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The diagram below shows a mass spectrometer, which can be used to determine the percentage
abundances of isotopes in an element.
(a)
(b)
Electric field
...........................................................................................................................
...........................................................................................................................
(1)
(ii)
Magnetic field
...........................................................................................................................
...........................................................................................................................
(1)
(c)
A sample of the element barium is made up of four isotopes. The data below were taken
from a mass spectrum of this sample.
Mass/charge ratio
% abundance
135
9.01
136
10.81
137
12.32
138
67.86
Calculate the relative atomic mass of the sample, giving your answer to one decimal
place.
(2)
(d)
79
81
The element bromine has two stable isotopes, Br and Br. How many peaks
+
corresponding to Br2 ions would be seen in the mass spectrum of bromine?
Justify your answer.
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.....................................................................................................................................
(2)
(e)
Suggest another application of mass spectrometry, other than to determine the relative
atomic mass of an element.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 9 marks)
2.
Which of the following features is shown by the mass spectra of propanone and propanal?
propanone
propanal
Fragmentation pattern
same
same
same
different
different
same
different
different
(Total 1 mark)
3.
The spectra of the compounds with the formulae CH 3CH(OH)CH3 and CH3CH2CH2OH can be
distinguished by
A
4.
Which of the following has two singlet peaks in its nmr spectrum?
A
Methanal, HCHO
Methanol, CH3OH
Chloromethane, CH3Cl
Dichloromethane, CH2Cl2
(Total 1 mark)
5.
, contains
(Total 1 mark)
6.
In the reaction of manganate(VII) ions with reducing agents in strongly acidic solution, the halfreaction for the reduction is
2+
+ 2H2O
2+
+ 4H2O
2+
+ 4H2O
MnO4 + 4H + 5e Mn
MnO4 + 8H + 3e Mn
MnO4 + 8H + 5e Mn
(Total 1 mark)
7.
The conditions needed for the E value of the standard hydrogen electrode to be exactly 0 V are
3
3
3
(Total 1 mark)
8.
The electrode potential for a cell can be used to calculate the equilibrium constant for the cell
reaction. This is because
ln E
In E
cell
is proportional to K.
cell
cell
is proportional to lnK.
is proportional to K.
(Total 1 mark)
Courier New;OOKHMJ+TimesNewRomanPSMT;Symbol;9.
Brass is an alloy of copper, zinc and,
in some cases, other metals too. There are over 30 varieties of brass for different applications.
The amount of copper in a brass can be found as follows:
A weighed sample of brass is reacted with the minimum amount of concentrated nitric
acid.
The solution is neutralized, a portion of it pipetted into a conical flask, and excess
potassium iodide solution is added.
(a)
The ionic equation for the reaction between copper metal and concentrated nitric acid is
shown below.
2+
Give the oxidation numbers of the copper and nitrogen in both the reactants and
products.
Copper: from..........................................to..........................................
Nitrogen: from.........................................to.........................................
(2)
(ii)
Write the two half-equations that can be combined to give the ionic equation shown
above.
(2)
(iii)
Explain why the standard electrode potentials for the two ionic half-equations that
you have written give an incorrect value for Ecell for this reaction as described
above.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(b)
The solution produced contains a mixture of zinc ions and copper ions.
(i)
State TWO observations that you would see if concentrated ammonia solution were
to be added, drop by drop, to the solution until in excess.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
Copper ions can be separated from the zinc ions in the solution by adding sodium
hydroxide solution in excess, followed by filtration of the mixture.
Write equations, including state symbols, for the THREE reactions that occur.
Equation 1
Equation 2
Equation 3
(3)
(iii)
(c)
A sample of Admiralty Brass of mass 3.00 g was treated with nitric acid and made up to a
3
3
neutral solution of volume 250 cm . Excess potassium iodide was added to 25.0 cm
portions of this solution, and the liberated iodine was titrated with sodium thiosulfate
3
3
solution, concentration 0.100 mol dm . The mean titre was 33.10 cm .
(i)
Write the ionic equation for the reaction between thiosulfate ions and iodine.
(1)
(ii)
The equation for the reaction between copper(II) ions and iodide ions is shown
below.
2Cu
2+
+ 4I 2CuI + I2
Hence calculate the percentage by mass of copper in Admiralty Brass. Give your
answer to three significant figures.
(6)
(iii)
When setting up the burette, a student failed to fill the jet of the burette.
Explain the effect that this would have on the value of the first titre.
If this first titre was included in the calculation of the mean titre, what effect would
this have on the value for the percentage of copper in the brass?
...........................................................................................................................
...........................................................................................................................
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(2)
(Total 23 marks)
10.
Paracetamol is possibly the most widely used analgesic (painkiller) in the world. It can be made
from phenol as shown below.
(a)
The nitration of phenol in step 1 uses dilute nitric acid at room temperature, whereas the
nitration of benzene requires a mixture of concentrated nitric and sulfuric acids at about
55C.
(i)
Give the mechanism for the nitration of benzene, including the equation for the
reaction that produces the electrophile.
(4)
(ii)
Explain why phenol can be nitrated under much milder conditions than those
required to nitrate benzene.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
10
(iii)
(iv)
(b)
11
(c)
The nmr spectrum of paracetamol is given below. The peaks at 6.7 and 7.4 ppm are due to
the protons on the benzene ring and are both doublets.
Explain why these two peaks are doublets but all the other peaks are singlets.
[There is no need to refer to your data booklet]
.....................................................................................................................................
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(2)
(Total 14 marks)
12
11.
More than half of the elements in the Periodic Table are transition elements. Vanadium, element
23, is a typical transition element.
(a)
(i)
(ii)
3+
(b)
Use your data booklet (page 15) to find the standard electrode (reduction) potential
2+
3+
for the reduction of vanadium(IV), VO , to vanadium(III), V .
...........................................................................................................................
(1)
(ii)
13
(iii)
Use your answer to (b)(i), and the data below, to calculate E cell for the formation
of vanadium(V) and vanadium(III) from vanadium(IV) in acidic solution. State if
the reaction is feasible under standard conditions and justify your answer.
+
2+
...........................................................................................................................
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(2)
(Total 10 marks)
12.
Chlorine has two isotopes with relative isotopic mass 35 and 37. Four m/z values are given
below. Which will occur in a mass spectrum of chlorine gas, Cl 2, from an ion with a single
positive charge?
A
35.5
36
71
72
(Total 1 mark)
14
13.
14.
15
What can be deduced about the structures of X and Y using all this information and the
data booklet? Justify your answer.
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(4)
(b)
16
nmr spectrum of Y
Use these nmr spectra and your answer to (a) to deduce the structural formulae of X and
Y. Justify your answer and explain why both nmr spectra are consistent with these
structures.
(6)
(Total 10 marks)
15.
17
63.2
63.4
63.6
64.0
(Total 1 mark)
16.
Which of the following ions would undergo the greatest deflection in a mass spectrometer?
A
35
2+
35
37
35
37
Cl
Cl
Cl
Cl Cl
(Total 1 mark)
17.
