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(Total 1 mark)
2.
This question is about methanol and the energy changes that accompany some of its reactions.
(a)
Complete the diagram (using dots and crosses) to show the bonding in methanol, CH 3OH.
You should show outer electrons only.
(2)
(b)
The Hess cycle below can be used to calculate the standard enthalpy change of
combustion of methanol, using standard enthalpy changes of formation.
(i)
(ii)
Define the term of a compound, making clear the meaning of standard in this
context.
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(3)
(iii)
Use your cycle and the data below to calculate the standard enthalpy change of
combustion of methanol, Hc
Hf /kJ mol
CO2(g)
393.5
H2O(l)
285.8
CH3OH(l)
239.1
(2)
(c)
An experiment was carried out, using the apparatus below, to estimate the standard
enthalpy change of combustion of methanol.
After burning the methanol for a few minutes, the temperature of water in the beaker had
risen by 20.7 C and the mass of methanol burnt was 0.848 g.
(i)
(ii)
Calculate the number of moles of methanol, CH 3OH, burnt during the experiment.
(1)
(iii)
Use your answers to (c)(i) and (ii) to calculate the experimental value for the
standard enthalpy change of combustion. Include a sign and units in your answer,
which should be given to three significant figures.
(1)
(iv)
Compare your answers to (b)(iii) and (c)(iii) and give TWO reasons to explain any
differences.
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(2)
(Total 14 marks)
3.
Which of the following is true for the exothermic reaction shown below?
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
A
positive
Ssurroundings positive
Ssystem
negative
Stotal
negative
(Total 1 mark)
4.
(a)
Crystals of hydrated cobalt(II) chloride, CoCl 2.6H2O, lose water when they are heated,
forming anhydrous cobalt(II) chloride, CoCl2.
CoCl2.6H2O(s) CoCl2(s) + 6H2O(l)
(i)
Calculate the entropy change of the system, S system, at 298 K. Include a sign and
units in your answer. You will need to refer to your data booklet.
(2)
(ii)
Explain whether the sign of your answer to (a)(i) is as expected from the equation
for the reaction.
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(1)
(iii)
The standard enthalpy change for the reaction, H , is +88.1kJ mol . Calculate
the entropy change in the surroundings, S surroundings, at 298 K for this reaction.
Include a sign and units in your answer.
(2)
(iv)
total,
(v)
Does your answer to (a)(iv) indicate whether hydrated cobalt(II) chloride can be
stored at 298 K without decomposition? Explain your answer.
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(1)
(b)
The student used a balance which reads to 0.01g, a 50.0 cm pipette, and a thermometer
which can be read to 0.25 C.
(i)
(ii)
Suggest ONE other change the student could make to give a result which is closer
to the accepted value. Justify your suggestion.
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(2)
(c)
The lattice energies of magnesium chloride, MgCl 2, calcium chloride, CaCl2, and
strontium chloride, SrCl2 are shown in the table below.
Chloride
(i)
MgCl2
2526
CaCl2
2258
SrCl2
2156
Use data on ionic radii, from your data booklet, to explain the trend in these values.
Estimate a value for the lattice energy of cobalt(II) chloride, giving ONE piece of
data to justify your estimate.
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(4)
(ii)
Explain how lattice energy values, together with other data, can be used to predict
the solubility of ionic compounds.
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(3)
(d)
Cobalt forms another chloride, CoCl 3, but scientists predict that MgCl3 cannot be made.
Suggest a reason for this.
You should consider the enthalpy changes in the Born-Haber cycle, which provide
evidence about why cobalt(III) chloride is known but magnesium(III) chloride is not.
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(2)
(Total 20 marks)
5.
Which equation represents the reaction for which the enthalpy change is the standard enthalpy
6.
Which equation represents the reaction for which the enthalpy change, H, is the mean bond
enthalpy of the CH bond?
A
7.
Magnesium chloride can be made by reacting solid magnesium carbonate, MgCO 3, with dilute
hydrochloric acid.
(a)
(b)
Give TWO observations you would make when the reaction is taking place.
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(2)
(c)
(ii)
What mass of magnesium carbonate, in grams, reacts with this amount of acid?
(1)
(iii)
Suggest why slightly more than this mass of magnesium carbonate is used in
practice.
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(1)
(iv)
How would you separate the magnesium chloride solution from the reaction
mixture in (iii)?
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(1)
(v)
The magnesium chloride solution was left to crystallise. The crystals were
separated and dried carefully. A sample of 3.75g of hydrated crystals, MgCl 2.6H2O,
1
which have molar mass 203.3 g mol , was obtained. Calculate the percentage
yield of this reaction.
(2)
(vi)
Give ONE reason why the yield of crystals is less than 100%, even when pure
compounds are used in the preparation.
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(1)
10
(d)
Lattice energies can be measured using the Born-Haber cycle, or calculated from
electrostatic theory. Lattice energies of magnesium chloride and magnesium iodide are
shown below
Lattice energy from
Born-Haber cycle using
experimental data
1
/ kJ mol
MgCl2
2526
2326
MgI2
2327
1944
Salt
(i)
/ kJ mol
What does this data indicate about the bonding in magnesium chloride?
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(1)
(ii)
11
(e)
Blood plasma typically contains 20 parts per million (ppm) of magnesium, by mass.
(i)
(ii)
Magnesium chloride can be used as a supplement in the diet to treat patients with
low amounts of magnesium in the blood. Suggest ONE property which makes it
more suitable for this purpose than magnesium carbonate.
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(1)
(Total 16 marks)
8.
What test would you use to distinguish between hexane and hex-1-ene? Give the results
of the test for each substance.
Test: ............................................................................................................................
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Result with hexane: ....................................................................................................
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Result with hex-1-ene: ................................................................................................
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(2)
12
(b)
(1)
(ii)
Explain why stereoisomerism can occur in alkenes, and why hex-2-ene has
stereoisomers but hex-1-ene does not.
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(2)
(c)
The enthalpy change of combustion of hexane was measured using a spirit burner to heat
a known mass of water in a calorimeter. The temperature rise of the water was measured.
The results of the experiment are shown below.
Mass of hexane burnt
0.32 g
50 g
22 C
68 C
1
Calculate the energy in joules produced by burning the hexane. Use theexpression
energy transferred = mass specific heat capacity temperature change.
(1)
(ii)
13
(iii)
The value for the enthalpy change of combustion in this experiment is different
from the value given in data books. Suggest TWO reasons for this difference.
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(2)
(iv)
(d)
14
(ii)
The enthalpy change of this reaction Hreaction can be calculated from the following
enthalpy changes of combustion.
Substance
Hex-1-ene, C6H12
4003
Hydrogen, H2
286
Hexane, C6H14
4163
Complete the Hess cycle by adding labelled arrows. Use your cycle to calculate the
enthalpy change Hreaction.
(3)
15
(iii)
The enthalpy change for the reaction of some other alkenes with hydrogen is
shown below.
Reaction
/ kJ mol
C3H6 + H2 C3H8
4003
C4H8 + H2 C4H10
286
C5H10 + H2 C5H12
4163
9.
at 100 C, water has a higher concentration of hydrogen ions than of hydroxide ions.
(Total 1 mark)
16
10.
Some mean bond enthalpy values are given in the table below.
Bond
HH
+436
II
+151
HI
+299
What is the enthalpy change for the reaction shown below in kJ mol ?
H2(g) + I2(g) 2HI(g)
A
11.
HF
HCl
HBr
HI
(Total 1 mark)
17
12.
The Born-Haber cycle for the formation of sodium chloride from sodium and chlorine may be
represented by a series of steps labelled A to F as shown.
18
(a)
(i)
Complete the table below by adding the letters A to F next to the corresponding
energy changes.
Energy change
Letter
H
1
/kJ mol
775
+109
+121
+494
411
(3)
(ii)
Calculate the first electron affinity of chlorine, in kJ mol , from the data given.
(2)
19
(b)
Lattice energies can be calculated from electrostatic theory (theoretical values) as well as
by Born-Haber cycles (experimental values).
(i)
Compound
NaCl
770
766
Agl
889
778
Comment on the fact that there is close agreement between the values for sodium
chloride, NaCl.
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(1)
(ii)
Explain, in terms of chemical bonding, why the experimental value for silver
iodide, AgI, is more exothermic than the value calculated theoretically for the same
compound.
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(2)
20
(c)
Suggest why the first ionization energies of the Group 1 elements decrease down the
group.
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(2)
(Total 10 marks)
21
13.
Propanone, C3H6O, undergoes complete combustion to form carbon dioxide and water.
C3H6O(l) + 4O2(g) 3CO2(g) + 3H2O(l)
(a)
(1)
(ii)
specific heat
energy transferred (J) = mass
capacity
temperature
change
to calculate the heat energy transferred to raise the temperature of 200 g of water
from 20.2 C to 78.4 C.
(2)
(iii)
Use your answers to (a)(i) and (ii) to calculate a value for the enthalpy change of
combustion of propanone. Give your answer to three significant figures and
include a sign and units.
(3)
22
(b)
In another experiment, the enthalpy change of combustion for butanone, C 4H8O, was
1
Suggest a reason why the value obtained in the experiment is so different from the
Data Book value.
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(1)
(ii)
This Data Book value (2440 kJ mol ) refers to the following equation.
C4H8O(l) +
11
How would the value be different if it referred to the formation of water in the
gaseous state? Justify your answer.
Difference.........................................................................................................
Justification.......................................................................................................
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(2)
(c)
Standard enthalpy changes of combustion can be used to calculate the standard enthalpy
change of formation of a compound.
(i)
Define the term standard enthalpy change of formation, making clear the
meaning of standard in this context.
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(3)
23
(ii)
Use the standard enthalpy changes of combustion, Hc , given in the table below
to find the standard enthalpy change of formation for ethanoic acid, CH 3COOH, in
1
kJ mol .
Substance
Hc
/ kJ mol
C(s, graphite)
394
H2(g)
286
CH3COOH(l)
870
14.
In the reaction profile below, which energy change would alter if a catalyst was added to the
reaction?
24
A
B
C
D
(Total 1 mark)
15.
Which equation represents the reaction for which the enthalpy change is the lattice energy of
sodium fluoride, NaF?
A
(Total 1 mark)
16.
Theoretical lattice energies can be calculated from electrostatic theory. Which of the following
+
affects the magnitude of the theoretical lattice energy of an alkali metal halide, M X ?
A
(Total 1 mark)
25
17.
enthalpy of reaction
enthalpy of combustion
bond enthalpy
(a)
H = p
A
B
C
D
(1)
(b)
H = 4q
A
B
C
D
(1)
26
(c)
H2C=CH2(g) + O2(g)
H = r
A
B
C
D
(1)
(Total 3 marks)
18.
Which of the equations shown below represents the reaction for which H is the standard
enthalpy change of formation, H f 298, for ethanol, C2H5OH. Ethanol melts at 156 K and boils
at 352 K.
