(iii) What are the physical state of krypton under P = 5.3 atm, T = -153oC and P = 65
atm and T = 250oC?
(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 78.5 C and 100oC
o

respectively. A solution of water and ethanol forms an azeotropic mixture with a

boiling point of 78.2oC. 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.

(i) This mixture does not obey Raoult’s 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)

10. (a) X, Y and Z represent elements with proton number 9, 19 and 34. Predict the type of
bonding and draw the dot-cross diagrams for the compounds formed between
(i) X and Y
(ii) X and Z
(6 marks)
(b) Predict, giving reasons the relative
(i) volatility
(ii) electrical conductivity
of the compound formed between X and Y compared with that formed between X
and Z.
(4 marks)
(c) (i) Define the term activation energy.
(ii) The endothermic reaction between substances P and Q can be represented by
the following equation:
P(g) + Q(g)  R(g) + S(g)
Draw the energy profile for this reaction.
 Indicate and label clearly the activation energy and the enthalpy change for the
reaction.
(iii) Explain how a catalyst affects the rate of a chemical reaction.
(5 marks)

11. The table below shows the variation of pV against p for 65.0 g of gas M at 298 K.
p (x103)/ kPa 0.20 0.40 0.60 0.80 1.00
pV/ kPa m3 6.82 6.81 6.80 6.79 6.78

(a) (i) Plot a graph of pV against p.

(ii) Add to your graph the line expected if gas M is an ideal gas.
(iii) Comment on the shape of your graph.
(iv) Use the data in the graph to calculate the relative molecular mass of M.
(8 marks)
(b) Sketch the phase diagram of carbon dioxide. Label the areas and explain why solid
carbon dioxide can sublime under room conditions.
(4 marks)
(c) (i) Write an expression for the ionic product, Kw of water.
(ii) Use the expression above to determine the pH value of 0.200 mol dm-3 sodium
hydroxide.
(3 marks)

12. (a) Carbonic acid, H2CO3 is formed when carbon dioxide dissolves in water. It is a weak
acid with the following dissociation constants:
K1 = 4.5 x 10-7 mol dm-3
K2 = 5.6 x 10-11 mol dm-3

(i) Write expressions for K1 and K2 and the acid dissociation constant, Ka for carbonic
acid.
(3 marks)
(ii) By using the expression for K1, calculate the pH of carbonic acid.
(2 marks)
(iii) 20.0 cm of 0.100 mol dm carbonic acid is added to 15.0 cm of 0.100 mol dm-3
3 -3 3

sodium hydroxide solution. State and explain one important application of the
solution formed.
(2 marks)
(b) Hydrogen bromide (boiling point -67oC) and water form an azeotropic mixture with a
boiling point of 126oC. The azeotrope contains 47% by mass of hydrogen bromide.
(i) Explain the term azeotrope.
(1 mark)
(ii) Sketch a fully labelled boiling point-composition diagram for the mixture of
hydrogen bromide-water.
(2 marks)
(iii) A mixture containing 60% by mass of hydrogen bromide is subjected to
fractional distillation. What is the composition of the first and second distillates?
(2 marks)
(iv) What kind of deviation from ideality is shown by such a mixture? Describe the
different kinds of forces that exist before and after mixing.
(3 marks)
13. (a) The boiling points of three fluorides are shown below.
Fluoride Boiling point/ oC
SiF4 -86
PF5 -75
SF6 -64
(i) Explain in terms of structure and bonding why these compounds are all gases at
room conditions.
(2 marks)
(ii) Draw diagrams to show the shapes and bond angles of each of the above
compounds.
(3 marks)
(iii) Both oxygen and sulphur are in the same group in the Periodic table. Explain why
compound OF6 does not exist.
(1 mark)
(iv) Xenon reacts with fluorine to form a compound XeF4. State whether the Xe-F
bond is polar or non-polar and hence explain the polarity of XeF4 molecule.
(3 marks)