Which of the following values for the mass/charge ratio for singly charged ions would be
present in the mass spectrum of propanal, CH3CH2CHO, but not of propanone, CH3COCH3?
A
15
29
43
58
(Total 1 mark)
18
18.
(a)
Describe briefly how positive ions are formed from gaseous atoms in a mass
spectrometer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
(iii)
(b)
The following data were obtained from the mass spectrum of a sample of chromium.
Mass/charge ratio
% abundance
50.0
4.3
52.0
83.8
53.0
9.5
54.0
2.4
Calculate the relative atomic mass of chromium in this sample. Give your answer to three
significant figures.
(2)
(c)
Explain why the four isotopes of chromium behave identically in chemical reactions.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
19
20
(d)
19.
Buckminsterfullerene is a carbon molecule with formula C60 which can trap metal ions in its
structure. Which of the following compounds of buckminsterfullerene would give a line of
mass/charge ratio at 837.3 in a mass spectrometer?
A
Na4C60
K3C60
Ca3C60
AgC60
(Total 1 mark)
20.
C2H2
C3H6
C3H8
C4H10
(a)
Which hydrocarbon has the same empirical formula as its molecular formula?
A
B
C
D
(1)
21
(b)
Which has a molecular ion in the mass spectrum at mass/charge ratio = 58?
A
B
C
D
(1)
(c)
(d)
22
21.
Describe the bonding in magnesium and explain why it is a good conductor of electricity.
.....................................................................................................................................
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.....................................................................................................................................
.....................................................................................................................................
(3)
(b)
Draw a diagram (using dots or crosses) for the ions in magnesium fluoride showing all
the electrons and the ionic charges on:
(i)
(1)
(ii)
(1)
(c)
23
(d)
80
re la tiv e a b u n d a n c e %
60
40
20
20
22
24
26
28
m a s s /c h a rg e ra tio
(i)
Use the data above to estimate the percentage isotopic composition of the sample
of magnesium. Hence calculate the average atomic mass of the sample of
magnesium.
(2)
24
(ii)
(e)
(i)
(2)
(ii)
X-ray diffraction can be used to locate atoms or ions in molecules like chlorophyll.
X-rays are scattered by the electrons in atoms and ions. In chlorophyll the atoms of
one of the elements still cannot be located with certainty by this technique.
Suggest which element is most difficult to locate.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 12 marks)
22.
(a)
A sample of an element can be analysed to show its isotopic composition using a mass
spectrometer.
(i)
25
26
(ii)
State the TWO properties of the ion that determine the path of the ion through the
magnetic field.
...........................................................................................................................
...........................................................................................................................
(2)
(b)
(c)
The following data were obtained from the mass spectrum of a sample of chromium.
Relative isotopic mass
Percentage abundance
49.95
4.345
51.94
83.79
52.94
9.501
53.94
2.364
(2)
27
(d)
2s
2p
3s
3p
3d
4s
(2)
(Total 10 marks)
23.
The formulae of five organic compounds (A, B, C, D and E) containing four carbon atoms per
molecule are shown below:
H 2N C H C O 2H
C H 2C O 2H
C H 3C H 2C H B rC H
N H
CH
C H
C H
C H
C H 3C H
C
C H 3C O N H C H 2C H
(a)
28
(b)
(c)
(d)
Which compound would give a cream precipitate when hot silver nitrate is added?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
(1)
(ii)
Which compound would give a purple colour when ninhydrin solution is added?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
(1)
29
(iii)
(iv)
Which TWO compounds would react with dilute hydrochloric acid to form salts?
..................................................
..................................................
(1)
(v)
Which TWO compounds react with water, under appropriate conditions, to form
alcohols?
..................................................
..................................................
(1)
(e)
(i)
Name compound E.
...........................................................................................................................
(1)
(ii)
Write the equation for the formation of compound E from ethylamine and another
suitable reagent, using structural formulae.
(1)
30
(f)
(i)
Compound A can react with itself to form a dipeptide under appropriate conditions.
Give the structural formula of this dipeptide.
(1)
(ii)
(g)
(i)
Which of the compounds A to E has the least number of peaks in the nuclear
magnetic resonance (NMR) spectrum?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
E
(1)
(ii)
31
(h)
Which of the compounds A to E would not have an absorption above 3000 cm in the
infrared spectrum?
Put a cross in the box ( ) of the correct answer.
A
B
C
D
E
(1)
(i)
Which of the compounds A to E would have peaks occurring in pairs in the mass
spectrum? Justify your answer.
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 18 marks)
24.
Vanillin, the main ingredient of vanilla essence, is one of the commonest flavouring ingredients
found in foods. Synthetic vanillin, which is identical to natural vanillin, can be manufactured
from methoxybenzene. One synthetic route is shown below:
SO 3H
O CH
O H
O CH
O H
O C H
O CH
CH O
m e th o x y b e n z e n e
(a)
(i)
2 -m e th o x y b e n z e n e
s u lp h o n ic a c id
2 -m e th o x y p h e n o l
v a n illin
32
(ii)
(b)
After the final stage, in which 2-methoxyphenol is converted to vanillin, the impure
product can be purified by recrystallisation. In this process the solid is dissolved in the
minimum volume of hot water. The mixture is then filtered whilst still hot. The filtrate is
cooled in an ice bath to produce crystals of vanillin. These can be removed by filtration
and dried.
(i)
(ii)
The impure vanillin may contain soluble and insoluble impurities. Describe how
each of these is removed during recrystallisation.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
How would you check the purity of the vanillin after recrystallisation, other than
by using an infrared spectrometer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
33
(c)
In order to establish whether or not vanillin had been formed, two infrared spectra were
obtained: a sample of pure 2-methoxyphenol and a sample of the product.
Study the spectra and data below.
In fr a re d S p e c tr u m o f 2 -M e th o x y p h e n o l
100
80
T ra n s m itta n c e
/%
60
40
20
3000
2000
W avenum ber/cm
1000
1
In fr a re d S p e c tr u m o f P ro d u c t
100
T ra n s m itta n c e
/%
80
60
40
3000
2000
W avenum ber/cm
1000
1
Wavenumber / cm
C C Stretching Vibrations
CH Stretching Vibrations
OH Stretching Vibrations
C O Stretching Vibrations
Arene
Arene
Alcohols and phenols
Aldehydes
Ketones
Carboxylic acids
Esters
1600 1450
3030
3750 3200
1740 1720
1700 1680
1725 1680
1750 1735
34
Comment as to whether any vanillin is likely to have been formed during the process.
Support your answer with relevant evidence.
.....................................................................................................................................
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(2)
(Total 10 marks)
25.
(a)
(i)
(ii)
State the HOH bond angle in water and explain why it has this value.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
35
(b)
(i)
Draw the boron trichloride molecule, BCl3, making its shape clear. Mark in the
bond angle on your diagram.
(2)
(ii)
(iii)
(iv)
36
37
(c)
A compound of phosphorus and chlorine has the composition by mass shown below.
