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CHEMISTRY 9701/42
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The number of marks is given in brackets [ ] at the end of each question or part question.
IB17 03_9701_42/6RP
© UCLES 2017 [Turn over
2
1.0 0.922
relative
0.5
intensity
0.047 0.031
28 29 30
m/e
Ar = .............................. [1]
(ii) Silicon forms a low boiling point chloride which reacts with water.
........................................................................................................................................ [1]
(iii) Draw a three-dimensional diagram showing the shape of the chloride. Give the Cl – Si – Cl
bond angle.
[2]
(iv) Silicon reacts with oxygen to form a high melting point oxide.
● Suggest, in terms of structure, why the oxide has a high melting point whereas the
chloride has a low boiling point.
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
[2]
(b) Element A is in the same period as silicon. Element A reacts with dilute nitric acid to form a
nitrate. This nitrate decomposes on heating to form an oxide.
........................................................................................................................................ [2]
........................................................................................................................................ [1]
[Total: 9]
2 (a) Complete the table using ticks () to indicate whether the sign of each type of energy change,
under standard conditions, is always positive, always negative or could be either positive or
negative.
electron affinity
ionisation energy
lattice energy
[2]
ΔH5
ΔH4
Mg2+(g) + 2Cl –(g)
Mg+(g) + 2Cl (g) + e–
ΔH3
Mg(g) + 2Cl (g)
ΔH2
Mg(g) + Cl 2(g) ∆H6
ΔH1
Mg(s) + Cl 2(g)
ΔH7
MgCl 2(s)
..............................................................................................................................................
........................................................................................................................................ [1]
(ii) What names are given to the enthalpy changes ΔH6 and ΔH7?
ΔH6 .......................................................................................................................................
ΔH7 .......................................................................................................................................
[1]
Suggest the trend in the first electron affinity of the elements in Group 17. Explain your answer.
.....................................................................................................................................................
.....................................................................................................................................................
............................................................................................................................................... [2]
(d) The equation for the formation of magnesium oxide from its elements is shown.
1
Mg(s) + 2 O2(g) MgO(s) ΔH o = – 602 kJ mol–1
substance S o / J K–1 mol–1
Mg(s) 32.7
O2(g) 205
MgO(s) 26.9
Use the equation and the data given in the table to calculate ΔG o for the reaction at 25 °C.
[Total: 10]
3 (a) T
he diagram shows the apparatus used to measure the standard electrode potential, E o, of
Fe3+(aq) / Fe2+(aq).
B D E
C F
A ................................................................. D ...............................................................
B ................................................................. E ................................................................
C ................................................................. F ................................................................
[3]
= .............................. V [1]
State and explain how the electrode potential changes if the concentration of Ni2+(aq) is
decreased.
..............................................................................................................................................
..............................................................................................................................................
........................................................................................................................................ [1]
Calculate the electrode potential when [Cr3+(aq)] is 0.60 mol dm–3 and [Cr2+(aq)] is
0.15 mol dm–3. Use the Nernst equation.
E = .............................. V [2]
[Total: 8]
The initial rate of the reaction was measured at different initial concentrations of Cl O2 and OH–.
The table shows the results obtained.
(i) U
se the data in the table to determine the rate equation, showing the order with respect to
each reactant. Show your reasoning.
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
(ii) C
alculate the value of the rate constant, k, using the data from experiment 2. State its
units.
(b) (i) Explain the difference between heterogeneous and homogeneous catalysts.
..............................................................................................................................................
..............................................................................................................................................
........................................................................................................................................ [1]
(ii) Complete the table using ticks () to indicate whether the catalyst used in the reaction is
heterogeneous or homogeneous.
(c) Some reactions are catalysed by one of the products of the reaction. This is called autocatalysis.
An example of autocatalysis is the reaction between acidified manganate(VII) ions, MnO4–,
and ethanedioic acid, (CO2H)2. Mn2+ ions catalyse this reaction. The reaction is slow in the
absence of a catalyst.
concentration
of reactant
time
On the axes below, sketch the curve you would expect for the autocatalysed reaction in (i).
concentration
of MnO4–
time
[2]
(d) (i) D
escribe, with the aid of a reaction pathway diagram, the effect of a catalyst on a reversible
reaction. Suggest why catalysts are used in industrial processes.
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
[3]
(ii) The reaction for the Haber process to produce ammonia is shown.
At 500 °C, when pressure is measured in atmospheres, the numerical value of Kp for this
equilibrium is 1.45 × 10–5.
Kp =
● alculate the partial pressure of NH3 at equilibrium at 500 °C, when the partial pressure
C
of N2 is 20 atm and that of H2 is 60 atm.
[2]
[Total: 17]
step 1
step 2
Cl 2(g)
step 3
NH2
compound H
intermediate G
reagents ...............................................................................................................................
conditions ............................................................................................................................
[2]
........................................................................................................................................ [1]
reagents ...............................................................................................................................
conditions ............................................................................................................................
