Answers

11 Equilibrium Answers to Exam practice questions
Pages 1719 Exam practice questions

[Sn 4 (aq)][Fe2 (aq)]2
1 a) i) Kc = [2]
[Sn2 (aq)][Fe3 (aq)]2
3 3
ii) Kc has no units [1]; the concentration terms cancel (mol dm ) appears on the top and
the bottom of the expression for Kc. [1]
The reciprocal of the value given in the question [1]: Kc = 1 10
10
b) i) [1]
The square root of the value given in the question [1]: Kc = 1 10 [1]
5
ii)
(0.070 mol dm3 )2
2 a) Kc = [1]
(0.010 mol dm3 ) (0.010 mol dm3 )
= 49 [1]; no units [1]
3
b) i) The quantity of iodine that has reacted = 0.0030 mol dm
3 3
This reacts with 0.0030 mol dm hydrogen and produces 0.0060 mol dm HI.
So the new concentrations are:
3 3
[H2(g)] = 0.017 mol dm [1] and [HI(g)] = 0.076 mol dm [1].
ii) Substituting in the expression for Kc gives:
(0.076 mol dm3 )2
= 48.5 [1]
(0.017 mol dm3 ) (0.0070 mol dm3 )
This is very close to the value for Kc calculated in (a). The system is again at equilibrium.
[1]
c) Doubling the hydrogen concentration causes a shift in the position of equilibrium to the right
giving more HI and less iodine [1]; some, but not all, of the added hydrogen reacts. [1]
3 a) At equilibrium the forward and backward reactions happen at the same rate so that overall
there is no change. [1] Nitrogen and hydrogen react to form ammonia as fast as ammonia
decomposes back to nitrogen and hydrogen. [1]
b) i) Mole fractions: NH3, 0.137 [1]; H2, 0.655 [1]; N2, 0.209 [1]
ii) Partial pressures: NH3, 1.37 atm; H2, 6.55 atm; N2, 2.09 atm [2]
(pNH3 )2
iii) Kp = [1]
pN2 (pH2 )3
= 3.20 10 [1]; atm [1]

3 2
4 a) Chemical equilibrium is dynamic [1]; on a molecular scale there is constant change with
opposing reactions cancelling each other out. [1] However, the overall macroscopic effect is
that nothing appears to be changing when the system is at equilibrium. [1]
b) Kc does not vary with concentration. [1] However, it is true that adding more of a reactant to
a system at equilibrium means that the mixture is no longer at equilibrium [1]; some of the
added chemical reacts and more products form until the system is again at equilibrium. [1]
c) Adding a catalyst does not affect the value of Kc. [1] At a constant temperature, the yield of
product at equilibrium is not changed by adding a catalyst [1]; however, many processes are
Andrew Hunt, Graham Curtis 2015

so slow that they never reach equilibrium in the absence of a catalyst, so in that sense an
added catalyst increases the yield by enabling the reaction mixture to reach equilibrium. [1]
d) This is true if the reaction to make products is endothermic. [1] If the reaction is exothermic,
then the equilibrium yield of product falls as the temperature rises. [1] However, as with
catalysts, raising the temperature can increase the yield of a product by allowing a reaction
mixture to reach equilibrium that reacts too slowly at room temperature. [1]
e) A reaction is feasible in the thermodynamic sense if the total entropy change for the process
is positive. [1] Adding a catalyst speeds up the rate of reaction but cannot change the
feasibility of a reaction at a particular temperature. [1] Only if the reaction is not going
because it is kinetically inert can a catalyst enable a reaction to happen at a particular
temperature. [1]
17
0.50 mol dm [1]
3
5 a) Concentration in aqueous layer =
10
3
= 0.85 mol dm [1]
6.0
0.01 mol dm [1]
3
b) Concentration in organic solvent =
10
3
= 0.006 mol dm [1]
0.85 mol dm3
c) Kc = = 140 [1]; no units [1]
0.006 mol dm 3
[PCl3 (g)][Cl2 (g)]
6 a) Kc = [1]
[PCl5 (g)]
1 3 1
b) Kc = = 125 [1] dm mol [1]
8 10 mol dm
3 3
c) [PCl3(g)] = [Cl2(g)] = x [1]

x2 3 3
= 8 10 mol dm [1]
5 10 mol dm3
2
2 3
x = 2 10 mol dm [1]
d) i) Some, but not all, of the added PCl5 decomposes [1] and increases the concentrations of
PCl3 and chlorine. [1]
ii) Increasing the pressure causes the equilibrium to shift in the direction that gives fewer
moles of gas [1]; so the concentration of PCl5 increases while the concentrations of PCl3
and chlorine decrease. [1]
iii) Raising the temperature causes the equilibrium to shift in the direction that is
endothermic [1]; so the concentration of PCl5 decreases while the concentrations of PCl3
and chlorine increase. [1]
e) i) Changing concentrations does not affect the value of Kc. [1]
ii) Changing the pressure does not affect the value of Kc [1]
iii) Kc increases [1] For an endothermic reaction the value of Kc gets larger as the
temperature rises [1]