Element
% by mass
14.9
Cl
85.1
(2)
(Total 11 marks)
26.
Two experiments are carried out under the same conditions except that in one experiment
the manganese(IV) oxide is a fine powder and in the other the same mass of coarse
granules is used.
Which experiment would show the faster rate of decomposition? Explain your answer in
terms of collision theory.
.....................................................................................................................................
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.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
38
(b)
(i)
(4)
(ii)
Mark on your graph a suitable value for the activation energy, Ea, for the reaction
between the gases. Use your drawing to account for the increase in reaction rate
with increasing temperature.
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...........................................................................................................................
...........................................................................................................................
(3)
39
(iii)
27.
The following data relate to the thermodynamic changes which occur when Group 2 hydroxides
dissolve in water.
1890 kJ mol
2+
1275 kJ mol
550 kJ mol
2995 kJ mol
2320 kJ mol
Enthalpy of hydration of Mg
Enthalpy of hydration of Ba
2+
Enthalpy of hydration of OH
(a)
(i)
40
(ii)
(b)
Why is the lattice energy of magnesium hydroxide more exothermic than that of barium
hydroxide?
.....................................................................................................................................
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.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
41
(c)
(i)
Draw a labelled Hesss law cycle to show how the lattice energy and the enthalpies
of hydration are related to the enthalpy of solution of magnesium hydroxide,
Mg(OH)2(s).
(3)
(ii)
Use your cycle and the data to calculate the enthalpy of solution of magnesium
hydroxide. Include a sign and units with your answer.
(2)
42
(d)
Use the data to explain how the solubility of barium hydroxide compares with that of
magnesium hydroxide.
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(3)
(Total 15 marks)
28.
This question is about a compound, A, used as a food flavouring. It has the molecular formula,
C9H8O.
(a)
For each of the following pieces of information, state what can be deduced about the a
structure of A.
(i)
(ii)
(iii)
(iv)
43
44
(v)
(vi)
(2)
45
(b)
(ii)
How would you check that the purification had been successful?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
46
(c)
(i)
Write the equation for the reaction which occurs when solid benzoic acid is added
to sodium carbonate solution. Include state symbols in your equation.
(2)
(ii)
Benzoic acid is slightly soluble in water. Write the equation for the dissociation of
benzoic acid and hence the expression for the acid dissociation constant, K a.
(2)
(iii)
(3)
47
(d)
Give the name or formula of an organic compound which, when mixed with a solution of
benzoic acid, forms a buffer solution.
(1)
(Total 21 marks)
29.
Paracetamol can be manufactured from phenol using the reaction sequence below.
O H
O H
O H
S te p 1
S te p 2
N O
A
(a)
O H
S te p 3
N H
C
N H CO C H
P a ra ce ta m o l
(b)
(c)
(i)
48
(ii)
Suggest a test and its results for the amino group in compound C.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(d)
(i)
Write a balanced equation for the reaction occurring when paracetamol is boiled
with an aqueous solution of sodium hydroxide.
(2)
(ii)
Would you expect paracetamol to react with sodium carbonate solution? Justify
your answer.
...........................................................................................................................
...........................................................................................................................
(1)
49
(e)
(i)
(ii)
(f)
Suggest which bond gives rise to the broadest absorption in the infrared spectrum of
paracetamol.
State the range of wavenumbers for this absorption.
...........................................................................................................................
...........................................................................................................................
(2)
(g)
(i)
Give the molecular formula of the ion with the highest molecular mass in the mass
spectrum of paracetamol.
...........................................................................................................................
(1)
50
(ii)
Suggest the formulae of the ions responsible for the peaks at mass / charge ratios
43 and 93.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(h)
Suggest ONE advantage of using paracetamol, rather than aspirin, as a pain reliever.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 20 marks)
30.
Draw a diagram of suitable apparatus for carrying out the air-oxidation of the
vanadium(II) chloride solution.
(1)
51
(ii)
Complete the half equation for acidified manganate(VII) ions acting as an oxidising
agent.
2+
(iii)
Calculate the number of moles of manganate(VII) ions used in the titration, and hence the
number of moles of electrons removed by the manganate(VII) ions.
3
Calculate the number of moles of vanadium(II) ions in the 10 cm of solution used. Find
the oxidation number of vanadium in the air-oxidised solution given that vanadium(V)
ions are formed in the titration.
(4)
52
(iv)
Suggest ONE reason why acidified potassium manganate(VII) is a useful oxidising agent
in redox titrations.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 7 marks)
31.
(a)
(i)
1s .......................................................................................................................
(1)
53
(ii)
st
nd
The grid below shows the relative values of the 1 and 2 ionisation energies of
rd
aluminium. Mark on the grid the relative values that you would expect for the 3
th
and 4 ionisation energies of aluminium.
E n e rg y
1 st
2 nd
Io n is a tio n E n e rg y
3 rd
th
(2)
(b)
(i)
(ii)
Write the half-equation for the reduction of oxygen gas to oxide ions, O .
...........................................................................................................................
(1)
54
(iii)
Combine these two half-equations to produce the redox equation for the reaction of
aluminium with oxygen to form aluminium oxide.
...........................................................................................................................
...........................................................................................................................
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(1)
(Total 6 marks)
32.
Iodine and propanone react together in the presence of dilute hydrochloric acid according to the
equation:
)
CH 3 COCH 3 I 2 H
(aq
CH 3 COCH 2 I HI
The rate of reaction can be measured by recording the decrease in the concentration of the
iodine.
Experiment
initial
[CH3COCH3]
3
/mol dm
initial [I2]
3
/mol dm
initial [H ]
3
/mol dm
Rate
3 1
/mol dm s
0.40
0.0040
0.40
1.5 10
0.80
0.0040
0.40
3.0 10
0.40
0.0020
0.40
1.5 10
0.80
0.0020
0.80
6.0 10
55
(a)
(i)
State the order of the reaction with respect to CH 3COCH3, I2 and H . Justify your
answer.
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(4)
(ii)
(b)
(3)
56
57
(c)
H +
S te p 1
H 3C
C H
I2
S te p 2
C H 3C O C H 2I
O H
Use your answers to (a)(i) to compare the relative rates of the two steps.
Explain your reasoning.
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.....................................................................................................................................
(2)
58
(d)
The graph below represents the change in concentration of iodine in Experiment 1 over a
5 minute period.
0 .0 0 5
0 .0 0 4
[I 2 ]
/ m ol dm
0 .0 0 3
0 .0 0 2
0 .0 0 1
0
0
T im e / m in
Add labelled lines to represent Experiment 2 and Experiment 3.
(3)
(e)
(i)
Propanone can also react with iodine to form a pale yellow precipitate of triiodomethane. What other reagent is needed for this reaction?
...........................................................................................................................
(1)
59
(ii)
(2)
(f)
State and explain how the n.m.r. spectra of propanone and propanal would differ.
.....................................................................................................................................
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(2)
(Total 18 marks)
60
33.
C3H6(g) + H2(g)
DH = +122 kJ mol
If the pressure is increased, what will be the effect on the yield of propene obtained at
equilibrium? Justify your answer.