A
19.
Airbags, used as safety features in cars, contain sodium azide, NaN3. An airbag requires a large
volume of gas to be produced in a few milliseconds. The gas is produced in this reaction:
2NaN3(s) 2Na(s) + 3N2(g)
H is positive
27
(a)
[The Avogadro constant = 6.02 10 mol . The molar volume of nitrogen gas under the
3
1
conditions in the airbag is 24 dm mol ].
(2)
(b)
Calculate the mass of sodium azide, NaN3, that would produce 50 dm of nitrogen gas.
(3)
(c)
What will happen to the temperature in the airbag when the reaction occurs?
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(1)
28
(d)
The airbag must be strong enough not to burst in an accident. An airbag which has burst
in an accident is hazardous if the sodium azide in it has decomposed.
Explain why this is so.
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(2)
(Total 8 marks)
20.
A student investigated a reaction which could be used to warm up coffee in self-heating cans.
Mg(s) + Cu(NO3)2(aq) Mg(NO3)2(aq) + Cu(s)
In the self-heating cans, the bottom has a compartment containing copper(II) nitrate solution.
When a button on the bottom of the can is pressed, the magnesium powder is released into the
compartment where it reacts with the copper(II) nitrate solution.
(a)
50.0 cm of 0.300 mol dm copper(II) nitrate solution into a 100 cm3 beaker and adding
1g (an excess) of magnesium powder.
The results are shown below.
Temperature of copper(II) nitrate solution at start
Temperature of mixture after reaction
(i)
= 22 C
= 43 C
Calculate the energy change which took place. The specific heat capacity of the
1 1
solution is 4.20 J g K .
Which is the correct value for the energy change in joules?
(1)
29
(ii)
(1)
(iii)
Calculate the enthalpy change for the reaction. You should include a sign and units
in your answer.
(2)
(iv)
Suggest two changes you would make to the equipment used in order to improve
the accuracy of the result.
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(2)
30
(b)
2+
H= 532 kJ mol
(ii)
(c)
The temperature in the self-heating can needs to increase by 60 C to produce a hot drink.
Suggest a change you could make to the mixture in the experiment in (a) to produce a
greater temperature rise. You are not expected to do a calculation.
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(1)
(Total 11 marks)
31
21.
The following data can be used in a Born-Haber cycle for copper(II) bromide, CuBr 2.
+111.9 kJ mol
+338.3 kJ mol
+746.0 kJ mol
+1958.0 kJ mol
342.6 kJ mol
141.8 kJ mol
(a)
2 B r(g )
C u B r2(s)
B
C
D ...........................................
C u (s ) + B r2(l)
(3)
(b)
Use the data to calculate a value for the lattice energy of copper(II) bromide.
Give a sign and units in your answer.
(3)
32
(c)
When the lattice energy of copper(II) bromide is calculated from ionic radii and charges,
the result is a value numerically about 10% less than the one obtained from the BornHaber cycle.
(i)
What does this suggest about the nature of the bonding in copper(II) bromide?
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(1)
(ii)
Draw a diagram to show how the smaller copper ion alters the shape of the larger
bromide ion.
(1)
(Total 8 marks)
33
22.
An experiment was carried out to measure the enthalpy change for the reaction of zinc with
aqueous copper(II) sulphate.
The equation for the reaction is
Zn + CuSO4 ZnSO4 + Cu
A measuring cylinder was used to transfer separate 50 cm3 samples of 1.25 mol dm3
copper(II) sulphate solution into polystyrene cups.
Each mixture was stirred thoroughly and the temperature rise noted with a thermometer
accurate to 0.5 C.
6 0 .0
5 0 .0
T e m p e ra tu re
c h a n g e / C
4 0 .0
3 0 .0
2 0 .0
1 0 .0
0 .0
0 .0 0
(a)
1 .0 0
2 .0 0 3 .0 0 4 .0 0 5 .0 0
M a s s o f z in c / g
6 .0 0
7 .0 0
Explain why the graph initially shows a rise in temperature and then levels off.
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(2)
34
(b)
(i)
Suggest why the mass of metal is not used in the calculation of the heat change.
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(1)
(ii)
The graph shows that the maximum temperature change is 63.5 C. Use this value
to calculate the maximum heat change, in joules, in this reaction.
3
You should assume that the density of the solution is 1.00 g cm and its heat
1
1
capacity is the same as water, 4.18 J g C .
(1)
(iii)
From the heat change calculated in (b)(ii) calculate the enthalpy change, in kJ mol
1
, for the reaction. Include the appropriate sign and give your answer to three
significant figures.
(4)
35
(c)
(i)
(ii)
Suggest a simple practical change to the method that would make the experiment
more accurate.
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(1)
(Total 10 marks)
23.
(a)
The following data were collected to use in a Born-Haber cycle for silver fluoride, AgF.
Value
1
/kJ mol
enthalpy of atomisation of silver
+285
+731
+79
205
958
36
On the following outline of a Born-Haber cycle, complete boxes A and B by adding the
formula and state symbol for the appropriate species. Write the name of the enthalpy
change at C.
A g + (g )
B ox
A
F (g )
A g F (s)
C ............................................
B ox
B
............................................
A g (s) + F 2(g )
(3)
(b)
Hlatt (theoretical) is the lattice energy calculated assuming the crystal lattice is
completely ionic.
Hlatt (experimental) is the lattice energy determined experimentally using the BornHaber cycle.
Values for the silver halides are listed below.
Formula of halide
Hlatt
(theoretical)
/ kJ mol
Hlatt
(experimental)
/ kJ mol
Hlatt (theoretical)
minus
Hlatt (experimental)
/ kJ mol
AgF
920
958
38
AgCl
833
905
72
AgBr
816
891
75
AgI
778
889
111
37
(i)
Explain why the theoretical lattice energies become less exothermic from AgF to
AgI.
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(3)
(ii)
Explain why the values of the theoretical and experimental lattice energies are
different.
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(2)
(iii)
Explain why the difference between the theoretical and experimental lattice
energies increases from AgF to AgI.
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(2)
(Total 10 marks)
38
24.
(i)
Use the data below to calculate a value for the enthalpy change of solution, Hsolution, for
silver fluoride.
Value
1
/kJ mol
lattice energy of AgF (s)
958
+
464
506
(2)
(ii)
Use your answer to part (c)(i) to suggest whether you would expect silver fluoride, AgF,
to be soluble or insoluble in water at room temperature.
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(2)
(Total 4 marks)
39
25.
However, by determining the enthalpy change for the neutralisation of the two potassium salts
with hydrochloric acid, H for the reaction above can be found. The equations for the
neutralisation reactions are:
K2CO3 + 2HCl 2KCl + H2O + CO2
H1
H2
30 cm of 2 mol dm hydrochloric acid (an excess) was placed in a polystyrene cup, and
its temperature measured to the nearest 0.1C.
A weighed quantity of the potassium salt (either the carbonate or the hydrogencarbonate)
was added to the acid with rapid stirring, and the temperature measured again when the
reaction was complete.
For the neutralisation using potassium carbonate, the results were as follows:
Amount of potassium carbonate used = 0.0187 mol
Initial temperature = 23.7 C
Final temperature = 30.1 C
(a)
40
(b)
Use the data for the neutralisation of potassium carbonate to calculate the value of H1 to
two significant figures. Remember to include a sign and units in your answer.
[Assume that the heat capacity of the solution is 4.18 J g
30 g.]
(3)
(c)
(i)
Show how the two equations for the neutralisation reactions and their H values
can be combined to find a value of H for the thermal decomposition of potassium
hydrogencarbonate.
Calculate this enthalpy change using your value for H1 from part (b), given that
1
H2 = + 29.3 kJ mol .
(3)
41
(ii)
Explain why you would need to include the enthalpy of vaporisation of H 2O(l), in
order to obtain an accurate value of the enthalpy of decomposition of potassium
hydrogencarbonate.
2KHCO3(s)
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(1)
(d)
State and explain the effect of a decrease in temperature on the value of the equilibrium
constant for the decomposition reaction and hence on the composition of the equilibrium
mixture.
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(2)
(Total 10 marks)
26.
The Hess cycle below can be used to find the enthalpy change, Hr, for the reaction between
hydrogen sulphide and sulphur dioxide, using standard enthalpy changes of formation.
S O 2 (g ) + 2 H 2 S (g )
H
3 S (s ) + 2 H 2O (l)
H
42
(i)
(ii)
(iii)
Use the cycle and the data below to calculate the enthalpy change of the reaction, Hr.
Hf / kJ mol
SO2 (g)
296.8
H2S (g)
20.6
H2O (l)
285.8
(2)
(Total 7 marks)
27.
This question is about ammonia, NH3, which is produced as shown in the following equation.
N2(g) + 3H2(g)
(a)
2NH3(g)
43
(b)
(i)
Use the average (mean) bond enthalpy data to calculate a value for the enthalpy
change for this reaction. You are reminded to show all your working.
Bond
NN
944
HH
436
NH
388
(3)
(ii)
The actual standard enthalpy change for this reaction is 92 kJ mol . Explain why
the value you calculated in (b)(i) is not the same as this.
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(1)
44
(iii)
45
(c)
The manufacturer of ammonia would like to achieve a high rate of reaction and a high
equilibrium yield of product.
(i)
State and explain, in terms of collision theory, TWO ways to increase the rate of
the reaction. An increase in pressure does not alter the rate in this process.
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(6)
46
(ii)
State and explain TWO ways to increase the equilibrium yield of ammonia.
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(4)
(Total 19 marks)
28.
The enthalpy change for the reaction between aqueous sodium hydroxide solution and aqueous
hydrochloric acid was determined by the following method:
3
Aqueous hydrochloric acid was titrated against 25.0 cm of 1.50 mol dm aqueous
sodium hydroxide solution using a suitable indicator. The mean (or average) titre was
3
22.75 cm .
25.0 cm of the sodium hydroxide solution was carefully measured into a polystyrene cup
3
and 22.75 cm of the hydrochloric acid was transferred to a clean dry beaker.
Both solutions were allowed to stand for five minutes before their temperatures were
noted.
The hydrochloric acid was then added to the sodium hydroxide solution, the mixture
stirred thoroughly and the highest temperature noted.
The experiment was repeated three times giving an average temperature change of
+10.5C.
47
(a)
(i)
and its
(2)
(ii)
(3)
(b)
State ONE assumption made when calculating this enthalpy change, other than those
stated in (a)(i).
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 6 marks)
48
29.
The Born-Haber cycle below represents the enthalpy changes when calcium hydride, CaH 2, is
formed from its elements.