pCO (pH2 )3
7 a) Kp = [2]
pCH4 pH2O
b) i) Kp does not change [1]

ii) Kp increases [1]
iii) Kp does not change [1]
c) i) Concentration of products decreases and the concentration of reactants increases. [1]
ii) Concentration of products increases and the concentration of reactants decreases. [1]
iii) Composition of the equilibrium mixture does not change. [1]
8 a) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) [2]
b) In theory the yield of NO at equilibrium is high if the temperature is low [1] and the pressure
low [1]; adding excess oxygen also favours the conversion of ammonia to NO. [1]
c) There is an excess of oxygen (even though only a fifth of the air is oxygen). [1] The
temperature has to be high because reaction only happens at a practicable rate if the catalyst
is hot. [1] Raising the pressure compresses the gases and this increases the mass of material
flowing through the reactor and hence the mass of product produced in a given time from a
given piece of plant. [1]
(The chosen pressure also depends on the price of platinum. Working at higher pressures
increases the wear on the catalyst and shortens the life of the catalyst gauzes.)
d) The gases flow through the solid catalyst gauzes and so the catalyst is used continuously and
does not have to be recovered from the reaction mixture. [1]
e) The gases flow through the catalyst gauzes so the mixture of product and unchanged
reactants is only in contact with the catalyst for a short time [1]; as soon as the gases flow
away from the catalyst reaction stops the mixture has time to approach equilibrium but not
reach equilibrium. [1]
f) The hot gases flow though a heat exchanger where they turn water to hot steam [1]; that can
be used in other processes or to generate electricity. [1]
9 a)
COCl2(g) CO(g) + Cl2(g)
Initial amount/mol 1 0 0
Amount at equilibrium/mol (1 )
Equilibrium partial pressure/Pa (1 )P P P
(1 ) (1 ) (1 )
Terms in second row of table [1]; total amounts in moles [1]; mole fractions [1];
partial pressures. [1]
2P
Kp = (working [1], answer [1])
(1 )(1 )
b) i) = 1.4 103 (working [1], answer [1])

ii) = 1.0 103 (working [1], answer [1])

10 a) i) Equal volumes of gases contain equal amounts, in moles, of gas. So the mole ratio is
1 : 1. [1] According to the equation 1 mol SO2 reacts with 0.5 mol O2, so the oxygen is in
excess. [1]
ii) According to the equilibrium law (and Le Chateliers principle), adding an excess of a
reactant tends to increase the conversion of other reactants to products. [1] Excess
oxygen favours the formation of sulfur trioxide. [1]
iii) The oxygen comes from the air and is mixed with nitrogen. [1] Adding more air would
dilute the sulfur dioxide so much that too little of the gas would be flowing into the
plant to produce product at a reasonable rate. [1]
b) 700 K is hot enough for the catalyst to be effective and for the reaction to be fast enough. [1]
The temperature is not higher because the reaction is exothermic and so the value of Kp falls
as the temperature rises. [1]
The equilibrium yield of product falls as the temperature rises. [1]
c) Raising the pressure would increase the yield of product at equilibrium because 3 mol
reactants combine to give 2 mol product. [1] Increasing the pressure would also increase the
mass of chemicals flowing through the plant. However a high-pressure plant costs more to
build and raises the running costs because of the energy needed to run the pumps. [1]
Since the conversion to SO3 is close to 100% it is generally not worth operating at a higher
pressure. [1]
d) The reaction is exothermic so at each stage the gas mixture tends to heat up. [1] The gas
mixture is cooled between catalyst beds to ensure that the equilibrium yield of product is as
high as possible. [1] (The energy is used to raise steam, which can be used in other processes
or used to generate electricity.)
e) Removing the product from the gas stream when the sulfur dioxide concentration is low
helps to shift the equilibrium to the right [1] to ensure that almost all the sulfur dioxide is
converted to sulfur trioxide. [1]
f) Sulfur dioxide is an acidic gas which causes acid rain. It is not acceptable to release any traces
of sulfur dioxide into the air. [1] There is a cost to removing the last traces of sulfur dioxide
from the remaining gases (which are mainly nitrogen and excess oxygen). [1]
11 a) 2HI(g) H2(g) + I2(g)
Initial amounts: HI(g) = 0 mol, H2(g) = 2 mol and [I2(g)] = 1 mol
Let the equilibrium amount of HI = 2x
Then the equilibrium concentrations:
2x (2 x) (1 x)
[HI(g)] = , [H2(g)] = and [I2(g)] = [1]
1 mol dm3 1 mol dm3 1 mol dm3
(2 x)(1 x)
Kc = = 0.020 [1]
4 x2
2
Hence: 0.92x 3x + 2 = 0.020 [1]