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.....................................................................................................................................
.....................................................................................................................................
(2)
(ii)
State why the yield of propene at equilibrium increases with increasing temperature.
.....................................................................................................................................
.....................................................................................................................................
(1)
(iii)
What effect does the catalyst have on the yield of propene at equilibrium?
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 4 mark)
61
34.
(a)
+347
+612
CH
+413
(3)
(b)
The enthalpy changes of atomisation and the boiling points of some alkenes are shown
below.
Alkene
Hat
/kJ mol
Ethene, C2H4
+2260
103.6
Propene, C3H6
+3440
47.3
But-1-ene, C4H8
(i)
Boiling point
/C
6.2
Pent-1-ene, C5H10
+5800
+30.0
Hex-1-ene, C6H12
+6990
+63.4
On the grid below, plot values for the enthalpy change of atomisation (vertical axis)
against the number of carbon atoms in the alkene molecule (horizontal axis).
(One page of graph paper should be provided).
62
(3)
63
(ii)
(iii)
Use your graph to estimate the value of the enthalpy change of atomisation for
but-1-ene.
....................................... kJ mol
(1)
(c)
(i)
(ii)
(iii)
...........................................................................................................................
...........................................................................................................................
(1)
64
65
C H 3C H 2C
(iv)
2-methylbut-1-ene,
C H
C H
3
, is an isomer of pent-l-ene.
Predict which of these isomers has the higher boiling point. Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(d)
By considering the intermolecular forces in water, suggest why liquid alkenes do not mix
with water.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 17 marks)
35.
One step in the manufacture of nitric acid is the reaction between nitrogen(II) oxide and oxygen
to form nitrogen(IV) oxide.
2NO(g) + O2(g)
(a)
(i)
2NO2(g)
H = 114 kJ mol
Use the equation to suggest the sign of Ssystem for the forward reaction. Justify
your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
66
(ii)
What is the sign of Ssurroundings for the forward reaction? Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(b)
(i)
Units ..............................................
(2)
67
(ii)
Suggest how the temperature and pressure could be altered to make nitrogen(IV)
oxide more economically. Justify your suggestions by considering both yield and
rate.
Temperature
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
Pressure
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
(c)
(i)
What property would allow you to follow the progress of this reaction? Justify your
answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
68
(ii)
[NO(g)]
3
/mol dm
[O2(g)]
3
/mol dm
Initial rate
3 1
/mol dm s
1.0 10
1.0 10
8.0 10
2.0 10
1.0 10
3.2 10
2.0 10
2.0 10
6.4 10
What is the order of the reaction with respect to NO(g)? Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
(1)
(iv)
69
(v)
Calculate the rate constant, k, for this reaction. Include units with your answer.
(2)
(d)
Suggest why this reaction takes place quickly at room temperature and pressure.
.....................................................................................................................................
(1)
(Total 20 marks)
36.
(a)
Step 1
CH3CH=CHCOOH
CH3CHBrCH2COOH
Step 2
CH3CHBrCH2COOH
CH3CH(OH)CH2COOH
Step 3
CH3CH(OH)CH2COOH
CH3COCH2COOH
(i)
70
71
(ii)
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b)
(1)
(ii)
(1)
(c)
3-oxobutanoic acid is a weak acid. The value of its acid dissociation constant, Ka, is
4
2.63 10 mol dm .
(i)
72
(1)
73
In parts (ii) and (iii) you may use HX as the formula for 3-oxobutanoic acid.
(ii)
Explain how a mixture of 3-oxobutanoic acid and its sodium salt can act as a buffer
solution when a small amount of alkali is added.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
74
(iii)
Calculate the mass of solid sodium 3-oxobutanoate that must be added to 100 cm
3
of a 0.500 mol dm solution of 3-oxobutanoic acid in order to make a buffer
solution of pH 3.80.
(5)
(Total 18 marks)
75
37.
(a)
Carboxylic acids react reversibly with alcohols, in the presence of a catalyst, to form an
ester and water.
When 24.8 g of ethane-1,2-diol, HOCH2CH2OH, was mixed with 66.0 g of ethanoic acid,
CH3COOH, in the presence of a catalyst, equilibrium was reached after 80.0% of the
3
CH3COOCH2CH2OOCCH3 + 2H2O
Write the expression for the equilibrium constant, Kc, and calculate its value. You should
make clear what units, if any, there are for Kc.
(7)
(b)
Ethane-1,2-diol can be made from ethene in a two-stage process. The overall reaction is:
1
C2H4 + H2O + 2 O2 HOCH2CH2OH
1054 g of ethane-1,2-diol was obtained from 560 g of ethene.
Calculate the percentage yield of the process.
(2)
76
77
(c)
Give the structural formula of a reagent that would react with ethane-1,2-diol to
make a polyester. Draw the structure of the polymer made from this reagent and
ethane-1,2-diol.
(3)
(ii)
Explain whether it would be sensible for protective clothing, made from this
polymer, to be used in an environment where acid spills are likely.
......................................................................................................................
......................................................................................................................
(1)
(d)
Explain why the ester methyl methanoate, HCOOCH3, has a much lower boiling
temperature than its isomer ethanoic acid, CH 3COOH, and why ethanoic acid has a lower
boiling temperature than propanoic acid, C2H5COOH.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(5)
(Total 18 marks)
78
79
38.
(i)
Draw a dot and cross diagram for methanol, showing outer shell electrons only.
(1)
(ii)
80
(b)
When methanol burns in a poor supply of air, one of the products is carbon monoxide.
A dot and cross diagram of carbon monoxide is shown below.
(i)
Draw the displayed formula for carbon monoxide. Show the TWO types of bond
which are present.
(1)
(ii)
The length of the bond between carbon and oxygen in methanol is 0.143 nm.
Would you expect the length of the bond between carbon and oxygen in carbon
monoxide to be longer, the same or shorter than this? Explain your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(c)
The energy of the bond between carbon and oxygen in methanol (the CO bond) can be
calculated from data on enthalpy changes of atomisation.
(i)
Write an equation, including state symbols, for the atomisation of one mole of
methanol vapour.
(1)
81
(ii)
Use the data below to calculate the energy of the CO bond in methanol.
at
= +2039 kJ mol
(2)
(iii)
Complete a balanced Hess cycle which you can use to calculate the standard
methanol vapour, DH at, given in (ii) and the data on enthalpy changes given
below. Write the correct numerical data beside the arrows in the cycle.
Equation
C(graphite) C(g)
O2(g) O(g)
H2(g) H(g)
82
(3)
(iv)
Methanol is a liquid at room temperature. Would you expect the standard enthalpy
change of formation of liquid methanol to be more or less negative than the value
you calculated in (iii)? Justify your answer.
................................................................................................................................
................................................................................................................................
(1)
(v)
(2)
Sri Lankan School
83
84
(d)
CH3OH(g)
H = 93.3 kJ mol
Decide whether a high or low temperature and a high or low pressure would give the
greater proportion of methanol at equilibrium. Justify your choice in each case.