C a 2+ (g ) + 2 e + 2 H (g )
H
C a 2+ (g ) + 2 e + H 2 (g )
H
C a 2+ (g ) + 2 H (g )
C a (g ) + H 2 (g )
C a (s) + H 2 (g )
H
C a H 2 (s)
(a)
(ii)
49
(b)
Use the data below to calculate the standard enthalpy of formation of calcium hydride,
CaH2(s).
value
1
/kJ mol
enthalpy of atomisation of calcium
+178
+1735
+218
73
2389
Calculation:
(2)
(c)
Explain why the lattice energy of magnesium hydride, MgH 2(s), is more exothermic than
the lattice energy of calcium hydride, CaH2(s).
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 7 marks)
50
30.
Two experiments were carried out in order to calculate the enthalpy change of formation of
magnesium carbonate, MgCO3.
A Hess cycle for these reactions is shown below.
M g
E x p e r im e n t 1
+ 2 H C l(aq )
M g C l2 (a q ) + H 2 (g ) + C
M g C O 3(s)
+ 2 H C l (aq )
E x p e r im e n t 2
H 2 = 6 8 0 k J m o l1
M g C l2 (a q ) + H 2O (l) + C O 2 (g )
(a)
Complete the Hess cycle above for the formation of magnesium carbonate from its
elements by balancing the equations and adding state symbols.
(2)
(b)
Temp / C
21.0
21.0
25.3
25.1
24.9
24.8
24.7
(i)
51
(ii)
(3)
(iii)
(2)
52
(iv)
Calculate the energy change in this experiment assuming the temperature rise is
4.5 C. Use the expression
Energy change (J) = 4.2 mass of solution temperature change
3
(1)
(v)
Use your answer to (iv) to calculate H1 for one mole of magnesium reacting with
hydrochloric acid. Include a sign and units in your answer.
(2)
(vi)
Suggest why a temperature rise of 4.5 C was used in the calculation in (iv).
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
53
(c)
2.2 g of magnesium carbonate was added to 100 cm of the same acid in Experiment 2.
The temperature changed from 21.0 C to 23.5 C resulting in an energy change of
1.05 kJ.
(i)
Calculate the mass of one mole of magnesium carbonate, MgCO3 and hence the
number of moles of magnesium carbonate used in this experiment.
Use the Periodic Table as a source of data.
(2)
(ii)
(1)
54
(d)
Using your answers to (b)(v) and (c)(ii), calculate the enthalpy change of formation, Hf,
of magnesium carbonate, MgCO3.
Include a sign and units in your answer.
(2)
(e)
31.
H f [SiCl4(g)].
Your answer should include a sign and units.
Use the Hess cycle below and the following data at 298 K.
H ato [Si(s)]
= +455.6 kJ mol
H ato [Cl ]
2
= +121.7 kJ mol
= +407.4 kJ mol
S i(g ) + 4 C l(g )
S iC l4(g )
H
[S iC l4(g )]
S i(s ) + 2 C l2(g )
(Total 3 marks)
55
32.
(a)
When excess chlorine and methane are mixed at room temperature and pressure no
reaction takes place but when ultraviolet light is shone into the mixture an explosion
occurs, producing carbon and hydrogen chloride.
uv
CH4(g) + 2Cl2(g) C(s) + 4HCl(g)
H = 219 kJ mol
(2)
56
(b)
Draw a labelled reaction profile for the reaction between methane and chlorine and use it
to explain why the reaction does not take place unless ultraviolet light is present.
E n th a lp y
P ro g re s s o f re a c tio n
Explanation
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(5)
(Total 7 marks)
33.
(a)
57
(b)
The following standard enthalpies of combustion are needed to calculate the standard
enthalpy of formation of ethanol, C2H5OH.
Standard enthalpy of
1
combustion /kJ mol
Substance
(i)
394
hydrogen, H2(g)
286
1371
Complete the Hesss Law cycle by filling in the box and labelling the arrows with
the enthalpy changes.
H
C 2H 5O H (l) + 3 O 2(g )
...........................
...........................
...........................
...........................
............................... + ...............................
(3)
(ii)
Use your Hesss Law cycle to calculate the standard enthalpy of formation of
ethanol.
(2)
(Total 8 marks)
58
34.
The apparatus used and the recordings made by a student, carrying out an experiment to
determine the enthalpy of combustion of methanol, are shown below.
Diagram
th e rm o m e te r
beaker
w a te r
s p irit la m p
m e th a n o l
Results
1
Observations
When the spirit lamp was being weighed its mass was continually falling.
A black substance formed on the bottom of the beaker as the methanol burned.
59
(a)
(i)
(2)
(ii)
Calculate the heat gained by the water. Give your answer in kJ.
(2)
(iii)
Use your values from (i) and (ii) to calculate the enthalpy of combustion of
1
methanol in kJ mol . Include a sign with your answer.
H = ........................................ kJ mol
(2)
(b)
(i)
(1)
60
(ii)
Calculate the maximum temperature change that could have occurred during the
experiment.
(1)
(c)
(i)
Give a reason why the mass of the spirit lamp fell as it was being weighed.
...........................................................................................................................
...........................................................................................................................
(1)
(ii)
Suggest the identity of the black substance that forms on the beaker. State the effect
on the value of the enthalpy of combustion obtained.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 11 marks)
61
35.
(a)
An incomplete Born-Haber cycle for the formation of magnesium oxide, MgO, from its
1
constituent elements is shown below. All numerical values are in kJ mol .
= +657
M g 2+ (g ) + O (g ) + 2 e
e n th a lp y o f a to m is a tio n
of oxygen = +249
M g 2+ (g ) +
1
2
O 2 (g ) + 2 e
f ir s t p lu s s e c o n d
io n is a tio n e n e rg y o f
m a g n e s iu m = + 2 1 8 6
la ttic e e n e rg y o f
m a g n e s iu m o x id e
M g (g ) +
H
O 2 (g )
1
2
O 2 (g )
= +150
M g (s) +
H
(i)
1
2
= 602
M g O (s)
Complete the empty box on the cycle by writing in the formulae of the missing
species. State symbols are required.
(1)
(ii)
62
(iii)
Use the Born-Haber cycle to calculate the lattice energy of magnesium oxide.
(2)
(b)
Magnesium iodide is another compound of magnesium. The radius of the magnesium ion
is 0.072 nm, whereas the radius of the iodide ion is much larger and is 0.215 nm.
(i)
Describe the effect that the magnesium ion has on an iodide ion next to it in the
magnesium iodide lattice.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(ii)
What TWO quantities must be known about the ions in a compound in order to
calculate a theoretical lattice energy?
...........................................................................................................................
...........................................................................................................................
(2)
63
(iii)
Suggest how the value of the theoretical lattice energy would compare with the
experimental value from a Born-Haber Cycle for magnesium iodide.
Give a reason for your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 11 marks)
36.
(i)
64
(ii)
The table below gives some information about the sulphates of the Group 2 elements
magnesium and barium.
sulphate
lattice energy
/ kJ mol
hydration
enthalpy of cation
1
/ kJ mol
MgSO4
2874
1920
BaSO4
2374
1360
solubility
3
/ mol dm
1.83
9.43 10
Use the lattice energy and hydration enthalpy values to explain the difference in the
solubility of the two salts.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(Total 6 marks)
65
37.
(b)
(i)
NH3(g)
46.1
NO(g)
+ 90.2
H2O(g)
242
(2)
66
(ii)
(1)
(c)
Whenever ammonia is oxidised, the two reactions occur at the same time: they are
competing reactions.
(i)
Suggest, with a reason, which reaction you would expect to be more likely
thermodynamically.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(ii)
Explain how the use of a catalyst can favour Reaction I over Reaction II.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(d)
In the nitration of benzene, a mixture of concentrated nitric and sulphuric acids is used at
a temperature not exceeding 55 C.
(i)
What is the reason for using sulphuric as well as nitric acid? Support your answer
with an equation.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
67
(ii)
On the basis of your answer to (d)(i), which of nitric and sulphuric acid is the
stronger acid? Give a reason.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(iii)
(3)
(iv)
(1)
(v)
Explain, in terms of structure and energetics, why benzene usually reacts via
substitution rather than addition.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(Total 18 marks)
68
38.
Calcium hydroxide decomposes on strong heating to form calcium oxide and water.
Ca(OH)2(s) CaO(s) + H2O(l)
Two samples of calcium hydroxide were taken, each weighing exactly 1.00 g.
3
The first sample was cautiously added to 25.0 cm of dilute hydrochloric acid contained in a
glass beaker. The temperature rise was measured and found to be 16.5 C.
The other sample was heated for some time. It was then allowed to cool and then added to
another 25.0 cm3 portion of hydrochloric acid as before. In this case the temperature rose by
25.5 C.
In both cases, the acid used was an excess.
(a)
(i)
Calculate the energy produced by the reaction of each solid with the acid.
Use the relationship
Energy produced = mass of solution
4.2 temperature rise
1 1
/J
/g
/ J C g
3
You may assume that 1.0 cm of solution has a mass of 1.0 g. Ignore the mass of
the solid.
For the solid calcium hydroxide
(1)
69
(ii)
(1)
(iii)
Using your answers to (a)(i) and (ii), calculate the enthalpy changes for each
reaction.
Give your answers to two significant figures. Include the sign and units for each
answer.
For the solid calcium hydroxide, H1
(2)
(b)
C a (O H )2(s)
2 H C l (a q )
H
re a c tio n
C a O (s ) + H 2O (l)
2 H C l (a q )
H
C a C l2 (a q ) + 2 H 2O (l)
70
(i)
Use this Hess cycle and your answers in (a)(iii) to calculate Hreaction. Include a
sign and units.
(2)
(ii)
Apart from the approximations involved in using the equation given in (a)(i), give
TWO other potential sources of error which are likely to affect the accuracy of the
results.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii)
71
39.
(a)
(b)
In the Haber process, ammonia is manufactured from nitrogen and hydrogen as shown in
the equation.
N2(g) + 3H2(g)
(i)
2NH3(g)
Use the bond enthalpies below to calculate the standard enthalpy of formation of
ammonia.
Bond
+945
+436
NN in N
HH in H
NH in NH
+391
(4)
72
(ii)
Draw a labelled enthalpy level diagram for the formation of ammonia in the Haber
process.
E n th a lp y
(2)
(iii)
State the temperature used in the Haber process and explain in terms of the rate of
reaction and position of equilibrium, why this temperature is chosen.
Temperature .......................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
73
(iv)
Identify the catalyst used in the Haber process and state what effect, if any, it has
on the equilibrium yield of ammonia.
Catalyst ................................................................
Effect on yield ...................................................................................................
(2)
(v)
(c)
(ii)
74
40.
The enthalpy change for the reaction of anhydrous aluminium chloride, AlCl 3, with water can be
found as follows:
3
(i)
= 4.00 g
= 104 g
= 17.5 C
= 43.5 C
1
1
= 4.09 J g C
(2)
(ii)
Assuming that 100 cm of water is a large excess, calculate the enthalpy change, in
1
kJ mol , when one mole of aluminium chloride reacts. Include a sign and unit in your
answer.
(3)
(Total 5 marks)
75
41.