Solving shows that x = 0.935 [1]
Hence the equilibrium concentrations are:
[I2(g)] = 0.065 mol, [H2(g)] = 1.06 mol and [HI(g)] = 1.87 mol [2]
b) C2H5OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)
Initial amounts/mol: 3.0 1.0 0 3.0 [1]
Equilibrium amounts: (3.0 x) (1.0 x) x (3.0 + x) [1]
x(3.0 x)
Kc = = 4.0 [1]
(3.0 x)(1.0 x)
because the volume terms cancel.
2
Hence: 3x 19x + 12 = 0 [1]
x = 0.71 [1]
Amount of ethyl ethanoate at equilibrium = 0.71 mol [1]

c) I3 (aq) I2(aq) + I (aq)
Initial amounts/mol: 0 0.01 0.01 [1]
3 x (0.01 x)2 (0.01 x)2

Equilibrium concentrations/mol dm : [1]
1 1 1
(0.01 x)2 3
Kc = = 1.5 10 [1]
x
2
x 0.0215x + 0.0001 = 0 [1]
x = 0.0068 [1]
The equilibrium concentrations are:
3 3
[I3 (aq)] = 0.0068 mol dm and [I (aq)] = 0.0032 mol dm [1]
d) CO(g) + Cl2(g) COCl2(g)
Initial amounts/mol: 0.20 0.10 0 [1]
3 (0.20 x) (0.10 x) x
Equilibrium concentrations/mol dm : [1]
3 3 3
3x
Kc = = 0.41 [1]
(0.20 x)(0.10 x)
2
0.41x 3.123x + 0.0082 = 0 [1]
x = 0.0262 [1]
3
The equilibrium concentration is [COCl2(g)] = 0.026 mol dm [1]
e) 2NO2(g) N2O4(g)
Initial amounts/mol: 0 1
Equilibrium amounts/mol: 2x (1 x) [1]
Total amount at equilibrium/mol =(1 + x)
2x (1 x)
Equilibrium partial pressures/atm: 1 1 [1]
(1 x) (1 x)
(1 x)(1 x)2
Kp = = 7.1 [1]
(1 x)4 x 2

2
29.4x 1 = 0
x = 0.184 [1]
1 0.184
So partial pressure of N2O4 = 1 = 0.69 atm [1]
1 0.184
2 0.184
and partial pressure of NO2 = 1 = 0.31 atm [1]
1 0.184

13.2 Entropy Answers to Exam practice questions
Pages 8485
1 a) At 0 K water is solid and the atoms are highly ordered. [1] The crystals are not disrupted by
molecular movement. [1]
b) The rises in entropy at T1 and T2 correspond to the changes of state:
melting and vaporising. [1]
There is a greater increase in disorder when molecules separate from a liquid and turn to gas
than when molecules melt [1] because of the much greater freedom of movement of
molecules in the gas phase. [1]
c) i) Water and steam are in equilibrium [1] at 373 K and 1 atmosphere pressure so there is
no tendency for the change to go in either direction. [1]
ii) G = H TS [1]
1 H
Since G = 0 kJ mol , S = [1]
T
41.1 kJ mol 1
S = [1]
373 K
1 1
= 0.110 kJ mol K
1 1
= 110 J mol K [1]
2 a) NH4NO3(s) N2O(g) + 2H2O(g) [1]
Solid decomposing to two gases. Increased disorder. S positive. [1]
b) KCl(s) + aq KCl(aq) [1]
Ordered crystals breaking up to produce hydrated ions in solution. Increased disorder.
S positive. [1]
c) N2(g) + 2O2(g) 2NO2(g) [1]
Three moles of gas combining to give two moles of gas. Less disorder. S negative. [1]
d) 2H2O2(aq) 2H2O(l) + O2(g) [1]
Two moles of reactant producing three moles of product, one of which is a gas. Increased
disorder. S positive. [1]
e) NH3(g) + HI(g) NH4I(s) [1]
Two moles of gas combining to give one mole of solid. Less disorder. S negative. [1]
3 a) Al2O3(s) + 3C(s) 2Al(s) + 3CO(g) [1]
b) Total enthalpy change of formation of products = 3 (111 kJ mol ) = 333 kJ mol [1]
1 1
1
Total enthalpy change of formation of reactants = 1669 kJ mol [1]
1 1
Overall enthalpy change = 333 kJ mol (1669 kJ mol ) [1]
1
= +1336 kJ mol

c) Total entropy of reactants = 50.9 J mol K + (3 5.7 J mol K ) = 68 J mol K [1]

1 1 1 1 1 1
Total entropy of products = (2 28.3 J mol K + (3 198 J mol K )