Temperature ..................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
Pressure .........................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(2)
(Total 17 marks)
39.
In the first stage of an industrial process for purifying nickel, carbon monoxide is passed over
impure nickel at 323 K. Gaseous nickel tetracarbonyl, Ni(CO) 4, is formed.
Ni(s) + 4CO(g)
(a)
(i)
Calculate S
system
Ni(CO)4(g)
H = 191 kJ mol
S
1 1
/J mol K
Substance
Ni(s)
+29.9
CO(g)
+197.6
Ni(CO)4(g)
+313.4
(2)
85
(ii)
Refer to the equation above and comment on the sign of your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)
(iii)
Calculate S
surroundings
(2)
(iv)
(b)
(i)
Write the expression for the equilibrium constant, Kp, for this reaction.
(1)
86
(ii)
100 moles of gaseous carbon monoxide is mixed with excess solid nickel at 323 K
in a vessel kept at 1.00 atmosphere pressure. At equilibrium, 1.00 mole of the
carbon monoxide has reacted.
Complete the table below and then calculate the value of Kp at this temperature.
Include the units of Kp in your answer.
Substance
Moles at start
Ni(CO)4
CO
100
Moles at
equilibrium
99.0
(4)
87
(iii)
As Kp has such a small value, suggest THREE ways in which this industrial
process could be improved to increase profitability. Justify each of your
suggestions.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(3)
(c)
The second stage of this process is to recover the nickel from the nickel tetracarbonyl,
Ni(CO)4. By considering your calculations of the entropy changes, suggest how this
could be done. Justify your suggestion.
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(2)
(Total 16 marks)
88
40.
Consider the esterification of the amino acid alanine, which has the formula
CH3CH(NH2)COOH.
CH3CH(NH2)COOH + C2H5OH
(a)
(i)
CH3CH(NH2)COOC2H5 + H2O
(1)
(ii)
Using the average bond enthalpies given below, show that enthalpy change, DH,
for this reaction would be calculated as zero.
Average bond enthalpies / kJ mol
CO 358
OH 464
(2)
89
(iii)
On the basis that DH is zero, state what the effect of increasing the temperature
will be on:
the value of Kc ............................................................................................................
......................................................................................................................
the rate of attainment of equilibrium ..........................................................................
......................................................................................................................
(2)
(b)
(1)
(ii)
(iii)
Using equations, show how alanine can react with both acid and alkali.
(2)
90
91
(c)
(ii)
(2)
(iii)
How could the optical isomers of alanine be distinguished from each other?
......................................................................................................................
......................................................................................................................
(1)
(Total 13 marks)
41.
Draw the structure of part of the polymer, showing TWO repeating units.
92
(2)
93
(b)
Indicate on the profile the activation energy for the catalysed process.
Add another energy profile to the diagram for the polymerisation where a catalyst is not
used.
(3)
(c)
Explain, in terms of activation energy and the collision theory, why the rate of
polymerisation is greater when
(i)
a catalyst is used
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(1)
94
(ii)
42.
(a)
During the Haber process, for the production of ammonia, the following reaction occurs.
N2(g) + 3H2(g)
(i)
2NH3(g)
DH = 92 kJ mol
(ii)
State, with a reason, the effect of an increase in temperature on the position of the
equilibrium.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
95
(iii)
State, with a reason, the effect of an increase in pressure on the position of the
equilibrium.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b)
(i)
(ii)
(iii)
(c)
Write the equation for the reaction of sulphuric acid with excess ammonia and state a
large-scale use of the product.
Equation .................................................................................................................
Use of product ........................................................................................................
(2)
(Total 14 marks)
96
97
43.
In the manufacture of beer, brewers often add small amounts of salts of Group 2 elements to the
water used. These salts influence the chemical reactions during the brewing process.
Two such salts are calcium sulphate and magnesium sulphate.
(a)
A flame test can be used to confirm that a sample of a salt contains calcium ions.
(i)
(ii)
A positive test results in a brick-red flame colour. Describe the changes that occur
in calcium ions to produce a colour.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(iii)
Impurities in the salt may lead to other colours being observed in the flame.
What metal ion is likely to be present if a yellow flame is seen?
............................................................................................................................
(1)
98
(b)
Magnesium sulphate can be used in its anhydrous form, MgSO 4(s), or in its hydrated
form, MgSO4.7H2O(s).
An experiment was carried out to find the enthalpy change when hydrated magnesium
sulphate dissolved completely in water.
excess water
MgSO4.7H2O(s) MgSO4(aq) + 7H2O(l)
12.3 g of hydrated magnesium sulphate was added to 100 g of water in a simple
calorimeter and the temperature was found to fall by 1.1 C.
(i)
Calculate the energy change, in joules, that occurred in the experiment, using the
relationship
Energy change (J) = 4.18 mass of water temperature change
(2)
(ii)
(2)
(iii)
Use your answers to (i) and (ii) to calculate the enthalpy change for the reaction.
Include a sign and units in your final answer, which should be given to 2
significant figures.
(2)
Sri Lankan School
99
100
(c)
(i)
(1)
(ii)
Use your expression in (c)(i) and your answer from (b)(iii) to calculate Hr.
Include a sign and units in your final answer, which should be given to 2
significant figures.
(2)
(Total 15 marks)
44.
(i)
(1)
Sri Lankan School
101
102
(ii)
Draw the shape you would expect for the phosphine molecule, suggesting a value
for the HPH bond angle.
(iii)
Explain the shape of the phosphine molecule you have given in your answer in (ii).
Justify your value for the HPH bond angle.
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
(2)
(b)
(i)
103
(ii)
Use your answer to (i) and the data below to calculate the standard enthalpy change
of atomisation of phosphine at 298 K. Include a sign and units in your answer.
5.4 kJ mol
-1
-1
H f[PH3(g)]
=+
H at[P(s)]
= + 314.6 kJ mol
-1
(3)
(iii)
Calculate a value for the bond energy of the bond between phosphorus and
hydrogen, using your answer to (ii).
(1)
(Total 10 marks)
45.
104
(b)
(i)
240 K
185 K
Name the intermolecular force responsible for the higher boiling point of ammonia.
...........................................................................................................................
(1)
(ii)
Use displayed formulae to show this intermolecular bond between two ammonia
molecules.
Clearly mark and label the bond angle between the molecules.
(2)
(Total 4 marks)
46.
(a)
H = -129 kJ mol
The entropy of one mole of each substance in the equation, measured at 298 K, is shown
below.
Substance
S
-1 -1
/J mol K
CO(g)
197.6
H2(g)
130.6
CH3OH(l)
239.7
105
(i)
Suggest why methanol has the highest entropy value of the three substances.
.............................................................................................................................
.............................................................................................................................
(1)
(ii)
system,
(2)
(iii)
Is the sign of S
system
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
(1)
(iv)
surroundings,
at 298 K.