(a)
(i)
Write the equation which represents the change occurring when the standard
enthalpy of atomisation of bromine is measured.
...........................................................................................................................
(2)
(ii)
(b)
M g 2+ (g ) + C l2(g ) + 2 e
M g 2+ (g ) + 2 C l(g )
M g + (g ) + C l2(g ) + e
M g (g ) + C l2(g )
M g (s ) + C l2(g )
M g C l2(s )
Value / kJ mol
Enthalpy of atomisation of magnesium
+150
+736
+1450
+122
642
2526
76
77
The theoretically calculated value for the lattice energy of magnesium chloride is
1
2326 kJ mol .
Explain, in terms of the bonding in magnesium chloride, why the experimentally
1
determined value of 2526 kJ mol is significantly different from the theoretical value.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(c)
The table shows values for the lattice energies of the metal chlorides of some Group 2
metals.
Group 2 metal
chloride
MgCl2
CaCl2
SrCl2
BaCl2
Lattice energy/
1
kJ mol
2526
2237
2112
2018
Explain why these lattice energies become less exothermic from MgCl 2 to BaCl2.
(3)
(Total 10 marks)
78
42.
An experiment was carried out to find the enthalpy change for the reaction of zinc powder with
copper(II) sulphate solution.
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
3
50cm of copper(II) sulphate solution, of concentration 1.0 mol dm , was put into a polystyrene
cup and the temperature of the solution measured. After one minute, 5.0 g of zinc powder was
added, the mixture stirred with a thermometer and the temperature measured every 30 s.
(a)
(i)
(ii)
(iii)
Write the equation for this reaction, omitting the spectator ion.
(1)
(b)
79
(c)
Give TWO reasons why it is better to use a polystyrene cup, rather than a metal container,
to obtain more accurate results.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(d)
Calculate the number of moles of each of the reactants and hence deduce which reactant
is completely used up.
Use the Periodic Table as a source of data.
Moles of zinc powder
(e)
60
90
120
150
180
210
Temperature /C
22
22
60
65
63
61
59
80
(i)
70
60
50
T e m p e ra tu re
/C
40
30
20
10
(ii)
40
80
120
T im e / s
160
200
240
(2)
81
(iii)
The maximum recorded temperature in this experiment was 65C. Use your graph
to estimate a more accurate maximum temperature.
...........................................................................................................................
(1)
(f)
(i)
Calculate the energy change in this experiment using your answer to (e)(iii) and the
relationship
energy change = mass of specific heat capacity temperature rise
solution
of solution
1 1
/J
/g
/J C g
/C
You may assume that
3
(1)
(ii)
Use your answers to (d) and (f)(i) to calculate H for this reaction. Include a sign
and units in your answer.
(3)
(Total 18 marks)
82
43.
(i)
0.500 g
21.0 C
39.0 C
1
1.35 kJ C
Calculate the number of kilojoules of energy transferred when the 0.500 g sample
of propane burns in this experiment.
(1)
83
(ii)
Use your answer to (i) to calculate Hc for propane in kJ mol . Give your answer
to three significant figures.
Use the Periodic Table as a source of data.
(2)
(iii)
The Book of data gives the value of Hc for propane as 2220 kJ mol .
Calibrating the apparatus means that the answer you calculated in (ii) allows for
errors due to heat loss.
Suggest the other main source of error which makes the experimental result
different from the data book value.
...........................................................................................................................
...........................................................................................................................
(1)
84
(b)
A value of Hc for propane can be calculated using mean bond energies and the Hess
cycle below.
(i)
Complete the Hess cycle, and use the mean bond energies to calculate H1.
Hence calculate Hc.
Mean bond energies
1
/kJ mol
C=O
805
HO
464
C 3 H 8 ( g ) + ..........O 2 ( g )
+ 6 4 9 0 k J m o l1
3 C O 2 (g ) + 4 H 2O (g )
H
= ........................................
3 C ( g ) + 8 H ( g ) + ..............................
Hc = ................................................................................................................
(3)
(ii)
Give ONE reason why the value you calculated in (b)(i) also differs from the value
for the heat of combustion of propane in the Book of data.
...........................................................................................................................
...........................................................................................................................
(1)
(c)
When propane reacts with chlorine in the presence of ultraviolet light one of the products
is 2-chloropropane.
(i)
85
(ii)
(d)
What would you see when the reaction is carried out with each halogenoalkane?
2-chloropropane ...............................................................................................
2-iodopropane ..................................................................................................
(2)
(ii)
Write an ionic equation showing how silver ions react in the mixture made from 2iodopropane and aqueous silver nitrate. Include state symbols in your answer.
(2)
(iii)
Both 2-chloropropane and 2-iodopropane form the same organic product in the
reaction with aqueous silver nitrate.
Name, or give the structural formula of, this organic product.
...........................................................................................................................
(1)
(Total 17 marks)
86
44.
This question is about some of the chemicals used in car engines and their reactions.
(a)
CH
H C C C C C H
H
(i)
CH
CH
Name X.
...........................................................................................................................
(1)
(ii)
(iii)
(1)
(iv)
What is the sign of the enthalpy change for the reaction in which decane is
cracked? Give a reason for your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
87
(v)
If the air supply in a car engine is poor, there is not enough air for carbon dioxide
to be produced.
Use this information to suggest ONE possible equation for the combustion of X in
this engine. Use the molecular formula of X in your equation.
(2)
(b)
When air enters a car engine, as well as the fuel burning, nitrogen and oxygen can react to
form nitrogen(II) oxide.
N2(g) + O2(g)
(i)
2NO(g)
H = + 180 kJ mol
(ii)
H = 746 kJ mol
Explain why this reaction speeds up when the car engine has been running for a
few minutes.
...........................................................................................................................
...........................................................................................................................
(1)
88
(iii)
A textbook says The catalytic converter converts the gases coming out of the
engine into less harmful ones.
State, with a reason, which of the four gases in the equation in (ii) you consider to
be least harmful.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(iv)
The diagram below shows the reaction profile for the change which occurs in the
catalytic converter.
E n e rg y
2 N O (g ) + 2 C O (g )
N 2 (g ) + 2 C O 2 (g )
P ro g re s s o f re a c tio n
On the diagram, show the activation energy, EA.
Add a line showing the reaction profile if no catalyst is present.
(2)
(Total 12 marks)
89
45.
(a)
(b)
(i)
PCl3(g) + Cl2(g)
Use the values of enthalpy of formation given to calculate H for the forward
reaction.
Hf /
kJ mol
PCl5(g)
399
PCl3(g)
306
(1)
(ii)
Explain, with reasons, the effect that raising the temperature would have on the
composition of the equilibrium mixture.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
90
(iii)
Other than by changing the temperature, suggest how the amount of PCl 5 present at
equilibrium could be increased. Give a reason for your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 8 marks)
46.
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)
91
(ii)
(b)
Why is the lattice energy of magnesium hydroxide more exothermic than that of barium
hydroxide?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
92
(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)
93
(d)
Use the data to explain how the solubility of barium hydroxide compares with that of
magnesium hydroxide.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 15 marks)
47.
Iron is produced from the ore haematite, which contains iron(III) oxide.
Some standard enthalpies of formation are given below.
Compound
Hf / kJ mol
Fe2O3 (s)
822
CO (g)
110
CO2 (g)
394
94
(a)
(i)
Write the equation for the complete reduction of iron(III) oxide by carbon
monoxide.
Calculate the enthalpy change for this reaction.
(3)
(ii)
H = +492 kJ mol
Explain whether the reduction process in (i) or (ii) is more likely to occur.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
95
(b)
Fe3O4(s) + 4H2(g)
At 600 C, a mixture of iron and steam is allowed to reach equilibrium. The equilibrium
partial pressures of hydrogen and steam are 1.6 atm and 1.2 atm respectively.
(i)
Write the expression for the equilibrium constant, Kp, for the reaction. Calculate its
value and state the units.
(2)
(ii)
State the effect, if any, on the value of Kp when the temperature is increased.
Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
96
(c)
When an iron nail is left in a test tube of water containing a little phenolphthalein, it starts
Z
Y
Write the half-equations for the reactions taking place in regions X and Y.
Name the green precipitate that forms in region Z.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
97
(d)
Anhydrous iron(III) chloride is made by passing dry chlorine gas over heated iron. It is
formed as a dark red covalent gas with formula Fe 2Cl6 and has a similar structure and
reactions to aluminium chloride.
Draw a diagram to show the structure of the Fe2Cl6 molecule. Label the types of bonding
present.
State the shape around each iron atom.
(3)
(e)
3+
ions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
98
48.
The enthalpy change for the thermal decomposition of calcium carbonate cannot be measured
directly, but can be found by carrying out two reactions as shown in the Hess cycle below.
H
C a C O 3 (s)
re a c tio n
C a O (s) + C O 2 (g )
E le m e n ts in th e ir s ta n d a rd s ta te s
(a)
(b)
Why is the calcium carbonate used in this experiment finely powdered, rather than
in lumps? Explain why this is important for an accurate result.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
99
(ii)
4.2
1
/J g K
/K
(1)
(iii)
Calculate the enthalpy change, H1. Include a sign and units in your answer.
1
(3)
100
(iv)
1
In another experiment, the value of H2 was found to be 181 kJ mol .
Use this result and your answer to (iii) to calculate the value of Hreaction.
(2)
(c)
The student checked the experimental results using information from the Book of data in
another Hess cycle.
H
C a C O 3 (s)
re a c tio n
C a C O (s) + C O 2(g )
E le m e n ts in th e ir s ta n d a rd s ta te s
101
49.
The Hess cycle below can be used to estimate the enthalpy change of formation, Hf, of the
unstable gaseous compound with the formula HOCl(g).
+ 6 6 7 k J m o l 1
H O C l(g )
G a s e o u s a to m s o f th e e le m e n ts
H
+ 5 8 9 k J m o l 1
E le m e n ts in th e ir s ta n d a rd s ta te s
(a)
(i)
Insert formulae, with state symbols, into the appropriate boxes, to show the correct
quantities of each element.
(1)
(ii)
Use the cycle to calculate a value for the enthalpy change of formation, H f
[HOCl(g)].
(1)
102
(iii)
Assuming that the HO bond energy is +464 kJ mol , calculate a value for the O
Cl bond energy.
(1)
103
(b)
(i)
Draw a dot and cross diagram for the HOCl molecule showing outer electrons
only.
(2)
(ii)
104
(c)
2HOCl(g)
What effect, if any, would an increase in pressure have on the proportion of HOCl(g) at
equilibrium? Justify your answer.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 9 marks)
50.
2SO3(g)
(b)
(i)
State the conditions of temperature and pressure used industrially for the
manufacture of SO3.
...........................................................................................................................
...........................................................................................................................
(2)
105
(ii)
Justify the choice of temperature for this reaction in terms of yield and rate.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(iii)
The yield of products would be greater if a higher pressure were to be used for the
reaction.