1 1 1 1
1 1
= 651 J mol K [1]
1 1 1 1
Overall entropy change = 651 J mol K 68 J mol K [1]
1 1
= 583 J mol K
d) i) G = H TS [1]
G = +1336 kJ mol (298 K 0.583 kJ mol K ) [1]
1 1 1
1
= +1162 kJ mol
ii) The reaction is not feasible at 298 K because the free energy change is positive. [1]
e) The reaction becomes feasible when H TS < 0. [1] This is when TS > H.
This happens when T = 1336 kJ mol 0.583 kJ mol K
1 1 1
= 2292 K [1]
f) Reactions between solids are slow. The reaction rate has to be very high for it to proceed at a
measurable rate. [1]
1 1 1 1 1 1 1 1
4 a) (6 205 J mol K ) + S (C6H12O6) (6 214 J mol K + 6 70 J mol K ) = 256 J mol K [1]
1 1
S (C6H12O6) = +218 J mol K [1]
1 1 1 1
b) G = +2879 kJ mol (298 K 0.256 kJ mol K ) [1] = +2955 kJ mol [1]
c) i) G is large and positive at 298 K so the reaction is not feasible under standard
conditions. [1] The entropy change is negative and so TS is positive at all
temperatures. [1] Changing the temperature cannot make the free energy change for
the reaction negative. [1]
ii) A plant leaf is not a closed system. It is the input of energy from the Sun which makes
photosynthesis possible. [1]
5 a) G = H TS [1]
G = 519 kJ mol (298 K 0.082 kJ mol K ) [1]
1 1 1
1
= 543 kJ mol
b) i)
Labelled axes and appropriate

scales [1]; accurate plot giving
straight line. [1]

ii) The gradient of the graph is S. [1] Since the graph is a straight line this shows that
S does not vary with temperature. [1]
c) i) G is negative across the whole temperature range [1], so the reaction is feasible at all
these temperatures. [1]
ii) At 298 K the activation energy of the reaction is too high (the bonds in the molecules are
too strong) [1] and the energy of collisions between molecules too low for the reaction
to happen at a measurable rate. [1]
d) In the reaction forming CO and steam, 2.5 mol gases react to form 3 mol of gas. [1] This
increases disorder so that the entropy change is substantially positive. [1] In the reaction
forming soot, 2 mol gases react to form an ordered solid and 2 mol gas. [1] Overall there is
little change in entropy. [1]
6 a) Bromine is a liquid under standard conditions while iodine is a solid. For comparable
substances, liquids generally have higher standard entropy values than solids.[1] This is
because there is greater randomness in the distribution of molecules and energy quanta in a
liquid compared to a solid. [1]
b) At the boiling point the liquid and vapour are in equilibrium and so Stotal = 0 [1]
Stotal = Ssystem + Ssurroundings
H H
0 = Ssystem , hence Ssystem = [1]
T T
26 000 J mol 1 1
= = 84.4 J K [1] for 84.4, [1] for units
308 K
c) i) Highly endothermic change: H +ve [1]
1 mol liquid produces 1.5 mol gas, so S positive. [1]
Reaction is the reverse of hydrogen burning and so not expected to be feasible,
so G positive. [1]
ii) Highly exothermic change: H negative [1]
1 mol liquid fuel reacts with oxygen to produce more moles of gas (CO2 and H2O),
so S positive. [1]
G must be negative [1]
d) i) G = H TS [1]
G = +132 kJ mol (298 K 0.233 kJ mol K ) [1]
1 1 1
1
= +62.5 kJ mol
G 62 500 J mol1
ii) ln K = = [1] for numerator, [1] for denominator
RT 8.31 J mol1 K1 298 K
= 25.2
25.2 11
K=e = 1.1 10 [1]

iii) The positive value of G suggests that the reaction is not feasible at 298 K. [1] This is
confirmed by the very small value of K, which shows that that the equilibrium is well
over to the left-hand side. [1]
iv) The reaction becomes feasible when TS > H [1]
This happens when
T = 132 kJ mol 0.233 kJ mol K
1 1 1
= 566 K [1]

14 Redox II Answers to Exam practice questions
Pages 113115
1 a) i) Nitrogen oxidised from 3 to 0. [1] Chlorine reduced from 0 to 1. [1]
ii) Copper oxidised from +1 to +2 [1] and reduced from +1 to 0. [1]
iii) Oxygen oxidised from 2 to 0. Nitrogen reduced from +5 to +3. [1]
Cr2O7 (aq) + 14H (aq) + 6e 2Cr (aq) + 7H2O(l) [1]
2 + 3+
b) i)
SO3 (aq) + H2O(l) SO4 (aq) + 2H (aq) + 2e
2 2 +
[1]
+ 8H (aq) + 3SO3 (aq) 2Cr (aq) + 4H2O(l) + 3SO4 (aq) [1]
2 + 2 3+ 2
ii) Cr2O7 (aq)
iii) The yellow/orange dichromate solution [1] turns green as chromium(III) ions form. [1]
iv) 3 [1]
Cl2(aq) + 2I (aq) 2Cl (aq) + I2(aq) [1]