(2)
106
(v)
(2)
(b)
When methanol is produced in industry, this reaction is carried out at 400 C and 200
atmospheres pressure, in the presence of a catalyst of chromium oxide mixed with zinc
oxide. Under these conditions methanol vapour forms and the reaction reaches
equilibrium. Assume that the reaction is still exothermic under these conditions.
CO(g) + 2H2(g)
(i)
CH3OH(g)
(ii)
107
(iii)
Write an expression for the equilibrium constant in terms of pressure, Kp, for this
reaction.
CO(g) + 2H2(g)
CH3OH(g)
(1)
(iv)
(2)
(c)
The diagram below shows the distribution of energy in a sample of gas molecules in a
reaction when no catalyst is present. The activation energy for the reaction is EA.
108
(i)
(ii)
Draw a line on the graph, labelled EC, to show the activation energy of the
catalysed reaction.
(1)
(Total 17 marks)
47.
This question is about the chemical reaction between two gases, oxygen, O 2, and nitrogen
monoxide, NO.
2NO(g) + O2(g)
(a)
(i)
2NO2(g)
109
(ii)
Use the data below to calculate the enthalpy change for the reaction between
oxygen and nitrogen monoxide.
DH f (NO) = + 90 kJ mol
DH f (NO2) = + 34 kJ mol
(2)
(iii)
(3)
110
(iv)
On the basis of your calculation in (ii), state why you would expect the reaction to
take place.
..........................................................................................................................
......................................................................................................................
(1)
(v)
Explain why a reaction, which is expected to take place, may actually proceed so
slowly as to appear never to happen.
......................................................................................................................
......................................................................................................................
(1)
(b)
2NO2(g)
(ii)
State, with a reason, the effect on the position of equilibrium of increasing the total
pressure of the system at constant temperature.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
111
(iii)
Although the reaction is an equilibrium reaction, industrially this and other similar
reactions do not usually achieve equilibrium. Suggest why this is so.
......................................................................................................................
......................................................................................................................
(1)
(Total 15 marks)
48.
(a)
2NH3(g)
DH = 92.4 kJ mol
The usual conditions for this process are a catalyst of iron, a temperature of 400 C and a
pressure of 200 atmospheres.
Draw, on the axes below, an energy profile diagram for the uncatalysed reaction. Mark
on your diagram the activation energy and the enthalpy change.
E n th a lp y
E x te n t o f re a c tio n ( re a c tio n c o -o rd in a te )
(4)
112
(b)
(i)
Draw, on the axis below, the Maxwell-Boltzmann distribution that could apply at
400C and mark on your diagram the activation energies for the catalysed and the
uncatalysed reaction.
F ra c tio n o f
m o le c u le s o f
e n e rg y E
E n e rg y
(3)
113
(ii)
Use your diagram to explain why the reaction is faster in the presence of the iron
catalyst.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(c)
A mixture of nitrogen and hvdro2en is kinetically stable at 25C but kinetically unstable
at 400C. Explain why this is so.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
(Total 13 marks)
49.
(a)
(b)
The above titration was repeated, but this time the pH was measured throughout the
3
titration until a total of 50 cm of aqueous hydrochloric acid had been added. Carefully
sketch the pH curve you would expect for this titration. Name an indicator suitable for the
titration and use the curve to justify your choice.
(7)
114
115
(c)
50.
The quality of written communication will be assessed in this question. To gain full marks
you must explain your ideas clearly using equations and diagrams where appropriate.
This question is about the reaction sequence shown below
(a)
Compound A has the composition, by mass, 70.5% carbon, 13.7% hydrogen and 15.8%
oxygen. Show that this percentage composition is consistent with the molecular formula
C6H14O.
(2)
116
(b)
Deduce the displayed formula for A showing how you used each of the following pieces
of information.
1
Infra-red spectrum.
Mass spectrum.
(6)
117
Infra-red spectrum of A.
118
(c)
By drawing part of the chain formed from two monomer units, show the structural
formula of the polymer C.
(1)
119
(d)
Draw diagrams to show the two optical isomers of compound D and suggest how
they could be distinguished.
..........................................................................................................................
..........................................................................................................................
(2)
(ii)
(e)
(f)
120
121
51.
Nitrogen and phosphorus are in the same group of the Periodic Table. Phosphorus and hydrogen
form the compound phosphine, PH3, and nitrogen and hydrogen form ammonia, NH3.
(a)
(i)
State the number of bond pairs and lone pairs of electrons in a molecule of
phosphine.
Bond pairs of electrons: ..................... Lone pairs of electrons: ....................
(2)
(ii)
Use your answer to (i) to draw the shape of the molecule and indicate on your
diagram the approximate HPH bond angle that you would expect.
(2)
(b)
List all the intermolecular forces that exist between molecules of ammonia.
....
....
....
....
(2)
(ii)
Explain why the boiling temperature of phosphine is lower than that for ammonia.
....
....
....
....
(2)
122
(c)
Ammonia forms a dative covalent bond with H ions to form the ammonium ion, NH4 .
(i)
(ii)
(iii)
52.
This question is about phenol and benzoic acid, which are acidic, and benzaldehyde,
which is neutral.
Ka = 1.28 10
(a)
10
mol dm
Ka = 6.3 10 mol dm
123
124
(b)
Suggest chemical tests, with results, which would distinguish each of these compounds
from the others.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(5)
(c)
(d)
(i)
(1)
(ii)
Write an expression for the dissociation constant of benzoic acid in terms of the
appropriate equilibrium concentrations.
Ka =
125
(1)
126
(iii)
(3)
(iv)
State ONE of the assumptions that you made in your calculation in (d)(iii).
............................................................................................................................
............................................................................................................................
(1)
(e)
Under suitable conditions phenol reacts with benzoic anhydride, (C 6H5CO)2O, to form an
ester.
(i)
(ii)
(2)
127
(f)
53.
Methane, CH4, chloromethane, CH3Cl, and methanol, CH3OH, have molecules with similar
shapes but they have different boiling temperatures.
Compound
(a)
Boiling temperature
/C
Methane
162
Chloromethane
24
Methanol
+65
Draw a dot and cross diagram to show the bonding in chloromethane. You need only
draw the outer electrons of the atoms.
(2)
128
(b)
Draw a diagram to show the shape of the chloromethane molecule and explain why it has
this shape.
.................................................................................................................................
................................................................................................................................
(2)
(c)
Explain why the boiling temperature of chloromethane is higher than that of methane.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)
(d)
Explain why the boiling temperature of methanol is higher than that of chloromethane.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(3)
(Total 11 marks)
129
54.
(a)
(ii)
Give the expression for the acid dissociation constant, Ka, for aqueous ethanoic
acid.
(1)
(iii)
(3)
(b)
When ethanoic acid and propan-1-ol are heated together in the presence of a little
concentrated sulphuric acid an ester is produced.
(i)
(2)
130
(ii)
(iii)
(c)
6.00g of ethanoic acid was mixed with 6.00g of propan-1-ol and 0.00100mol of
concentrated sulphuric acid was added. The mixture was heated under reflux until no
further reaction was detectable. The mixture was then cooled rapidly to room temperature
3
3
and titrated with 1.00 mol dm sodium hydroxide solution. 35.0 cm of the 1.00 mol dm
3
sodium hydroxide solution was required for complete neutralisation.