Suggest a reason why a higher pressure than you have given in (i) is not used.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(c)
(i)
Calculate H for the forward reaction, given the enthalpies of formation below.
Hf / kJ mol
SO2(g)
297
SO3(g)
395
O2(g)
(2)
106
(ii)
(d)
(i)
(ii)
Draw an enthalpy level diagram to show the reaction profiles of the uncatalysed
and catalysed reactions.
(3)
(iii)
107
(e)
Suggest why the sulphur trioxide produced is passed into concentrated sulphuric acid
rather than water to form sulphuric acid at the end of the process.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 18 marks)
51.
(a)
(b)
Calculate the enthalpy change for this reaction, using the bond enthalpies
given below.
Bond enthalpy
1
/ kJ mol
CH
+435
O=O
+498
C=O
+805
HO
+464
(3)
(ii)
108
(iii)
The value of this enthalpy change, under standard conditions, is 890 kJ mol .
State the meaning of standard conditions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iv)
Suggest, with a reason, why the enthalpy change calculated in (i) is different from
the standard value quoted in (iii).
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(c)
Although the reaction between methane and oxygen is exothermic, it does not occur
unless the mixture is ignited.
Use these facts to explain the difference between thermodynamic and kinetic stability.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(Total 14 marks)
109
52.
A student carried out an experiment to find the concentration of a solution of nitric acid and also
its enthalpy of neutralisation.
The solutions of nitric acid and sodium hydroxide were allowed to reach the
same temperature.
3
A burette was filled with a solution of 2.0 mol dm sodium hydroxide, NaOH.
The initial temperature of the acid was recorded.
3
This was repeated until 45 cm of the sodium hydroxide solution had been added.
110
30
28
26
T e m p e ra tu re
/ C
24
22
20
18
16
0
10
15
20
V o lu m e o f 2 .0 m o l d m
(a)
25
3
30
35
40
45
50
s o d iu m h y d ro x id e s o lu tio n a d d e d / c m
Complete the graph by drawing two intersecting straight lines of best fit.
(1)
111
(b)
The point where the lines cross represents the neutralisation of the nitric acid by the
sodium hydroxide solution.
Use the graph to find:
(i)
the volume of 2.0 mol dm sodium hydroxide solution, NaOH, that reacts exactly
3
with the 50 cm of the nitric acid.
...........................................................................................................................
(1)
(ii)
(c)
The information in (b)(i) and the equation below can be used to calculate the
concentration of the nitric acid.
NaOH(aq) + HNO3(aq) NaNO3(aq) + H2O(l)
(i)
(1)
(ii)
(iii)
(2)
112
(d)
(i)
Use the data from (b) to calculate the heat change for this reaction.
The density of the mixture produced at neutralisation is 1.0g cm
1
1
heat capacity of the mixture is 4.2 J g C .
(2)
(ii)
Use your answer from (d)(i) and (c)(iii) to calculate the enthalpy of neutralisation
per mole of nitric acid, HNO3. Include a sign and units with your answer.
(3)
(e)
The enthalpy of neutralisation found by this method may be less exothermic than the
data book value because of heat loss.
Suggest ONE way to reduce the error due to heat loss.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 13 marks)
113
53.
(a)
(2)
(b)
The equation for the reaction of lithium with hydrochloric acid is shown below.
2Li(s) + 2HCl(aq) 2LiCl(aq) + H2(g)
(i)
(1)
114
(ii)
Draw a dot and cross diagram of lithium chloride showing all the electrons.
Indicate charges clearly on your diagram.
(2)
(iii)
The value of the standard enthalpy change for the reaction, H , is 557 kJ mol .
State TWO of the reaction conditions necessary for this enthalpy change to be
standard.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 7 marks)
115
54.
This question is about the arene, naphthalene. The structure of naphthalene can be shown as
(a)
(b)
(i)
H = 120 kJ m ol
+ 5H
H = ...................... kJ mol
(1)
(ii)
116
(iii)
(c)
(ii)
55.
(a)
The enthalpy change to convert methane into gaseous atoms is shown below.
CH4(g) C(g) + 4H(g)
H = +1664 kJ mol
(1)
117
(ii)
Use the data in the table below and your answer to (a)(i) to calculate the enthalpy
change for
2C(g) + 2H2(g) + Br2(g) CH2BrCH2Br(g)
Bond
Average bond
1
enthalpy / kJ mol
Bond
Average bond
1
enthalpy / kJ mol
CC
+348
HH
+436
BrBr
+193
CBr
+276
(3)
(b)
37.8 kJ mol .
Suggest the main reason for the difference between this value and your calculated value
in (a)(ii).
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)
(Total 5 marks)
118
56.
(a)
(1)
(ii)
(b)
(i)
(ii)
119
(c)
Butane, C4H10(g)
(i)
Hc /kJ cm
0.12
Ethanol, C2H5OH(l)
30
21
2,2,4-trimethylpentane, C8H18(l)
48
33
(2)
(ii)
Use the information in the table to compare the advantages and disadvantages of
these three compounds as fuels for a motor vehicle.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
(Total 13 marks)
120
57.
2+
stir the solution with the thermometer and record the temperature to the nearest 0.5 C
at exactly 3.5 minutes, add the zinc powder to the aqueous copper(II) sulphate, stirring
continuously
record the temperature of the solution every minute from 4.0 to 9.0 minutes.
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
20.0
20.0
20.0
20.0
63.0
60.5
59.0
57.0
55.5
53.0
121
(a)
(i)
6 0 .0
5 0 .0
T e m p e ra tu re
/ C
4 0 .0
3 0 .0
2 0 .0
1 0 .0
0
0
1 .0
2 .0
3 .0
4 .0
5 .0
6 .0
7 .0
8 .0
9 .0
1 0 .0
T im e / m in u te s
(ii)
(2)
Use the graph to calculate the maximum temperature change, T. Show clearly on
the graph how you obtained your answer.
T = ................................................C
(2)
122
(iii)
Give ONE reason why a series of temperature readings is obtained instead of just
the starting and maximum temperatures.
......................................................................................................................
......................................................................................................................
(1)
(b)
(i)
C .
(1)
(ii)
What assumption have you made about the solution in your calculation in (i)?
......................................................................................................................
......................................................................................................................
(1)
(iii)
(1)
123
(iv)
(2)
(c)
124
58.
The values of the lattice energies of potassium iodide and calcium iodide experimentally
determined from Born-Haber cycles and theoretically calculated from an ionic model are shown
below.
(i)
Experimental lattice
energy
1
/kJ mol
Theoretical
lattice energy
1
/kJ mol
651
636
2074
1905
Explain why the experimental lattice energy of potassium iodide is less exothermic than
the experimental lattice energy of calcium iodide.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
125
(ii)
Explain why the experimental and theoretical values of the lattice energy are almost the
same for potassium iodide, but are significantly different for calcium iodide.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
(Total 6 marks)
59.
(a)
(i)
Draw a labelled Hesss Law cycle for the dissolving of solid calcium hydroxide in
water, and use it and the data below to calculate the lattice energy of calcium
hydroxide.
H/ kJ mol
2+
1650
460
16.2
(4)
126
(ii)
State and explain the trend in solubility in water of the Group 2 hydroxides.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
(b)
The dissolving of sparingly soluble calcium hydroxide in water can be shown by the
equilibrium reaction
Ca(OH)2(s) + (aq)
2+
H = 16.2 kJ mol
127
(ii)
(c)
When concentrated sulphuric acid is added to solid calcium chloride, one acidic gas is
given off.
When concentrated sulphuric acid is added to solid calcium bromide, three gases are
given off.
Identify the three gases given off in the reaction with calcium bromide. Explain why only
one gas is given off in the reaction with calcium chloride.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)
(Total 18 marks)
60.
When solutions of potassium carbonate and calcium chloride are mixed together, the following
reaction takes place
CaCl2(aq) + K2CO3(aq) CaCO3(s) + 2KCl(aq)
(a)
Re-write the above equation as an ionic equation. Include state symbols, but omit any
spectator ions.
(2)
128
(b)
An experiment was carried out to measure the enthalpy change for this reaction. 50 cm
3
3
of a 1.00 mol dm solution of potassium carbonate was added to 50 cm of a
3
1.00 mol dm solution of calcium chloride. The temperature fell by 1.5 C.
(i)
Calculate the energy taken in from the surroundings using the relationship
energy =
mass of
solution
/J
/g
/J g C
/C
C .
(ii)
(1)
(iii)
Calculate the enthalpy change for the reaction, giving your answer to two
significant figures. Include a sign and units in your answer.
(2)
129
(iv)
Which measurement is likely to have caused the major source of error in this
experiment? Explain your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(1)
(v)
What apparatus should be used to contain the reaction mixture during this
experiment?
................................................................................................................................
(1)
(c)
If the experiment in (b) was repeated, but using only 25 cm of each solution, predict
what the fall in temperature would be.
.......................................................................................................................................
(1)
(Total 9 marks)
61.
(i)
Draw a dot and cross diagram for methanol, showing outer shell electrons only.
(1)
130
(ii)
(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)
131
(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)
(ii)
Use the data below to calculate the energy of the CO bond in methanol.
at
= +2039 kJ mol
(2)
132
(iii)
Complete a balanced Hess cycle which you can use to calculate the standard
methanol vapour, H 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)
(3)
133
(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)
(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)
134
62.
(a)
(i)
(ii)
Use the diagram to explain why the rate of a reaction increases with an increase in
temperature.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
135
(iii)
136
(b)
Describe, with the aid of a diagram, an experiment you could do to follow the
progress of this reaction at different temperatures.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)
137
(ii)
Would you expect Ssystem to be positive or negative for this reaction? Justify your
answer with TWO pieces of evidence.
................................................................................................................................
...............................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(iii)
63.
Methane, CH4, is used as a domestic and industrial fuel and as a reagent in the petrochemical
industry.
(a)
138
(b)
H (g ) + 2 O
O (g )
O (g ) + 2 H
H (g )
H
Use the average bond enthalpy data shown below to calculate the enthalpy change of this
reaction.
Bond
+435
O==O
+498
C==O
+805
+464
(3)
139
(e)
CH4(g)
75
CO2(g)
394
H2O(g)
242
(4)
(Total 10 marks)
64.
In an experiment to find the enthalpy of neutralisation of a monobasic acid, HX, with an alkali,
the following procedure was followed:
3
Step 1
25.0 cm of 1.00 mol dm dilute aqueous acid, HX, was measured into a
polystyrene cup.
Step II
A 0-100 C thermometer was placed in the acid. The temperature of the acid was
immediately read and recorded.
Step III
5.00 cm portions of aqueous sodium hydroxide were added to the acid from a
burette. After each addition, the temperature of the solution was read and recorded.
The thermometer was removed and rinsed with water between each addition. A
3
total of 50.0 cm of aqueous sodium hydroxide was added.