2 a) i)
2S2O3 (aq) + I2(aq) S4O6 (aq) + 2I (aq) [2]
2 2
ii)
b) Starch [1]
c) On mixing the swimming pool water with excess potassium iodide the colourless solutions
react to give a dark yellow-brown solution. [1] During the titration the colour of the solution
becomes paler. Eventually it turns pale yellow. [1] On adding starch the solution turns blue-
black. At the end-point the black colour disappears to give a colourless solution. [1]
d) Amount of sodium thiosulfate added to reach the end-point
= 0.0194 dm 0.0050 mol dm
3 3
= 0.000 097 mol [1]

3
This reacted with the iodine displaced by the chlorine in 20 cm of the water. [1]
From the equations 2S2O3 (aq) Cl2(aq), so the amount of chlorine in the 20 cm water
2 3
= 0.5 0.000 097 mol [1]

So the concentration of chlorine in the water
0.5 0.000 097 mol 3
= = 0.00242 mol dm [1]
0.020 dm3
3 a) Fe (aq) + e Fe (aq) [1] reduction
3+ 2+
Cu(s) Cu (aq) + 2e
2+
[1] oxidation [1]
b) Fe is reduced from +3 to +2 [1]
Cu is oxidised from 0 to +2 [1]
2+ 3+ 2+
c) Cu(s)|Cu (aq)Fe (aq), Fe (aq)|Pt(s) [2]
Cell e.m.f. = Ecell = +0.77 0.34 = +0.43 V [1]
4 a) Using filter paper soaked in saturated KNO3(aq) or a U-tube of agar gel containing saturated
KNO3(aq). [1]
Cu(s) Cu (aq) + 2e
2+
b) i) [1]
Ag (aq) + e Ag(s) [1]
+
ii)
c) 2Ag (aq) + Cu(s) 2Ag(s) + Cu (aq) [1]
+ 2+

d) Ecell = 0.34 V + 0.80 V [1] = +0.46 V [1]

+
e) At the silver electrode [1] where Ag ions gain electrons. Silver changes oxidation number
from +1 to zero. [1]
f) Any two of the following points for [2]:
temperature was not standard
concentration(s) were not standard
conditions were not standard.
+
5 b) i) O2(g) + 4H (aq) + 4e 2H2O(l)
2H2(g) 4H+(aq) + 4e [1]
Overall: O2(g) + 2H2(g) 2H2O(l) [1]
ii) From the hydrogen half-cell [1]
b) Fuel cells differ from storage cells in that:
instead of recharging the cells, the reactants are fed into the cell continuously [1]
the products are drawn off continuously [1]
the voltage in the cell remains constant so long as fuel and oxygen are supplied. [1]
c) Fuel cells produce electric power from the chemical free energy of the fuel and oxygen [1]
much more efficiently. [1]
Fuel cells do not pollute the atmosphere with pollutants from combustion [1] such as oxides
of nitrogen and particulates; and they do not pollute rivers with warm water. [1]
d) This question assesses a students ability to show a coherent and logically structured answer
with linkages and fully sustained line of reasoning. Assess the quality of the answer taking
into account both the key points made (up to 4 marks) and the logic and coherence of the
discussion (up to 2 marks).
Points to make in the answer:
Advantage that a fuel cell is more efficient as a power source than a combustion engine.
Advantage that there is no local air pollution (no CO2, no particulates, no oxides of
nitrogen) because the only product is steam.
Advantage, in the future, that it may become practicable to make the hydrogen using
replenishable energy sources.
Disadvantage that hydrogen is currently made from fossil fuels.
Disadvantage there are many technical difficulties associated with the handling, transport
and storage of hydrogen for use in vehicles.
Disadvantage that hydrogen fuel cells are more costly than combustion engines and have
a shorter life.
Disadvantage that the public may not be willing to accept the use of hydrogen as a fuel
because of perceptions of its flammability and the danger of explosions.
6 a) MnO4 + 8H + 5e Mn + 4H2O
+ 2+

C2O4 2CO2 + 2e
2
5 mol C2O4 2 mol MnO4 [1]

2
2 7.445 g dm3 3
Concentration of C2O4 = = 0.05556 mol dm [1]
134 g mol1
25.00
Amount of C2O4 reacting = dm 0.055 56 mol dm = 0.001389 mol dm [1]
2 3 3 3
1000
3 2 0.001 389
Amount of MnO4 in 28.85 cm solution = mol [1]
5
2 0.001 389
Concentration of the KMnO4 solution =
3
= 0.01926 mol dm [1]
5 0.028 85
b) The half-equations for the reaction are:
MnO4 + 8H + 5e Mn + 4H2O and (Fe Fe + e ) 5
+ 2+ 2+ 3+
5 mol Fe 1 mol MnO4 [1]