(i)
Calculate the volume of sodium hydroxide solution that would have been needed if
only the 0.00100mol of concentrated sulphuric acid had been in the flask.
(2)
(ii)
Calculate the volume of sodium hydroxide solution that must have been needed to
react with the ethanoic acid remaining in the cooled mixture.
(1)
(iii)
131
(1)
132
(iv)
Hence, calculate the amount (in moles) of propan-1-ol, ester and water in the final
cooled mixture.
(3)
(v)
Calculate the value of the equilibrium constant under these conditions. The
3
volume of the reaction mixture should be taken as 100 cm .
(2)
(d)
Concentration of
sodium
hydroxide
3
/mol dm
0.1
1.0
6 10
0.1
2.0
1.2 10
0.2
2.0
2.4 10
Experiment
Rate of
reaction
/mol dm
3 1
s
4
133
(i)
sodium hydroxide...........................................................................................
(1)
(ii)
Calculate the value of the rate constant, k, for this reaction including its units.
(3)
(Total 23 marks)
55.
2NH3
DH = 92.4 kJ mol
(b)
Explain why raising the equilibrium temperature results in less ammonia being produced.
.................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)
134
(c)
State why, despite the lower yield of ammonia, the industrial process operates at about
450C.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)
(d)
(e)
(i)
(ii)
Draw an energy level diagram (energy profile) for the reaction with and without a
catalyst and use it to explain how a catalyst works.
E n e rg y
......................................................................................................................
......................................................................................................................
......................................................................................................................
Sri Lankan School
135
(4)
136
(iii)
(f)
(g)
The first stage in the conversion of ammonia to nitric acid involves mixing it with hot air
and passing the mixture over a catalyst.
Complete the equation for the first stage.
.... NH3 +.... O2 .... NO + .... H2O
(1)
(h)
The next stage involves the conversion of NO to nitrogen dioxide, NO by adding cold
air.
(i)
(ii)
56.
(a)
When solid sodium nitrate is heated with concentrated sulphuric acid the reaction shown
below occurs:
NaNO3 + H2SO4
HNO3 + NaHSO4
..........
..........
..........
..........
137
(i)
Identify the two conjugate acid-base pairs in this reaction. Write your answer in
the spaces below the equation.
(2)
138
(ii)
The nitric acid produced is evolved as a gas under these conditions. Explain the
effect of this on the position of equilibrium on heating the mixture in an open
container.
......................................................................................................................
......................................................................................................................
(2)
(iii)
O H
Draw a diagram of the likely shape of this molecule and justify your prediction.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(b)
Dilute sulphuric acid is a strong acid but very concentrated sulphuric acid is weak acid.
Explain the meanings of the terms weak and dilute as applied to acids.
Weak.......................................................................................................................
................................................................................................................................
Dilute.......................................................................................................................
................................................................................................................................
(2)
139
(c)
(ii)
Relate the ease of decomposition of the two nitrates to the relative sizes and
charges of the cations.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
(Total 13 marks)
57.
(a)
Phosgene, COCl2, was used in the First World War as a poison gas. It can be prepared by
reacting carbon monoxide with chlorine.
CO(g) + Cl2(g)
COCl2(g)
DH = 112 kJ mol
1.0 mol of carbon monoxide and 1.0 mol of chlorine were placed in a vessel and heated to
200 C. When equilibrium had been reached, it was found that the total pressure was
1.3 atm and that 85% of the carbon monoxide had reacted.
(i)
(1)
140
(ii)
(5)
(iii)
State and explain the effect that an increase in temperature would have on the value
of the equilibrium constant.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b)
The bond enthalpy of the bonds in carbon monoxide is +1065 kJ mol . The average C
1
1
O bond enthalpy is +360 kJ mol and that of C==O is +743 kJ mol . Use these data to
suggest the number of bonds in carbon monoxide.
(1)
(c)
Both phosgene and ethanoyl chloride, CH3COCl, contain a C==O group. Suggest an
equation for the reaction of phosgene with excess ammonia.
................................................................................................................................
(2)
141
(d)
The following reactions are those of compounds containing the C==O group. Draw the
structural formulae of the organic products of the reactions between:
(i)
(1)
(ii)
(1)
(iii)
(1)
(e)
(1)
(Total 15 marks)
142
58.
(a)
Benzocaine reacts with dilute acids to form the ion C 9H12O2N and with ethanoyl
chloride to form C11H13O3N.
When benzocaine is heated under reflux with aqueous sodium hydroxide and the
solution obtained is neutralised, two compounds X and Y are formed.
X has a formula of C7H7O2N and is a solid with a melting temperature of 190 C. It is
soluble in water.
Y is a volatile liquid with a formula C2H6O which gives steamy fumes with
phosphorus pentachloride.
X reacts with sodium hydrogencarbonate solution to give a gas which turns lime water
milky. It also reacts with a solution of sodium nitrite and hydrochloric acid between 0
C and 5 C to produce a substance which reacts with phenol to give an orange
precipitate, Z.
C 9H
12O 2
H + (a q )
C 9 H 11 O 2 N
B e n z o c a in e
C H 3C O Cl
11
13O 3
1 . N a O H ( a q ) h e a t/r e f lu x
2 . H C l(a q ) u n til n e u tra l
C 7H 7O 2N
X
N a H C O 3 (a q )
C 7H 6O 2N N a
(i)
C 2 H 6O
Y
1 . H N O 2 b e tw e e n 0 C a n d 5 C
2. phenol
o ra n g e p p t. Z
Deduce a structural formula for benzocaine and explain its three reactions shown
above. You may either describe the types of reaction or write the equations for the
reactions.
(6)
143
(ii)
Write equations for the two reactions of X. Include in your answer the structural
formula of Z.
(3)
(iii)
Explain why substance X has a fairly high melting temperature and why it is
soluble in water.
(3)
(b)
Substance X is a weak monobasic acid and for the purpose of the remainder of this
question you may write its formula as HA.
X has a relative molecular mass of 137, with a pKa value of 4.92 at 25 C.
(i)
(ii)
50.0 cm of this solution was mixed with 50.0 cm of a 0.100 mol dm solution of
sodium hydroxide. Calculate the concentration of the salt of X produced, and the
concentration of the acid X left unreacted.
Hence calculate the pH of the mixed solution.
(4)
(c)
The standard enthalpy change at 25 C for the neutralisation of a strong acid by a strong
1
base is 57.2 kJ mol .
The standard enthalpy change for the ionisation of the weak acid HA in water is
1
+8.3 kJ mol .
(i)
Write the ionic equation for the neutralisation of a strong acid by a strong base and
hence calculate the standard enthalpy of neutralisation of the acid HA.
(3)
(ii)
State and explain how the value of Ka of the acid X and hence the pH of the
solution in (b)(i) would change if the temperature of the solution were increased.