(b) Carbon monoxide, CO, nitrogen monoxide, NO and oxygen react together to form
nitrogen dioxide, NO2 as one of the products. Several experiments were carried out
to determine the rate equation for the reaction. The results are shown in the table
below.
Exp [CO(g)] / [NO(g)] / [O2(g)] / Initial rate of
mol dm-3 mol dm-3 mol dm-3 reaction /
mol dm-3 s-1
1 1.00 x 10-3 1.00 x 10-3 1.00 x 10-1 4.40 x 10-4
-3 -3 -1
2 2.00 x 10 1.00 x 10 1.00 x 10 4.40 x 10-4
3 2.00 x 10-3 3.00 x 10-3 1.00 x 10-1 3.96 x 10-3
-3 -3 -1
4 5.00 x 10 1.00 x 10 3.00 x 10 1.32 x 10-3

(i) Write an equation for the reaction between CO, NO and O2.
(1 mark)
(ii) Determine the order of the reaction with respect to each of the reactants and
hence the rate equation.
(4 marks)
(iii) Determine the rate constant for the reaction.
(2 marks)

14. (a) Define

(i) pH
(ii) buffer solution
(2 marks)

(b) Calculate the pH of

(i) 0.100 mol dm-3 aqueous ethanoic acid
(ii) a buffer solution formed by dissolving 16.4 g of sodium ethanoate in 750 cm3 of
water and then adding to 250 cm3 of 0.100 mol dm-3 ethanoic acid.
(Ka for ethanoic acid = 1.75 x 10-5 mol dm-3)
(6 marks)
 (c) 0.500 g of solid aluminium chloride is heated to 200oC at a pressure of 1.00 x 105 Pa.
The volume of vapour formed at this temperature and pressure was found to be
73.6 cm3. Calculate the relative molecular mass of the vapour at this temperature
and pressure. Draw a displayed formula to show the types of bonding in the
molecules of the vapour.
(4 marks)
(d) Explain with the help of equations why an aqueous solution of aluminium sulphate
has a pH of 4.8.
(3 marks)

15. (a) State the Le Chatelier’s principle.

(2 marks)

(b) Equilibrium I:
H2O(g) + C(s) ↔ H2(g) + CO(g) ΔH = +131 kJ mol-1
Equilibrium II:
2CrO4-(aq) + 2H+(aq) ↔ Cr2O72-(aq) + H2O(l)

Use the Le Chatelier’s principle to predict and explain the effect of

(i) increasing pressure in equilibrium I
(ii) increasing the temperature in equilibrium I
(iii) increasing concentration of H+ ions in equilibrium II
(6 marks)

(c) The Contact process is important in producing sulphuric acid.

2SO2(g) + O2(g) ↔ 2SO3(g) ΔH = -197 kJ mol-1

When sulphur dioxide and oxygen in the ratio of 2: 1 at an initial total pressure of 3
atm are passed over catalyst at 430oC, the partial pressure of sulphur trioxide is 1.9
atm.
(i) Calculate the partial pressure of SO2 and O2 at equilibrium, the total pressure at
equilibrium and the percentage of SO2 that is converted into SO3.
(ii) Write an expression for the equilibrium constant, Kp and calculate its value.
(7 marks)

16. (a) When 0.269 g of dibase (diprotic) organic acid A is vapourised at 120oC into a 10.0
dm3 vessel, the pressure measured is 1.00 x 103 Pa. Calculate the relative molecular
mass, Mr for acid A. Predict with reasons whether acid A is likely to behave ideally in
the conditions given above.
(5 marks)
(b) The mass spectrum of acid A consists of peaks at m/e values 17, 28, 45, 46, 56 and a
maximum value of 90. Identify acid A and the species which give rise to these peaks.
(4 marks)
(c) Explain the following observations in terms of structure and bonding.
(i) Trimethylamine, (CH3)3N has a lower boiling point than dimethylamine, (CH3)2NH
(ii) The relative molecular mass of methanoic acid, HCOOH as determined in an
aqueous solvent (water) is 46 but is doubled when is determined in a non-
aqueous solvent (benzene).
(6 marks)
17. (a) Hunds rule and Aufbau principle are two fundamental principles used in electronic
configuration of element.
(i) Hunds rule states that in a set of degenerate orbitals, the orbitals are each filled
with one electron with parallel spins before pairing occurs. State the meaning of
degenerate orbitals and give example of a set of degenerate orbitals.
(ii) Using Aufbau principle, explain how the valence electron configuration of
nitrogen is written.
(6 marks)

(b) Give the electronic configuration of iron in the oxidation states of +2 and +3. Hence,
explain why iron(III) compounds are more stable than iron(II) compounds.
(4 marks)

(c) Explain the overlapping of orbitals in ammonia molecule.