2+
26.75 0.535
dm 0.0200 mol dm =
3 3
Amount of MnO4 reacting = mol [1]
1000 1000
0.535 2.675
Amount of Fe reacting = 5 mol =
2+
mol [1]
1000 1000
2.675
mol 55.8 g mol = 0.15 g [1]
1
So the mass of iron in the ore =
1000
0.15 g
Percentage iron in the iron ore = 100 = 11.2% [1]
1.34 g
c) The half-equations for the reaction are:
MnO4 + 8H + 5e Mn + 4H2O and (Fe Fe + e ) 5
+ 2+ 2+ 3+
5 mol Fe 1 mol MnO4

2+
Zinc reduces iron(III) to iron(II): Zn Zn + 2e [1]

2+
In the first titration:

18.00 3 0.360
dm 0.0200 mol dm =
3
Amount of MnO4 reacting = mol
1000 1000
0.360
Amount of Fe in 25.00 cm of the solution = 5 mol
2+ 3
1000
0.360
5 mol = 0.0720 mol dm [1]
2+ 3
Concentration of Fe in the solution =
1000 0.0250
In the second titration, after reduction of iron(III) to iron(II):
22.50 0.450
dm 0.0200 mol dm =
3 3
Amount of MnO4 reacting = mol
1000 1000
0.450
Amount of Fe and Fe in 25.00 cm of the solution = 5 mol [1]
2+ 3+ 3
1000
0.450
5 mol = 0.0900 mol dm
2+ 3+ 3
Concentration of Fe and Fe in the solution =
1000 0.0250
2+ 3+ 3
Total concentration of Fe and Fe = 0.0900 mol dm [1]

3+ 3 3
Concentration of Fe = (0.0900 0.0720) mol dm = 0.0180 mol dm [1]
7 a) 1 mol S2O3 1 mol electrons [1]
2
2
Amount of S2O3 (aq) needed in the titration
= 0.0180 dm 0.0760 mol dm = 0.001 37 mol [1]
3 3
Amount of copper ions in the pipette volume of solution

3.405 g
= 0.1 = 0.001 36 mol [1]
249.5 g mol1
So there is a change of 1 mol of electrons per mol of copper(II) ions
when they oxidise iodide ions. [1]
Copper(II) is reduced to copper(I). [1]
b) 2Cu (aq) + 4I (aq) 2CuI(s) + I2(aq)
2+
I2(aq) + 2S2O3 aq) 2I aq) + S4O6 aq)

2 2
2 mol S2O3 1 mol I2 2 mol Cu [1]

2 2+
22.5
dm 0.14 mol dm
2 3 3
Amount of S2O3 reacting =
1000
3.15
= mol [1]
1000
2+ 3.15
So the amount of Cu reacting = mol [1]
1000
3.15
Mass of copper reacting = mol 63.5 g mol = 0.20 g [1]
1
1000
0.20 g
Percentage of copper in the alloy = 100 = 72.7% [1]
0.275 g
Fe(s) + I2(aq) Fe (aq) + 2I (aq) or Cd(s) + I2(aq) Cd (aq) + 2I (aq) [1]

2+ 2+
8 a) i)
because each of these reactions would have a large positive Ecell . [1]
Fe(s) + Cd (aq) Fe (aq) + Cd(s) [1]
2+ 2+
ii)
because this produces a very small positive Ecell . [1]
b) i) Labels on the diagram should point to
Fe(s) electrode, in Fe (aq) solution, [1] 1 mol dm [1]
2+ 3
Pt electrode [1], in a solution containing I2(aq) and I (aq), both at 1 mol dm [1]
3
salt bridge. [1]

ii) Arrow from Fe electrode to Pt electrode and labelled electron flow. [1]
iii) Ecell = + 0.54 ( 0.44) = + 0.98 V
[1] for magnitude, [1] for sign to correspond to that of the right-hand electrode
2+
iv) There would be a greater tendency for Fe(s) to form Fe (aq) [1], which would make the
2+
Fe |Fe electrode more negative [1], thus increasing the magnitude of the cell e.m.f. [1]

c) i) +0.34 V [1]
2+ 2+ 3
ii) When log[Cu (aq)] = 0, [Cu (aq)] = 1.0 mol dm [1] and the value of E is the standard
electrode potential. [1]
2+
iii) There is a linear relationship between the electrode potential and log[Cu (aq)]. [1]
The equation for a linear equation takes the general form: y = mx + c
In this instance this can be written as: E = constant log[Cu (aq)] + E
2+
[2]