140
(a)
Suggest ONE change that could be made at Step II and ONE change that could be made
at Step III to improve the accuracy of the experiment.
Step II ...................................................................................................................
...............................................................................................................................
Step III ..................................................................................................................
...............................................................................................................................
(2)
(b)
The readings of temperature and volume are plotted on the grid. Draw two separate
straight lines of best fit, extending the two lines so that they intersect.
25
T e m p e ra tu re
/ C
20
15
10
20
30
40
V o lu m e o f s o d iu m h y d ro x id e a d d e d / c m
50
3
(2)
141
(c)
From the graph, read off the maximum temperature rise, T, and the volume of aqueous
sodium hydroxide added at neutralisation, VN.
T = ..................................... C
VN = ................................ cm
(2)
(d)
(i)
Use the formula below to calculate the heat evolved in the neutralisation.
VN 25 T 4.18
Heat evolved =
1000
kJ
(1)
(ii)
Given that the amount (moles) of acid neutralised was 0.025 mol, calculate the
1
enthalpy of neutralisation, Hneut, in units of kJ mol .
(2)
(Total 9 marks)
142
65.
(a)
(b)
L i(g ) +
L i(s ) +
1
2
1
2
C l 2(g )
C l 2 (g )
C l 2(g )
H
H
la tt
L iC l(s )
Enthalpy change
1
/kJ mol
Enthalpy of formation of lithium chloride(s)
409
+161
+122
st
+519
349
143
(i)
(2)
(ii)
(c)
(i)
State TWO properties of ions that affect the value for the lattice energy of ionic
compounds.
......................................................................................................................
......................................................................................................................
(2)
144
(ii)
The calculated value for the lattice energy of potassium chloride is almost exactly
the same value as that found experimentally.
1
Why is the theoretical value for the lattice energy of silver chloride, 833 kJ mol ,
l
so different from the experimentally determined value of 905 kJ mol ?
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(d)
(i)
Draw a Hesss law cycle to show how the lattice energy and the enthalpy of
hydration are related to the enthalpy of solution of an ionic compound, MX(s).
(2)
(ii)
How are the enthalpy values used to suggest whether MX(s) is soluble in water.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
145
(iii)
The table below gives some information about the sulphates of two of the elements
in Group 2.
formula of sulphate
lattice energy
/kJ mol
hydration enthalpy of
the cation
1
/kJ mol
solubility
/mol dm
CaSO4
2480
1650
4.7 10
BaSO4
2374
1360
9.4 10
Comment on the trend in the solubility of these sulphates in relation to the lattice
energies and hydration enthalpies as shown in the table.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(Total 17 marks)
66.
146
(b)
The enthalpy change for this reaction can be calculated from standard enthalpy changes
of formation.
(i)
(ii)
Complete the Hess cycle for the reaction so that you can calculate the enthalpy
change of the reaction from standard enthalpy changes of formation.
(3)
(iii)
147
(iv)
Calculate H r for the reaction using the following data. Remember to include a
sign and units in your answer.
Hf [(NH4)2Cr2O7(s)]
1810 kJ mol
242 kJ mol
1140 kJ mol
Hf [H2O(g)]
Hf [Cr2O3(s)]
(3)
(c)
In this reaction, water vapour is formed which condenses to liquid water on cooling.
Is this reaction H2O(g) H2O(l) exothermic or endothermic?
Justify your answer.
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
(2)
(Total 13 marks)
148
67.
Hydrochloric acid, formed when hydrogen chloride is dissolved in water, can be converted to
chlorine using an aqueous solution of hydrogen peroxide:
2HCl(aq) + H2O2(aq) Cl2(g) + 2H2O(l)
(i)
(ii)
(iii)
Explain why the oxidation numbers you have given in (i) are consistent with the fact that
two moles of hydrochloric acid react with one mole of hydrogen peroxide.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 4 marks)
149
68.
Hf [Cl2O(g)]
+ 80.3 kJ mol
+121.7 kJ mol
+249.2 kJ mol
Hat [Cl2(g)]
Hat [O2(g)]
(i)
Insert the appropriate formulae, showing the correct quantities of each element, into the
box above. Include state symbols in your answer.
(1)
(ii)
Insert arrows between the boxes, writing the correct numerical data alongside the
appropriate arrows.
(1)
150
(iii)
(1)
(iv)
(1)
(Total 14 marks)
69.
(a)
(b)
The complete combustion of the fuel methane is shown in the following equation.
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
151
(i)
Formula of
Substance
CH4(g)
O2(g)
CO2(g)
394
H2O(l)
286
Use the data in the table above to calculate the standard enthalpy change for the
complete combustion of methane.
(3)
(ii)
Explain the significance of the sign of the value of this enthalpy change.
......................................................................................................................
......................................................................................................................
(1)
(c)
Ethanol, C2H5OH, is also a fuel. Write the equation for the complete combustion of
ethanol.
...............................................................................................................................
(2)
152
(d)
Methane
Liquid
Gas
500
50
30
56
Use these data to suggest advantages and disadvantages of ethanol and methane as motor
car fuels.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
(e)
153
(f)
Ethanol can be dehydrated to produce ethene. State the reagent and conditions required
for this conversion.
Reagent ...................................................................................................................
Conditions ...............................................................................................................
(2)
(Total 16 marks)
70.
In two similar, separate experiments the enthalpy changes for the reactions of sodium
hydrogencarbonate and sodium carbonate with excess dilute hydrochloric acid were determined.
(a)
The first experiment was to find the enthalpy change, H1, for the reaction
NaHCO3(s) + HCl(aq) NaCl(aq) + CO2(g) + H2O(l)
Measurement
Mass of solid sodium hydrogencarbonate added to
hydrochloric acid.
Reading
5.00 g
3
50.0 cm
22.0 C
15.5 C
84.0 g mol
1
4.18 J g C
154
(i)
(1)
(ii)
(2)
155
(iii)
(2)
(b)
In the second experiment the enthalpy change for the reaction between sodium carbonate
and dilute hydrochloric acid was measured.
Na2CO3(s) + 2HCl (aq) 2NaCI(aq) + CO2(g) + H2O(l)
The molar enthalpy change, H2, was calculated to be 35.6 kJ mol
(i)
Give TWO ways in which the temperature change differs when equal molar
amounts of sodium hydrogencarbonate and sodium carbonate react separately with
the same volume of hydrochloric acid.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(ii)
Give ONE assumption that has been made in calculating the values of H1, and
H2 from experimental results.
......................................................................................................................
......................................................................................................................
(1)
(Total 8 marks)
156
71.
(a)
+ H
(i)
+ 2H
......................................................................................................................
(1)
(ii)
+ 3H
......................................................................................................................
(1)
(iii)
157
(b)
Benzene, C6H6, reacts with bromine to form bromobenzene, C6H5Br, and hydrogen
bromide.
(i)
Give the formula of the catalyst that is needed for the reaction.
......................................................................................................................
(1)
(ii)
Give the mechanism for the reaction, making clear the role of the catalyst.
(4)
(iii)
State the type of mechanism that is commonly found with reactions of benzene and
its derivatives.
......................................................................................................................
(1)
(Total 11 marks)
158
72.
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)
159
(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)
160
(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)
73.
(i)
(1)
161
(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)
162
(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.
H f[PH3(g)]
=+
5.4 kJ mol
H at[P(s)]
= +314.6 kJ mol
1
1
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)
74.
H = 129 kJ mol
163
(a)
The entropy of one mole of each substance in the equation, measured at 298 K, is shown
below.
S
Substance
(i)
/J mol
CO(g)
197.6
H2(g)
130.6
CH3OH(l)
239.7
Suggest why methanol has the highest entropy value of the three substances.
.............................................................................................................................
.............................................................................................................................
(1)
(ii)
system,
(2)
(iii)
Is the sign of S
system
.............................................................................................................................
.............................................................................................................................
.............................................................................................................................
(1)
164
(iv)
surroundings,
at 298 K.
(2)
(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)
165
(ii)
(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)
166
(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.
(i)
(ii)
Draw a line on the graph, labelled EC, to show the activation energy of the
catalysed reaction.
(1)
(Total 17 marks)
75.
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)
167
(ii)
Use the data below to calculate the enthalpy change for the reaction between
oxygen and nitrogen monoxide.
H f (NO) = + 90 kJ mol
H f (NO2) = + 34 kJ mol
(2)
(iii)
(3)
168
(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)
169
(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)
76.
The apparatus shown in the diagram below may be used to find the enthalpy of combustion of
alcohols.
w a te r
s p irit la m p +
e th a n o l
Using the apparatus, a student recorded the results included in the table below.
Alcohol = ethanol, C2H5OH
Molar Mass (C2H5OH) = 46.0 g mol
Volume of water in beaker = 200 cm
mass of water in beaker = 200 g
Weighings
Spirit lamp + ethanol before combustion = 198.76 g
Spirit lamp + ethanol after combustion = 197.68 g
Temperatures
Water before heating = 19.5 C
Water after heating = 38.1 C
Specific heat capacity of water = 4.18 J g
170
(a)
What assumption is the student making about water to be able to state that its mass is
numerically equal to its volume?
...............................................................................................................................
(1)
(b)
Calculate the heat gained by the water. Give your answer in kJ.
(2)
(c)
(2)
171
(d)
Using your values from (b) and (c), calculate the enthalpy of combustion of ethanol. Give
your answer to a number of significant figures consistent with the readings in the table.
Include a sign and units in your answer.
(3)
(e)
(i)
Explain why the spirit lamp and ethanol lost mass even when not in use.
......................................................................................................................
......................................................................................................................
(1)
172
(ii)
Suggest the identity of the black solid. Explain why its formation will lead to a low
value for the enthalpy of combustion.
Identity ..........................................................................................................
Explanation ...................................................................................................
......................................................................................................................
(2)
(Total 11 marks)
77.
(a)
(i)
Write an ionic equation for the reaction between magnesium powder and copper(II)
ions. Include state symbols, but omit any spectator ions.
(2)
(ii)
Show how the standard enthalpy change for this reaction could be calculated from
the standard enthalpies of formation of copper(II) ions and magnesium ions. You
should include a Hess cycle in your answer.
(3)
173
(b)
(2)
(ii)
(1)
(iii)
(1)
174
(c)
Suggest TWO reasons why the temperature of the coffee may not increase by as much as
60 C.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
(Total 11 marks)
78.
The reaction between chlorine and methane, in the presence of ultraviolet light, involves the
formation of free radicals and includes the following steps:
(a)
Cl2 2Cl
= +4 kJ mol
= 97 kJ mol
Cl + Cl Cl2
Cl + CH3 CH3Cl
(i)
= +242 kJ mol
= 339 kJ mol
175
(ii)
Draw a dot-and-cross diagram, showing outer shell electrons only, for a chlorine
free radical.
(1)
(iii)
(b)
(c)
(i)
Write the equation for the overall reaction between one mole of chlorine and one
mole of methane molecules.
