Summer 2003 C4

1. (a) Give the equations for the reactions between

(i) magnesium and oxygen;

......................................................................................................................
(1)

(ii) silicon and oxygen;

......................................................................................................................
(1)

(iii) sulphur and oxygen.

......................................................................................................................
(1)

(b) State the acid-base character of

(i) magnesium oxide;

......................................................................................................................
(1)

(ii) silicon(IV) oxide.

......................................................................................................................
(1)

(c) (i) Sodium oxide is a basic oxide.

Write the equation for the reaction of sodium oxide with water.

......................................................................................................................
(1)

(ii) State the type of bonding in sodium oxide and explain how particles react to form
the product in (c) (i).

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

......................................................................................................................
(3)
(Total 9 marks)

1
Summer 2003 C4

2. (a) As atomic number increases in group 4 the metallic character of the elements increases.
Explain how this increase in metallic character is demonstrated in the acid-base properties
of carbon dioxide and of lead(II) oxide.

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

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

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

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

...............................................................................................................................
(3)

(b) The reactions of tin(IV) oxide and of lead(IV) oxide with concentrated hydrochloric acid
are:

SnO2 + 4HCl → SnCl4 + 2H2O

PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O

(i) What are the oxidation states of tin and of lead in these two chlorides?

tin: ...............................................................................................................

lead: ............................................................................................................
(2)

(ii) Suggest a reason for the difference in behaviour of SnO2 and PbO2 with
concentrated hydrochloric acid.

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

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

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

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

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

......................................................................................................................
(3)
(Total 8 marks)

3. (a) Define the term partial pressure.

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

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

...............................................................................................................................
(1)

2
Summer 2003 C4

(b) If phosphorus pentachloride is heated in a sealed tube the following equilibrium is set up

PCl5(g) PCl3(g) + Cl2(g)

(i) Write an expression for the equilibrium constant, Kp, for the above reaction.

(1)

(ii) At a given temperature T a sample of phosphorus pentachloride is 40.0%

dissociated, the total equilibrium pressure being 2.00 atm. Calculate the partial
pressures of each of the components of the equilibrium mixture, to three significant
figures. Hence calculate the value of Kp under these conditions.

(5)

(c) At a higher temperature, T + t, the equilibrium mixture in (b) contains a greater proportion
of phosphorus trichloride and chlorine.

(i) State, with a reason, whether the dissociation of phosphorus pentachloride is

exothermic or endothermic.

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

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

......................................................................................................................
(2)

(ii) How does Kp change when the temperature is increased?

......................................................................................................................
(1)

3
Summer 2003 C4

(d) If calcium carbonate is heated in a sealed vessel in the absence of air the following
equilibrium is set up:

CaCO3(s) CaO(s) + CO2(g)

(i) Write the expression for Kp for this equilibrium.

......................................................................................................................
(1)

(ii) At 1030 °C the total pressure in the vessel is 16 atm. What is the value of Kp?

......................................................................................................................
(1)
(Total 12 marks)

4. Propanoic acid is a weak acid which dissociates according to

CH3CH2COOH(aq) + H2O(l) CH3CH2COO–(aq) + H3O+(aq)

(a) (i) Indicate, in the space provided below the equation, the two acid/base conjugate
pairs.
(2)

(ii) Write the expression for the acid dissociation constant, Ka, for propanoic acid.

(1)

4
Summer 2003 C4

(iii) Calculate the pH of a 0.100 mol dm–3 solution of propanoic acid, for which
Ka = 1.3 × 10–5 mol dm–3.

(3)

(iv) Calculate the concentration of hydroxide ions, OH–, in this same solution of
propanoic acid. Kw = 1.00 × 10–14 mol2 dm–6 at the temperature of the solution.

(3)

(b) If sodium propanoate is dissolved in water, the pH of the resulting solution is not 7, but is
near to 8. By writing the equation for the reaction occurring suggest why this is so.

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

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

................................................................................................................................
(2)

(c) A mixture of sodium propanoate and propanoic acid behaves as a buffer solution.

(i) What is meant by a buffer solution?

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

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

......................................................................................................................
(2)

5
Summer 2003 C4

(ii) Calculate the pH of a buffer solution that is made by mixing equal volumes of
0.0500 mol dm–3 propanoic acid and 0.100 mol dm–3 sodium propanoate.

(3)
(Total 16 marks)

5. (a) Define the terms

(i) lattice energy;

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

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

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

......................................................................................................................
(3)

(ii) enthalpy of hydration.

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

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

......................................................................................................................
(2)

6
Summer 2003 C4

(b) Lattice energy and enthalpies of hydration can sometimes be used to rationalise the
solubility trend in a series of related salts.

(i) Draw a labelled Hess’s Law cycle that would enable the enthalpy of solution, ∆Hsol,
of an ionic solid M+X– to be calculated from the lattice energy and enthalpies of
hydration of the ions.

(3)

(ii) Express the enthalpy of solution ∆Hsol in terms of the other quantities.

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

......................................................................................................................
(1)

(iii) The approximate relative solubility (relative to magnesium sulphate) of the

sulphates of the elements of group 2 are given below.

Salt Relative solubility

MgSO4 1
CaSO4 10–2
SrSO4 10–4
BaSO4 l0–6

7
Summer 2003 C4

Explain the reasons for this trend in solubility in terms of changes of lattice
energies and enthalpies of hydration.

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

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

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

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

......................................................................................................................
(4)
(Total 13 marks)

6. (a) 2-aminobutane, CH3CH2CH(NH2)CH3, is a chiral molecule that can be optically active. It

can be made from CH3CH2CH(CONH2)CH3.

(i) What is a chiral molecule?

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

......................................................................................................................
(1)

(ii) How is optical activity detected experimentally?

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

......................................................................................................................
(1)

(b) State the reagents and conditions necessary to convert CH3CH2CH(CONH2)CH3

to 2-aminobutane.

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

...............................................................................................................................
(3)

(c) (i) CH3CH2CH(CONH2)CH3, D, can be made from 2-bromobutane in four steps

shown below.

i) CO 2
Mg ii) HCl(aq)
CH 3 CH 2 CHBrCH 3 Grignard A B

PCL 5
CONH 2

CH 3 CH 2 C CH 3 C

H
D
Give the structural formulae of the three intermediate compounds A, B and C.

8
Summer 2003 C4

(3)

(ii) Grignard reagents are often made in a solvent of dry ethoxyethane. Why must the
ethoxyethane be dry?

......................................................................................................................
(1)

(iii) Give the reagents and conditions for the conversion of C to D.

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

......................................................................................................................
(2)

(d) Butanone can be made from 2-bromobutane by a synthetic route involving two steps, the
first using aqueous sodium hydroxide and the second potassium dichromate(VI) solution
acidified with dilute sulphuric acid.

(i) Give the structural formula of the intermediate compound in this synthetic route.

(1)

9
Summer 2003 C4

(ii) Butanone reacts with 2,4-dinitrophenylhydrazine solution but not with Fehling’s
solution. Why is this?

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

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

......................................................................................................................
(2)

(iii) Butanone also reacts with iodine in sodium hydroxide solution. What structural
feature of butanone is shown by this reaction?

(1)

(iv) Give the structural formulae of both the organic products from the reaction in (iii).

(2)
(Total 17 marks)

10