15 Transition metals Answers to Exam practice questions
Pages 144146
2 2 6 2 6 1 2
1 a) i) 1s 2s 2p 3s 3p 3d 4s [1]
2 2 6 2 6 10 1
ii) 1s 2s 2p 3s 3p 3d 4s [1]
2 2 6 2 6 9
iii) 1s 2s 2p 3s 3p 3d [1]
b) In d-block elements, the last electron added enters a d sub-shell [1]; which applies to
both Sc and Cu.
Transition elements have at least one stable ion [1]; with a partially filled d sub-shell. [1]
c) i) Tetraamminediaquacopper(II) [1]
ii) Octahedral [1]
2+
d) In the Cu ion, the energy levels of the five d-orbitals are split [1] by ligands. Electrons in the
slightly lower 3d level can absorb energy from certain wavelengths in the visible spectrum [1]
and jump to the slightly higher 3d level. [1]
The light transmitted is therefore richer in certain wavelengths than others in the visible
spectrum, so it appears coloured [1].
2 a) i) A transition metal is an element with at least one stable ion [1] with a partially filled d
sub-shell. [1]
Example: electron configuration of a transition metal ion with the 3d orbitals shown
1 9
between d and d . [1]
ii) An oxidation number is a number assigned to an atom or ion [1] to describe its relative
state of oxidation or reduction. [1]
Example: oxidation number of Fe in any iron(II) compound is +2. [1]
iii) A complex ion is an ion in which a number of molecules and/or anions (ligands) [1] are
bound to a central metal ion by co-ordinate bonds. [1]
2+
Example: Cu(H2O)6 [1]
b) This question assesses a students ability to show a coherent and logically structured answer
Precipitation reactions example with equation and colour of precipitate.
Complexing (ligand substitution) example with equation and colours of complex ions.
Redox reactions example with equation (half-equations) and colour change.
Catalytic action example with equation(s) and evidence of catalytic activity.
3 a) +6 [1]
b) Yellow [1]; to orange [1]
2CrO4 (aq) + 2H (aq) Cr2O7 (aq) + H2O(l) [1]
2 + 2

3+
c) Green [1]; Cr [1]
2 + 3+
d) i)
20
dm 0.100 mol dm = 0.002 mol [1]
3 3
ii)
1000
iii) 0.002 6 = 0.012 mol [1]
iv) 0.012 mol of VOClx gives up 0.012 mol of electrons. Therefore 1 mol of VOClx gives up
1 mol of electrons. So, vanadium changes its oxidation state by +1. [1]
v) Oxidation state of vanadium in VOClx is +4. So the formula of the oxochloride is VOCl2.
[1]
4 a) i) Heterogeneous [1]
ii) Homogeneous [1]
iii) Heterogeneous [1]
iv) Heterogeneous [1]
b) In the presence of a catalyst, the reaction pathway has an activation energy which is much
lower than when there is no catalyst. [1] Tungsten metal adsorbs hydrogen onto the crystal
structure as single atoms. [1] So the catalyst breaks the bonds between the atoms in one of
the reactants. [1] The pathway with a lower activation energy allows the reaction to proceed
much faster. [1]
2+
5 a) A contains [Cu(H2O)6] [1]
B contains Cu(OH)2(H2O)4 [1] (accept Cu(OH)2)
2
C contains [CuCl4] [1]
2+ 2+
D contains [Cu(NH3)4(H2O)2] [1] (accept Cu(NH3)4 )
b) The yellow/green solution changes colour through green [1] to blue. [1]
When conc. HCl is added to the blue copper(II) sulfate solution (A), the following
equilibrium [1] is set up:
2+ 2
Cu(H2O)6 (aq) + 4Cl (aq) CuCl4 (aq) + 6H2O(l) [2]
blue yellow
In excess HCl, the equilibrium lies to the right so the solution appears yellow/green. [1] As
excess water is added, the equilibrium shifts to the left [1]; and the solution becomes blue.
(maximum 6 marks)
c) Cu(H2O)6 (aq) + 2OH (aq) Cu(H2O)4(OH)2(s) + 2H2O(l) [1]
2+
(accept Cu (aq) + 2OH (aq) Cu(OH)2(s))

2+
4
EDTA is a very powerful [1]; hexadentate [1]; ligand. [1]
It forms a chelated complex/chelate [1]; with copper(II) ions and prevents them from reacting

with OH ions. [1] (maximum 5 marks)

6 a) Homogeneous catalysis involves catalysis in which the catalyst and the reactants are in the
same phase. [1]
The most important feature of transition metal ions in homogeneous catalysis is that they can
change their oxidation state. [1]
2I (aq) + S2O8 (aq) I2(aq) + 2SO4 (aq)
2 2
b) i)
[1] for balanced equation, [1] for state symbols
ii) Either the reactants are both negative ions which will repel each other;
2 2
or there are bonds to break in the S2O8 to form SO4 . [1]
2Fe (aq) + 2I (aq) 2Fe (aq) + I2(aq) [1]
3+ 2+
iii)
2Fe (aq) + S2O8 (aq) 2Fe (aq) + 2SO4 (aq) [1]
2+ 2 3+ 2
c) i) Adsorption of gases on the metal surface is so strong that reactions cannot occur [1];
adsorption of gases on the metal surface is so poor that there are insufficient atoms for
the reaction to occur at a useful rate. [1]
ii) Adsorption is neither too strong nor too weak [1]; reactants can be adsorbed in sufficient
numbers, react and then get desorbed from the metal surface at a good rate. [1]
d) Pt alloy or Pt or Pt/Rh [1]; the reducing agent is CO/carbon monoxide [1];
2CO(g) + 2NO(g) 2CO2(g) + N2(g) [1]
7 a) H2NNH2(aq) + 4OH (aq) N2(g) + 4H2O(l) + 4e