(1)
(ii)
(2)
176
(d)
(i)
(ii)
(e)
The overall reaction was repeated using bromine gas instead of chlorine gas.
Would you expect step A for bromine to be more or less endothermic than step A for
chlorine? Justify your answer.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
(Total 11 marks)
79.
Urea, which is used as a fertillser in much of mainland Europe, Asia and Africa, is manufactured
by the reaction of ammonia and carbon dioxide.
2NH3(g) + CO2(g) NH2CONH2(s) + H2O(l)
(a)
, of urea.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
177
(b)
Substance
Hf
/ kJ mol
NH3(g)
46.2
CO2(g)
393.5
NH2CONH2(s)
632.2
H2O(l)
285.8
(3)
(Total 6 marks)
80.
(a)
(b)
(i)
Identify the reagent and conditions necessary for the conversion of iodoethane to
ethylamine, C2H5NH2.
Reagent:.........................................................................................................
Conditions:.....................................................................................................
......................................................................................................................
(3)
178
(ii)
State why the rate of reaction would be slower if bromobutane were used in place
of iodoethane, with all other conditions remaining the same.
......................................................................................................................
......................................................................................................................
(1)
(c)
Hf
Bond enthalpy
1
/ kJ mol
= +36 kJ mol
I bond enthalpy.
Bond
Bond enthalpy
1
/ kJ mol
413
298
347
358
464
(3)
179
(d)
Ethanol was heated under reflux with an excess of a mixture of potassium dichromate(VI)
and dilute sulphuric acid. Draw the full structural formnula of the organic product.
(1)
(Total 10 marks)
180
81.
(a)
2NH3(g)
H = 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)
(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)
181
(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)
82.
(a)
Consider the following equilibrium, which illustrates one industrial method used to
produce hydrogen:
CH4(g) + 2H2O(g)
CO2(g) + 4H2(g)
container of volume 4 dm . At equilibrium, 2.0 moles of hydrogen, H2, had formed. Write
an expression for the equilibrium constant, Kc, for the system, and use the data to
calculate a value for Kc, with units.
(8)
182
(b)
The following table shows some data for enthalpies of formation, Hf.
Substance
H f /kJ mol
CH4(g)
76
H2O(g)
242
CO2(g)
394
Use these data to calculate the enthalpy change for the reaction in (a).
(3)
(c)
83.
(a)
The equation below shows the reaction which occurs when ammonia is dissolved in
water.
NH3(g) + H2O(1)
(i)
NH 4 (aq) + OH (aq)
(ii)
183
(b)
Ammonia reacts with oxygen to form the gases nitrogen(II) oxide and steam.
(i)
Complete the Hess cycle below so that Hreaction can be calculated using standard
enthalpy changes of formation. Include state symbols.
(2)
(ii)
Include a sign and units in your answer and give your answer to three significant
figures.
(3)
(Total 7 marks)
184
84.
(i)
Draw a dot and cross diagram for a molecule of hydrogen cyanide, showing outer
shell electrons only.
(1)
(ii)
(b)
Write a balanced equation for the combustion of hydrogen cyanide in oxygen, assuming
that the products are water, carbon dioxide and nitrogen.
(1)
185
(c)
Hydrogen cyanide is an extremely toxic, volatile liquid that is used to make useful
compounds, such as Perspex. Do you think it is acceptable for it to be used in this way?
Justify your answer.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(1)
(d)
H at/kJ mol
H2(g) H(g)
C(s, graphite) C(g)
1
2
N2(g) N(g)
+ 218
+ 717
+ 473
186
(i)
Insert formulae, showing the correct quantities of each element, into the
appropriate boxes.
(2)
(ii)
Insert arrows between the boxes and write the correct numerical data alongside the
appropriate arrows.
(2)
(iii)
Use the cycle to calculate H at[HCN(g)] and then the carbon to nitrogen bond
energy in hydrogen cyanide.
(1)
(Total 10 marks)
85.
(a)
Define the term standard enthalpy of combustion, making clear the meaning of
standard in this context.
...
...
...
...
...
(3)
187
(b)
Use the enthalpies of combustion given below to find the enthalpy change for
the reaction:
2C(graphite) + 2H2(g) + O2(g) CH3COOH(l)
Hcombustion/kJ mol
C(graphite)
394
H2(g)
286
CH3COOH(l)
874
(3)
(c)
With reference to ethanoic acid, CH3COOH, what is the enthalpy change obtained
in (b) called?
...
(1)
188
(d)
Draw an enthalpy level diagram to represent the enthalpy change for the combustion of
graphite. Show both the enthalpy levels of the reactants and products and an energy
profile which represents the activation energy for the reaction.
(3)
(Total 10 marks)
86.
(a)
This question is about finding the formula of copper hydroxide. The method is as follows:
189
A burette was filled with aqueous sodium hydroxide, of concentration 2.00 mol dm .
3
2.00 cm of sodium hydroxide solution was run into the solution of the copper salt and
the temperature was measured immediately.
As soon as possible a further 2.00 cm of sodium hydroxide solution was run in and
the temperature measured again.
3
This process of adding 2.00 cm portions of sodium hydroxide solution and measuring
3
the temperature was continued until a total of 36.0 cm of the sodium hydroxide solution
had been added.
30
29
T e m p e ra tu re / C
28
27
26
25
24
23
22
21
20
0
12
16
20
24
28
32
36
40
3
V o lu m e o f N a O H (a q ) / c m
190
(i)
Explain why the temperature reaches a maximum and then falls slightly on addition
of further sodium hydroxide solution.
....
....
....
(2)
(ii)
From the graph, what volume of the aqueous sodium hydroxide was required
for complete reaction?
....
(1)
(iii)
(1)
(iv)
Calculate the amount (number of moles) of copper ions that have reacted.
(1)
(v)
(1)
(vi)
(1)
191
(b)
The data call be used to find the enthalpy change for the reaction between sodium
hydroxide and the copper salt.
(i)
Use the graph to find the temperature rise that occurs for complete reaction.
....
(1)
(ii)
Find the heat change, q, that occurs in the polystyrene cup for complete reaction.
Use the formula
q = 168 T joules
(1)
(iii)
Use your results from (a)(iv) and (b)(ii) above, to find the molar enthalpy change,
H, for the reaction. Give the correct sign and units to the answer.
(3)
(c)
Identify one potential source of error in this experiment, and say what you would do
to reduce its effect.
......
......
......
......
......
(2)
(Total 14 marks)
192
87.
(1)
(b)
Calculate the enthalpy change, H, in kJ mol for this reaction given that:
energy change =
/J
specific
heat capacity
mass of
solution
temperature
change
/g
/K
/J g
Assume that the mass of solution is 20.0 g and the specific heat capacity of the solution
1 1
is 4.18 J g K .
(2)
(Total 5 marks)
88.
(a)
A mixture of hydrogen iodide, hydrogen and iodine (all in the gaseous state) establishes
dynamic equilibrium if a constant temperature is maintained.
2HI (g)
(i)
H2 (g) + I2 (g)
H = +9.6 kJ mol
193
(ii)
(iii)
The reaction is catalysed by metals such as gold and platinum. How, if at all, would
the proportion of hydrogen iodide present at equilibrium change if the reaction
were to be catalysed? Justify your answer.
............................................................................................................................
............................................................................................................................
(1)
194
(b)
Part of an energy profile for this reaction is shown below. It is not intended to be to scale.
the products;
labelled arrows to indicate the activation energies of both the uncatalysed and
catalysed reactions.
(4)
(Total 9 marks)
89.
1
2
O2(g)
195
(b)
(ii)
The overall order of the reaction is one. Give the rate equation for the reaction.
Rate =
(1)
(iii)
How would you use a graph of hydrogen peroxide concentration against time to
show that the reaction is first order?
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(c)
The data in the table show the effect of temperature on the rate of this reaction.
T
/K
Rate
3 1
/ mol dm s
1/T
1
/K
ln(rate)
293
1.6 10
3.41 10
13.3
302
4.2 10
3.31 10
12.4
314
14.4 10
3.19 10
11.1
323
33.8 10
3.10 10
10.3
196
(i)
On the axes below, sketch graphs for two temperatures, T1 and T2, where T2 is
greater than T1, and use them to explain why increasing temperature has a dramatic
effect on the rate of this reaction.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(4)
197
(ii)
(3)
198
(iii)
Use your graph and the equation below to calculate the activation energy, EA, for
this reaction.
EA
ln(rate) = constant R
(1/T)
You should include the sign and units with your answer which should be given to
two significant figures.
(3)
(Total 16 marks)
90.
The reaction of an acid with a base to give a salt is an exothermic reaction. In an experiment to
3
determine the enthalpy of neutralisation of hydrochloric acid with sodium hydroxide, 50.0cm
3
3
3
of 1.00 mol dm HCl was mixed with 50.0 cm of 1.10 mol dm NaOH. The temperature rise
obtained was 6.90 C.
(a)
(b)
Assuming that the density of the final solution is 1.00 g cm and that its heat capacity is
1 1
4.18 J K g , calculate the heat evolved during the reaction.
(3)
199
(c)
kJ mol .
(2)
(d)
91.
(a)
(i)
(ii)
The values for the standard enthalpy of combustion of graphite and carbon
monoxide are given below:
Hc /kJ mol
C (graphite)
394
CO(g)
283
200
Use these data to find the standard enthalpy change of formation of carbon
monoxide using a Hesss law cycle.
1
C(graphite) + 2 O2(g) CO(g)
(3)
(iii)
(iv)
Draw an enthalpy level diagram below for the formation of carbon monoxide from
graphite.
(1)
201
(b)
Natural gas consists of methane, CH4. When methane burns completely in oxygen the
reaction occurs as shown in the equation
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
Hc = 890 kJ mol
92.
A student was required to determine the enthalpy change for the reaction between iron and
copper sulphate solution.
A p ie c e o f ir o n , m a s s a b o u t 3 g , w a s p la c e d in a g la s s b e a k e r . 5 0 c m 3 o f
0 .5 m o l d m 3 a q u e o u s c o p p e r s u lp h a t e s o lu t io n w a s m e a s u r e d u s in g a
m e a s u r in g c y lin d e r a n d a d d e d t o t h e b e a k e r . T h e t e m p e r a t u r e o f t h e
m ix t u r e w a s m e a s u r e d im m e d ia t e ly b e f o r e t h e a d d it io n a n d e v e r y m in u t e
a f t e r w a r d s u n t il n o f u r t h e r c h a n g e t o o k p la c e .
Fe + CuS O
T im in g
before
a d d it io n
T e m p e ra tu re / C
22
FeSO
+ Cu
1 m in
2 m in s
3 m in s
4 m in s
5 m in s
27
29
26
24
22
202
(a)
Suggest two improvements you would make to this experiment. Give a reason for each of
the improvements suggested.
Improvement 1 ...........................................................................................................