(2)
(Total 25 marks)
144
59.
Consider the following data for the hydrides of the Group 4 elements.
element
formula
of
hy
dri
de
boiling
temperat
ure
/K
relative
molecul
ar
mass
carbon
CH4
109
16
silicon
SiH4
161
32
germanium
GeH4
185
77
tin
SnH4
221
123
lead
PbH4
145
(a)
Represent the trend in the boiling temperature with relative molecular mass for these
hydrides.
350
B o ilin g
te m p e ra tu re
/K
300
250
200
150
100
50
50
100
150
200
250
R e la tiv e m o le c u la r m a s s
(2)
(b)
(i)
Account for the increase in boiling temperature as the relative molecular mass
increases.
............................................................................................................................
............................................................................................................................
(2)
146
(ii)
Use your diagram in (a) to suggest a likely value for the boiling temperature of
PbH4.
............................................................................................................................
(1)
(iii)
PbH4 is actually thermally unstable and unlikely to have the boiling temperature
you have suggested. Suggest why PbH4 is thermally unstable
............................................................................................................................
............................................................................................................................
(2)
(c)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(d)
(i)
147
(ii)
The successive ionisation energies of silicon are given in the table below.
number of ionisation
ionisation energy/kJ
-1
mol
789
1580
3230
4360
16100
19800
23800
29200
33900
10
38800
11
45900
12
505000
13
235000
14
258000
60.
(a)
148
(ii)
5.67 of propan-1-o1 was oxidised in a reaction with a 64% yield. Calculate the
mass of propanoic acid produced.
(3)
(b)
(i)
DH
= +6kJ mol
State and explain the effect on the position of this equilibrium of:
an increase in temperature;
............................................................................................................................
............................................................................................................................
(2)
(ii)
How does the addition of sodium propanoate affect the pH of the solution of
propanoic acid?
............................................................................................................................
(1)
149
(c)
(i)
Sketch, with reasonable accuracy, how the pH changes during the titration of
3
25cm of a weak acid, such as propanoic acid, with sodium hydroxide solution of
the same concentration.
14
12
10
pH
8
6
4
2
0
10
20
30
40
50
v o lu m e N a O H /c m
(ii)
pKind
Acid colour
Alkaline
colour
Bromophenol blue
4.0
yellow
blue
Bromothymol blue
7.0
yellow
blue
Thymol blue
8.9
yellow
blue
State which of these indicators would be best for this titration. Give a reason for
your choice.
Indicator ...........................................................................................................
Reason ..............................................................................................................
...........................................................................................................................
(2)
150
(d)
The standard enthalpy change of neutralisation of some acids with sodium hydroxide is
tabulated below:
Acid
(i)
DH /kJ
1
mol
51
12
57
57
Why are the values for the enthalpy change of neutralisation of the two strong
acids the same?
..........................................................................................................................
..........................................................................................................................
(1)
(ii)
Why is the enthalpy change of neutralisation of hydrocyanic acid so much less than
that of hydrochloric acid?
..........................................................................................................................
..........................................................................................................................
(2)
(Total 19 marks)
61.
(a)
DH /kJ
1
mol
C (graphite)
393.5
H2(g)
285.8
ethane C2H6(g)
1560.0
151
(i)
(ii)
Complete the following thermochemical equation for the standard enthalpy change
of combustion of ethane.
..C2H6(..)+..O2(..) ..CO2(..)+..H2O(..)
DH
=............................................
(3)
(iii)
Use the data to calculate the standard enthalpy change of formation of ethane.
Draw a Hesss Law cycle as part of your answer.
(3)
(b)
DH
= 112.6 kJ mol
This reaction does not proceed at room temperature in the absence of light, but reacts
rapidly when exposed to a bright light. Use these facts to illustrate the concept of
thermodynamic and kinetic stability.
Thermodynamic stability ...........................................................................................
....................................................................................................................................
Kinetic stability .........................................................................................................
....................................................................................................................................
(2)
152
(c)
Ethane and chlorine react in a homolytic free radical substitution reaction when
exposed to light. The two propagation steps are
H
C H
step 2
(i)
C l
C H
step 1:
C H
C
H
C l
C l
C H
Cl
C l
Cl
(ii)
(iii)
(iv)
153
(d)
The reaction of ethane with bromine proceeds in a similar way. Given the following
1
average bond enthalpies in kJ mol
CH + 412
HBr + 366
calculate the enthalpy change for step 1 of the reaction involving bromine.
(2)
(e)
[CN ]/mol dm
[C2H5Br]/mol
3
dm
Initial rate/mol dm
3 1
s
0.060
0.020
1.0 10
0.060
0.040
2.0 10
0.120
0.020
2.0 10
(3)
(f)
CN
+ C H 3C H 2B r
H
C H 3
N C .... C .......... B r
C H 3CH 2C N + Br
154
Route II
C H 3C H 2B r
s lo w
then C H 3 C H
(i)
+
2
C H 3C H
+ CN
fast
+
2
+ B r
CH 3CH 2CN
(ii)
This exothermic reaction is catalysed by iodide ions. Draw the enthalpy level
diagram for both the uncatalysed reaction, labelling each clearly.
e n th a lp y
(3)
(Total 24 marks)
62.
(a)
(i)
PCl3(g) + Cl2(g)
(ii)
155
(2)
156
(iii)
Given that PCl5 is 33% dissociated at 700 K and 1.1 atm total pressure, find the
value of Kp under these conditions.
(3)
(iv)
The enthalpy of formation of PCl5(g) is 399kJ mol , and that for PCl3(g) is
1
(v)
State and explain the effect on the equilibrium position of this reaction if the
temperature were to be increased.
(2)
(c)
Phosphorus pentachloride also reacts with alcohols, but cannot be used as a definitive
qualitative test for them. Why is the reaction of alcohols with phosphorus pentachloride
not a definitive test?
(1)
(d)
(e)
Chloroalkanes can be made from alcohols and sodium chloride in 50% aqueous sulphuric
acid. A similar reaction is unsuitable for the production of iodoalkanes using sodium
iodide. By comparison of the reactions of sodium chloride and sodium iodide with
sulphuric acid, explain why this is so.
(4)
(Total 17 marks)
63.
157
158
(a)
(ii)
State, with a reason, the number of geometric isomers that sorbic acid has.
(2)
(b)
(ii)
Write the chemical equations that are relevant to the functioning of the mixture as a
buffer, and use them to explain how buffering action arises. You may represent
sorbic acid as RCOOH and potassium sorbate as RCOOK.
(5)
(c)
Write an equation for the complete reaction of sorbic acid with bromine.
(1)
(ii)
(d)
The bromine-containing product from (c)(i) can be reacted with sodium hydroxide in
aqueous ethanol to give a substitution reaction.
(i)
Explain why aqueous ethanol is used as the solvent rather than, say, ethanol alone.
(2)
(ii)
159
(e)
(ii)
Soaps are in general made by the alkaline hydrolysis of fats. Write an equation to
illustrate this reaction.
(3)
(Total 25 marks)
160