(5 marks)

18. (a) What do you understand by the term dynamic equilibrium?

(2 marks)

(b) In an experiment, 0.100 mole of dinitrogen tetraoxide is allowed to dissociate into

nitrogen dioxide in a 1.00 dm3 container at 383 K. The graph of concentrations of
both gases against time is shown below.

(i) Calculate the equilibrium constant, Kc for the above reaction at 383 K.
(ii) Calculate the pressure in the container after the system had achieved equilibrium
at 383 K.
(8 marks)
(c) The graph below shows the percentage of ammonia gas in an equilibrium mixture
for the system N2(g) + 3H2(g) ↔ 2NH3(g) at various temperatures and pressures.

Explain the conclusions that can be obtained from the graph above.
(5 marks)
19. (a) The reaction 2NO(g) + Cl2(g) ↔ 2NOCl(g) was studied at -10oC. The following data
were obtained.
Experiment Initial concentration Initial concentration Initial rate of
[NO]/ mol dm-3 [Cl2] / mol dm-3 formation of NOCl/
mol dm-3 min-1
1 0.10 0.10 0.18
2 0.10 0.20 0.35
3 0.20 0.20 0.45

What is the order of the reaction with respect to NO and Cl2 and what is the value of
the rate constant? State clearly the unit of the rate constant.
(4 marks)
(b) Sucrose decomposes in acid solution into glucose and fructose according to a first
order rate law, with a half-life of 3.33 hours at 25oC. What fraction of a sample of
sucrose remains after 9 hours?
(3 marks)
(c) The values of Ksp for the slightly soluble salts MX and QX2 are each equal to 4.0 x 10-
18
. Which salt is more soluble? Explain your answer.
(5 marks)

20. (a) Sketch the graphs of

(i) p against V
(ii) p against 1/V
(iii) pV against p
(iv) pV against V
for a constant number of moles of an ideal gas at a constant temperature.
(4 marks)
(b) Plot on separate sketched graphs
(i) V against T (oC)
(ii) V against T (K)
for a constant number of moles of an ideal gas at constant pressure.
(2 marks)
(c) 0.50 g of volatile liquid was introduced into a globe of 1000 cm3 capacity. The globe
was heated to 91oC so that all the liquid vaporised. Under these conditions the
vapour pressure exerted a pressure of 0.25 atm. What is the relative molecular mass
of the liquid?
(R = 8.31 or 0.0821)
(3 marks)
(d) A balloon can hold 1000 cm of air before bursting. The balloon contains 975 cm3 of
3

air at 5oC. Will it burst if it is taken into a house at 29oC? Assume the pressure of the
gas in the balloon remains constant.
(3 marks)
(e) Knowing that the density of ice is less than that of water, explain why the slope of
the solid-liquid equilibrium line in the phase diagram of water is accord with Le
Chatelier’s principle.
(3 marks)
21. Interpret each of the following observations as fully as you can.
(a) The first ionisation energy of nitrogen is higher than that of either of the elements
immediately preceding or following it in the Periodic table.
(3 marks)
o
(b) The boiling point of ammonia, NH3 (-33 C) is higher than that of phosphine, PH3 (-
87oC)
(3 marks)
(c) The bond energy in the nitrogen-nitrogen bond in the nitrogen molecule is 944 kJ
mol-1 whereas the bond energy of the carbon-oxygen bond in carbon monoxide,
which is isoelectronic with nitrogen is 1074 kJ mol-1.
(3 marks)
(d) The equilibrium constant, Kc for the reaction
N2(g) + 3H2(g) ↔ 2NH3(g)
decreases as the temperature rises whereas Kc for the reaction
N2(g) + O2(g) ↔ 2NO(g)
increases as the temperature rises.
(2 marks)
(e) A solution containing NH3(aq) and NH4Cl(aq) acts as buffer solution, resisting
changes in pH when acids and alkalis are added. Explain with the help of equations
how this mixture acts as a buffer.
(4 marks)