....................................................................................................................................
Reason 1 ....................................................................................................................
....................................................................................................................................
Improvement 2 ...........................................................................................................
....................................................................................................................................
Reason 2 ....................................................................................................................
....................................................................................................................................
(4)
(b)
Using this data and taking the specific heat capacity of all aqueous solutions as
1
1
4.18 Jg deg calculate the heat change.
(1)
(ii)
(1)
203
(iii)
(2)
(Total 8 marks)
93.
(a)
O H
E /V
+ 2H
O H
+ 2 e + 0 .7 0
O
H 2O
(i)
+ 2H
+ 2e
2H 2O
+ 1 .7 7
Write the overall equation for the reaction and show that the reaction is feasible.
(3)
(ii)
The beetle makes use of an enzyme catalyst in the reaction. Explain in general
terms how catalysts increase the rate of a chemical reaction using a graph of the
Maxwell-Boltzmann distribution of molecular energies.
(5)
204
(iii)
(b)
(c)
(i)
(ii)
2+
The MnO 4 ions are reduced to Mn during the reaction. Derive the overall
equation for the reaction between H2O2 and acidified KMnO4.
(2)
(iii)
205
94.
(a)
(i)
(ii)
Formula
Hf /kJ mol
ethene
C2H4(g)
+52.3
hydrogen bromide
HBr(g)
36.2
bromoethane
C2H5Br(g)
60.4
Use the data in the table above to calculate the standard enthalpy change for the
following reaction.
C2H4(g) + HBr(g) C2H5Br(g)
(2)
(iii)
State the significance of the sign of the value obtained in part (a)(ii) above.
..........................................................................................................................
..........................................................................................................................
(1)
206
(b)
Enthalpy changes can also be calculated using average bond enthalpy data.
Bond
C == C
+612
+348
+412
Br
+276
Br
+366
Use the data in the table above to recalculate the enthalpy change for the reaction in part
(a)(ii).
C2H4(g) HBr(g) C2H5Br(g)
(3)
(c)
Suggest why the value obtained in part (b) above is likely to be less accurate than that
obtained in part (a)(ii).
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
(Total 11 marks)
207
95.
The formation of magnesium chloride from magnesium and chlorine may be represented by the
following Born-Haber cycle:
M g
M g
2+(
g ) + C l 2(g ) + 2 e
2+(
g ) + 2 C l(g ) + 2 e
M g
2+
(g ) + 2 C l (g )
M g (g ) + C l 2(g )
M g (s) + C l2 (g )
M g C l 2(s)
(a)
Enthalpy of atomisation.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
(b)
(i)
208
(ii)
Use the data below to calculate the first electron affinity of chlorine.
Enthalpy change
+150
+736
+1450
642
+121
2493
(2)
(c)
Hydrogen gas reacts with sodium metal to form an ionic solid, NaH, which contains
sodium cations.
Draw a Born-Haber cycle which could be used to determine the electron affinity of
hydrogen.
(3)
(Total 11 marks)
209
96.
(a)
The Born-Haber cycle for the formation of sodium chloride is shown below.
N a + (g )
N a + (g )
1
2
C l( g ) + e
C l2 (g ) + e
N a + (g )
N a (g )
N a (s)
1
2
C l (g )
C l2 (g )
1
2
C l2 (g )
N a+ C l (s)
Use the data below to calculate the lattice enthalpy of sodium chloride.
Enthalpy change
Value of the
enthalpy change
1
/kJ mol
+109
+494
411
+121
364
(2)
210
(b)
Sodium chloride and magnesium oxide have very similar crystal lattices. Suggest why
the lattice enthalpy of magnesium oxide is very much larger than that of sodium chloride.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(c)
The lattice enthalpy of silver iodide can be calculated but the experimental value does not
match the calculated value as well as those for sodium chloride match each other.
Explain why the calculated and experimental values for silver iodide are different.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(Total 6 marks)
97.
(a)
(ii)
Apart from the nitrogen content, suggest two advantages of using urea as a
fertiliser compared with using ammonium nitrate.
(2)
(b)
211
(c)
(d)
State the reagents and conditions for carrying out the conversion.
(3)
(ii)
Suggest the formula of the likely product if urea were used instead of ethanamide
in this conversion.
(1)
(e)
H= 23 kJ mol
NH3(g) + HNO3(g)
H = + 171 kJ mol
State why the expression for Kp for the reversible change does not include
ammonium nitrate.
(1)
(ii)
6.00 g of ammonium nitrate was gently heated in a sealed vessel until equilibrium
2
was reached. The equilibrium constant was found to be 15.7 atm under these
conditions. Calculate the partial pressure of ammonia present at equilibrium and,
hence, the percentage of the ammonium nitrate which has dissociated.
(One mole of gas under these conditions exerts a pressure of 50 atm.)
(5)
(iii)
Explain the concepts of thermodynamic and kinetic stability with reference to these
two reactions.
(5)
(Total 25 marks)
212
98.
(a)
(b)
(c)
(i)
H + 3O
2O
O + 3H
Calculate the enthalpy change for this reaction using the average bond enthalpy
values given below.
Bond
Average bond
1
enthalpy/kJ mol
Bond
Average bond
1
enthalpy/kJ mol
+412
+348
+360
+463
+496
C O
+743
(3)
213
(ii)
e n th a lp y
(2)
(Total 10 marks)
99.
(a)
hydrogen, H2
280
octane, C8H18
5510
Calculate the enthalpy change per unit mass for each of the fuels.
Hydrogen:
Octane:
(3)
214
(b)
Suggest, giving two reasons, which substance is the more useful as a fuel for motor cars
and give your reasoning.
Reason 1.................................................................................................................
...............................................................................................................................
Reason 1.................................................................................................................
...............................................................................................................................
(2)
(c)
100. In an experiment to find the enthalpy change when copper is displaced from a solution of
3
3
copper ions excess zinc was added to 50.0 cm of 1.00 mol dm aqueous copper(ii) sulphate in
a plastic cup.
2+
2+
215
T e m p e ra tu r e / C
70
60
50
40
30
20
10
(a)
9
10
T im e /m in u te s
Suggest two reasons why a series of temperature readings is taken rather than simply
initial and final readings.
First reason..............................................................................................................
................................................................................................................................
Second reason..........................................................................................................
................................................................................................................................
(2)
216
(b)
Use the graph to calculate the maximum temperature change, T, as the reaction takes
place.
T = ...........................................C
(2)
(c)
Calculate the enthalpy change for the reaction using the formula below, giving your
answer to an appropriate number of significant figures.
H = 4.18 T kJ mol
(2)
(Total 6 marks)
101. (a)
Define:
(i)
(ii)
217
(b)
Calculate the standard enthalpy of formation of benzene, C 6H6(l), using the following
enthalpy of combustion data:
Substance
H c /kJ mol
C6H6(l)
3273
H2(g)
286
C(s)
394
(3)
(c)
If the standard enthalpy of formation is calculated from average bond enthalpy data
assuming that benzene has three C==C and three CC bonds, its value is found to be
1
+215 kJ mol .
Explain, with reference to the structure and stability of benzene, why this value differs
from that calculated in (b). Use an enthalpy level diagram to illustrate your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)
218
(d)
Benzene reacts with bromine when gently warmed in the presence of a catalyst of
anhydrous iron(III) bromide.
(i)
The reaction is first order with respect to benzene and first order with respect to
bromine. Write the rate equation for the reaction.
......................................................................................................................
(1)
(ii)
S te p 1 .
B r+
B r
B r
S te p 2 .
Br
+H
102. (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)
H = 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.
219
(i)
(1)
(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)
220
(c)
Both phosgene and ethanoyl chloride, CH3COCl, contain a C==O group. Suggest an
equation for the reaction of phosgene with excess ammonia.
................................................................................................................................
(2)
(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)
221
(e)
(1)
(Total 15 marks)
103. (a)
(i)
Draw dot and cross diagrams to show the electronic structure of the ammonia and
of the boron trifluoride molecules. Hence deduce their shapes and suggest values
for the HNH and FBF bond angles in these molecules.
(5)
(ii)
Explain, in terms of the intermolecular forces involved, the variation of the boiling
temperatures of the Group 5 hydrides listed below.
Hydride
Boiling Temperature/ K
Ammonia, NH3
240
Phosphine, PH3
183
Arsine, AsH3
218
Stibine, SbH3
256
(5)
(b)
When ammonia and boron trifluoride are mixed, an addition compound, H3NBF3, is
formed.
(i)
Suggest how the nitrogen-boron bond forms between the two molecules in the
addition compound.
(1)
(ii)
Suggest how the HNH and the FBF bond angles would change when the addition
compound forms.
(2)
222
(c)
One of the early rocket fuels was hydrazine. It burns in oxygen as follows:
H2NNH2(g) + O2(g) N2(g) + 2H2O(g)
4
Bond
Bond enthalpy
1
/kJ mol
Bond
Bond enthalpy
1
/kJ mol
NH
+388
O==O
+496
NN
+944
HO
+463
(4)
(Total 17 marks)
104. (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.
223
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)
(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)
224
(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)
105. (a)
H /kJ mol
C (graphite)
393.5
H2(g)
285.8
ethane C2H6(g)
(i)
1560.0
(ii)
Complete the following thermochemical equation for the standard enthalpy change
of combustion of ethane.
..C2H6(..)+..O2(..) ..CO2(..)+..H2O(..)
=............................................
(3)
225
(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)
= 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)
(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
226
(ii)
(iii)
(iv)
(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)
227
(e)
Experiment
[CN ]/mol dm
[C2H5Br]/mol dm
3 1
Initial rate/mol dm 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
H
C H 3
N C .... C .......... B r
+ C H 3C H 2B r
C H 3CH 2C N + Br
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
228
(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)
106. The Born-Haber cycle for the formation of sodium chloride from sodium and chlorine may be
represented by a series of stages labelled A to F as shown.
N a + (g ) + C l(g ) + e
A
1
2
N a (g ) +
+
C l2 (g ) + e
B
N a(g ) +
1
2
C l2 ( g )
N a(s) +
1
2
C l2 (g )
N a + (g ) + C l (g )
C
D
E
N a C l( s )
229
(a)
(i)
Write the letters A to F next to the corresponding definition in the table below
definition
letter
H/kJ mol
st
+494
st
364
+109
+121
770
(ii)
Calculate the enthalpy of formation of sodium chloride from the data given.
(2)
(b)
The lattice enthalpies can be calculated from theory as well as determined experimentally.
Experimental H/kJ
1
mol
Theoretical
1
H/kJ mol
Sodium chloride
770
766
Silver iodide
889
778
230
Why is the experimental value of the lattice enthalpy of silver iodide (889kJmol ) so
different from the value calculated theoretically?
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(2)
(c)
Explain the trend in first ionisation energies of the elements of Group 1 in the Periodic
Table.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(3)
(Total 10 marks)
231