[2]
............................................................................................................................................... [1]
(c) C
ompare the relative basicities of ammonia, phenylamine and compound H. Explain your
answer.
.....................................................................................................................................................
.....................................................................................................................................................
............................................................................................................................................... [2]
[Total: 9]
[1]
Ni 1s22s22p63s23p6 ................................................
(b) (i) Complete the diagram to show how the presence of ligands around an isolated transition
metal ion affects the energy of the d orbitals.
energy
degenerate
d orbitals
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
........................................................................................................................................ [2]
..............................................................................................................................................
..............................................................................................................................................
........................................................................................................................................ [1]
absorption
explanation .................................................................................................................................
............................................................................................................................................... [2]
(d) (i) In the presence of chloride ions, [V(H2O)6]3+ reacts to form a mixture of isomeric octahedral
complexes.
V V
isomer 1 isomer 2
[2]
(ii) State the type of isomerism shown by isomer 1 and isomer 2 in (i).
........................................................................................................................................ [1]
(e) (i) The complex [V(H2O)6]3+ also reacts with ethane-1,2-diamine (en), H2NCH2CH2NH2, to
form a mixture of isomeric octahedral complexes.
V V
isomer 1 isomer 2
[2]
(ii) State the type of isomerism shown by isomer 1 and isomer 2 in (i).
........................................................................................................................................ [1]
(f) The reaction of [Ni(H2O)6]2+ with aqueous ammonia produces the complex [Ni(NH3)6]2+.
Kstab =
[1]
State which complex is produced in the larger amount. Explain your answer.
..............................................................................................................................................
..............................................................................................................................................
........................................................................................................................................ [1]
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
........................................................................................................................................ [2]
[Total: 18]
7 The compound Advantame is a sweetener that tastes approximately 25 000 times sweeter than
sucrose.
RO
O
H
N O
HO N CH3
H
O O
OH
Advantame
On the diagram of Advantame, circle all the chiral carbon atoms. [1]
(b) The decomposition of Advantame produces three molecules, J, K and L. The RO– group in
Advantame is unreactive.
RO
O
H
N
HO OH
+ +
OH
O H2 N
OH O
J K L
........................................................................................................................................ [1]
........................................................................................................................................ [1]
(c) (i) Aqueous bromine was added dropwise to a solution of J until the bromine was in excess.
State what you would observe.
..............................................................................................................................................
........................................................................................................................................ [1]
(ii)
J has the molecular formula C14H19O6N.
Use this formula to write an equation for the reaction of excess aqueous sodium hydroxide
with one mole of J.
........................................................................................................................................ [2]
(d) (i) State what you would observe when an excess of aqueous bromine is added to a solution
of K.
........................................................................................................................................ [1]
(ii)
K can be polymerised.
Draw the structure of the polymer showing two repeat units. The linkage between the
monomer units should be fully displayed.
[2]
(e) Use the Data Booklet to help you answer this question.
OH
H2N
O
K
........................................................................................................................................ [1]
(ii) T
he chemical shifts, δ, due to two of the carbon atoms x and y present in K are given in
the table.
On the structure of K, circle and label two carbon atoms which could correspond to x and y.
[1]
[Total: 12]
8 he root of the ginger plant contains compounds with medicinal and flavouring properties. Three of
T
the more important compounds are gingerol, shogaol and zingerone.
(a) The structure of gingerol is shown. The CH3O– group in gingerol is unreactive.
O OH
HO
CH3O
gingerol
State the type of reaction and the functional group change which occurs during this reaction.
HO
CH3O
shogaol
(i) State the type of reaction needed to convert gingerol into shogaol.
........................................................................................................................................ [1]
(ii) State the reagents and conditions needed to convert gingerol into shogaol.
reagents ...............................................................................................................................
conditions ............................................................................................................................
[1]
hogaol reacts with hot, concentrated acidified manganate(VII) ions to form two organic
(iii) S
products, Q and R.
Q R
[2]
benzenediazonium chloride,
red ppt.
5 °C, alkaline solution
[2]
[Total: 7]
100
80
60
relative
intensity
40
20
0
50 75 100 125 150
m/e
x = .............................. [2]
........................................................................................................................................ [1]
........................................................................................................................................ [1]
100
transmittance
50
V W
0
4000 3000 2000 1500 1000 500
wavenumber / cm–1
Identify the type of bond responsible for each of the peaks V and W.
Use the Data Booklet to help you.
3H 3H
4H
11 10 9 8 7 6 5 4 3 2 1 0
δ / ppm
3.9
7.2–7.9
[1]
(ii) The peak at δ = 2.4 ppm is due to a proton attached to a saturated carbon atom.
1. ..........................................................................................................................................
2. ..........................................................................................................................................
[1]
(iii) Adding D2O to T does not change its proton NMR spectrum.
What does this tell you about the functional groups present in T?
........................................................................................................................................ [1]
(d) Use the information to draw two possible structures of T which are functional group isomers of
each other.
[2]
[Total: 10]
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