22. (a) Boron has two isotopes with relative isotopic masses of 10 and 11. When 1.000 g of
boron reacts completely with hydrogen, 1.278 g of boron hydride, B2H6 is produced.
(i) Define relative isotopic mass.
(2 marks)
(ii) Calculate the relative atomic mass of boron.
(3 marks)
(iii) Determine the relative intensity of boron 10 and 11.
(2 marks)
(iv) Sketch a labelled mass spectrum for boron.
(2 marks)

(b) (i) Using ethanoic acid as an example, define acid according to Bronsted-Lowry
theory.
(2 marks)
(ii) Name the conjugate base of ethanoic acid.
(1 mark)
(iii) Calculate the pH of 2.00 dm3 of a buffer solution prepared by dissolving 1.00
mole of CH3COOH and 0.900 mole of CH3COONa in sufficient amount of water.
(Ka of ethanoic acid = 1.80 x 10-5 mol dm-3)
(2 marks)
(iv) Write an equation to show how the buffer in (iii) maintain its pH upon adding a
little base.
(1 mark)
23. (a) The boiling point-composition phase diagram for the solution of ethanol in water is
shown below.

(i) Discuss the type of deviation from Raoult’s law for the above solution.
(ii) The alcoholic solution formed from the fermentation of carbohydrates contains
about 12% to 15% of ethanol. Explain why pure ethanol cannot be obtained from
the alcoholic solution by fractional distillation.
(7 marks)

(b) Water and ethanol are two separate solvents normally used in the lab. A graph of
vapour pressure against temperature of water and ethanol is shown below.

(i) Define the term vapour pressure.

(ii) Using the kinetic theory, explain the change in vapour pressure with the change
in temperature in water.
(iii) Explain the difference between the vapour pressure of water and ethanol at
60oC.
(9 marks)

24. (a) Explain what is meant by the Bronsted-Lowry theory of acids and bases.
(2 marks)
(b) The Ka values for some organic acids are shown below.
Acid Ka value/ mol dm-3
CH3COOH 1.7 x 10-5
ClCH2COOH 1.3 x 10-3
Cl2CHCOOH 5.0 x 10-2
(i) Explain the trend in Ka values in terms of the structure of these acids.
(ii) Calculate the pH of a 0.10 mol dm-3 solution of ClCH2COOH.
(iii) Use the following axes to sketch the titration curve you would obtain when 20
cm3 of 0.10 mol dm-3 NaOH is added gradually to 10 cm3 of 0.10 mol dm-3
ClCH2COOH.
(iv) Suggest a suitable indicator for this titration.
(9 marks)
(c) (i) Write suitable equations to show how a mixture of ethanoic acid, CH3COOH and
sodium ethanoate act as buffer solution to control the pH when acid or alkali is
added.
 (ii) Calculate the pH of a buffer solution containing 0.10 mol dm-3 ethanoic acid and
0.20 mol sodium ethanoate.
(4 marks)

25. (a) Predict the shape of NH3 molecule and NH4+ ion, explain the differences in their
bond angles.
(4 marks)
(b) Draw labelled diagrams to show the overlapping of orbitals in
(i) H2O
(ii) C2H4
(4 marks)
(c) The boiling point of H2O is higher than HF. Explain.
(2 marks)
(d) The rate of decomposition of acidic hydrogen peroxide can be analysed through
titration. Hydrogen peroxide samples with a fixed volume are taken at specific times
and were titrated with potassium manganate(VII) solution. The results are as follow.
Time/ min 0 10 20 30
3
Volume of KMnO4 (aq)/ cm 45.5 27.4 16.4 9.9

(i) Using the data above, plot a graph to determine the half-life of this reaction.
(ii) What is the order of this reaction?
(5 marks)

26. (a) State the Le Chatelier’s principle.

(2 marks)
(b) Referring to the equilibrium:
4NH3(g) + 5O2(g) ↔ 4NO(g) + 6H2O(g) ΔH = -908 kJ mol-1
Explain
(i) the effect on the yield of NO when pressure on equilibrium mixture is increased
(ii) the effect on equilibrium constant, Kc when temperature on the equilibrium
mixture is decreased
(4 marks)
(c) If 0.40 mol of NH3 and 0.50 mol of O2 in a 1 dm3 container are allowed to react in the
presence of catalyst platinum/ rhodium until an equilibrium is established, the yield
of NO is 30% by mole. Calculate the number of mol of NO produced.
(2 marks)
(d) Given that the reaction A  B is a second order reaction.
(i) Sketch the graphs of concentration of A versus time and rate versus concentration
of A
(ii) If the graph of 1/[A] versus time is as given below,

Calculate the rate constant and the initial concentration of A.

(iii) Suggest the mechanism of the reaction A  B.
(7 marks)
27. (a) The line spectrum of atomic hydrogen in the ultraviolet region of the
electromagnetic spectrum is shown below.

(i) Explain why this spectrum consists of lines which are convergence.
(ii) Using a labelled energy level diagram, show how the line marked Y on the
spectrum is formed.
(iii) If the frequency of convergence limit in Lyman series is 3.24 x 1015 Hz, calculate
the ionisation energy of hydrogen atom in kJ mol-1.
(iv) Write an equation of ionisation of hydrogen atom.
(7 marks)
(b) Hydrogen peroxide, H2O2 is a strong oxidising agent. It is used as a bleaching agent
for cloth and hair. The structural formula for hydrogen peroxide is H-O-O-H.
(i) Draw the Lewis structure of hydrogen peroxide.
(ii) State the hybridisation of oxygen atom in hydrogen peroxide.
(iii) Predict the molecular shape of hydrogen peroxide with respect to oxygen atoms.
Draw the molecular structure of hydrogen peroxide.
(5 marks)
(c) The mechanism of the oxidation of iodide ion by hydrogen peroxide in the presence
of acid is shown below.
H2O2 + I-  H2O + IO- (slow)
H+ + IO-  HIO (fast)
+ -
HIO + H + I  H2O + I2 (fast)

(i) Write the overall equation for the above reaction.

(ii) Write the rate equation for the reaction above.
(iii) What is the overall order of the reaction above?
(3 marks)

28. (a) (i) What is meant by dynamic equilibrium?

(ii) For the reversible reaction
N2(g) + 3H2(g) ↔ 2NH3(g)
Ammonia is produced in an equilibrium mixture at a temperature of 400oC and
pressure of 3 x 107 Pa, when hydrogen and nitrogen are mixed in the mole ratio
of 3: 1. Under these conditions, 61% of nitrogen are converted to ammonia. At
equilibrium, 0.39 mol of nitrogen gas, 1.17 mol of hydrogen gas and 1.22 mol of
ammonia are formed. Calculate the partial pressure equilibrium constant, Kp for
the reaction.
(5 marks)
(b) (i) A buffer solution is prepared by dissolving 1.0 mol of propanoic acid and 1.0 mol
of sodium propanoate in water and the solution is made up to 1 dm3. Calculate
the pH of this buffer solution.
(Ka of propanoic acid = 1.30 x 10-5 mol dm-3)
(3 marks)
(ii) Calculate the pH of the buffer solution when 0.10 mole of barium hydroxide is
added into it.
(3 marks)
(c) Two liquids A and B form an ideal mixture. A mixture of 70% of A and 30% of B is
fractionally distilled at a temperature of 373 K, at which temperature of the vapour
pressure of pure A is 48 kPa and of pure B is 36 kPa.
(i) What is the total pressure inside the distillation apparatus?
(ii) What is the composition of the first distillate?
(4 marks)