[2]
b) Its E value is more positive than +0.66 V [1] but less positive than +1.32 V. [1]
c) The two half-equations are:
H2NNH2(aq) + 4OH (aq) N2(g) + 4H2O(l) + 4e

and

+ H2O(l) + e VO (aq) + 2OH (aq)) 4
+ 2+
(VO2 (aq) [1]

N2(g) + 4VO (aq) + 4OH (aq)
+ 2+
Overall: H2NNH2(aq) + 4VO2 (aq) [1]
d) i) Disproportionation is the simultaneous oxidation and reduction of atoms or ions of the
same element. [1]
+ 2+
For example, Cu ions can disproportionate to Cu and Cu. [1]
ii) Disproportionation requires the oxidation state of an element to both rise to a higher
state and fall to a lower state. [1]
2VO (aq) V (aq) + VO2 (aq) [1]
2+ 3+ +
iii)
VO (aq) + H2O(l) + e V (aq) + 2OH (aq) E = 1.32 V
2+ 3+
iv)
VO2 (aq) + 2OH (aq) VO2 (aq) + H2O(l) + e E = +0.66 V
+ +
This disproportionation will not occur under standard conditions in alkaline solution,
+
because VO2 (aq) (the oxidised form of the more positive electrode system) [1] tends to
3+ 2+
oxidise V (aq) (the reduced form of the less positive electrode system) to VO (aq). [1]
So vanadium(V) and vanadium(III) tend to react to give vanadium(IV), which is the
reverse of disproportionation. [1]

8 a) A complex is a molecule or ion in which ligands [1] are attached to a central metal cation by
co-ordinate bonds. [1]
A stereoisomer is one of two or more molecules or ions with the same molecular/ionic
formula and the same structural formula [1], but different stereo formulae (different
positions of the atoms in space). [1]
b) i) +2 [1]
ii) +3 [1]
c) i) 4 [1]
ii) 6 [1]
d) i) Diamminedichloronickel(II) [1]
ii) Tetraamminedichlorocobalt(III) [1]
e)
2 marks for each diagram: [1] for lone pairs on N; [1] for correct shape.
f)
2 marks for each diagram: [1] for lone pairs on N; [1] for correct shape.

16 Kinetics II Answers to Exam practice questions
Pages 167168
1 a) H2O2(aq) + 2H (aq) + 2I (aq) 2H2O(l) + I2(aq) [1]
+

b) Rate = k[H2O2(aq)][I (aq)] [2]
c) Second order [1]
d) The first step [1], which includes the two species that feature in the rate equation. [1]
2 a) Labelled axes [1]; accurate plot [1]; smooth curve. [1]
b) Three half-lives = 40 10 s [2]; half-life of first order reaction independent of initial
3
concentration. [1]
3 1
c) Method of calculating gradient [1]; values for gradients [2]; units: mol dm s . [1]
d) Axes [1]; accurate plot with straight line. [1]
k = 1.8 10 s [1] for value, [1] for units
5 1
3 a) Axes [1]; plot and curve. [1]

Half-life from 20 10 mol dm : 3.6 10 s [1]
3 3 3
Half-life from 12 10 mol dm : 7.6 10 s [1]

3 3 3
Lower starting concentration higher half-life. [1]

b) Tangents drawn [1]; gradients calculated [1]; concentration units included. [1]
c) Log(rate) and log(concentration) values quoted. [2]
Graph correctly plotted with labelled axes. [2]
Order 2 derived from line of best fit. [2]
4 a) i) Changing [X] does not affect the rate [1]; zero order. [1]
ii) Rate quadruples if [Y] doubles [1]; second order. [1]
2
b) Rate = k[Y] [2]
(1 10 4 mol dm3 s 1)
= 1 10 dm mol s
2 3 1 1
c) k = [1] for value, [1] for units
(1 10 1 mol dm 3)2
d) Rate-determining step involves two Y molecules. [1]

Y + Y Y2 slow [1]
Y2 + X XY2 fast [1]
e) Range of answers possible (1 mark for each point made up to 3). Such as:
Rate equations help to deduce reaction mechanisms; this information can inform
methods of chemical synthesis.
Understanding catalytic activity (including enzymes) can lead to the development of more
efficient manufacturing processes or guide drug design and development.
Rate measurements are important in controlling chemical changes in laboratory and
industrial processes; chemical engineers use rate data when designing chemical plants.

5 a) The concentrations of all the reacting chemicals are known at the start before they have
begun to be used up. [1] It is then only necessary to follow the concentrations of one of the
reactants long enough to determine the initial rate from a concentrationtime graph. [1]
b) i) The reaction is second order with respect to hydrogen. [1]
ii) The reaction is first order with respect to NO. [1]
2
c) Rate = k[H2] [NO] [1]
(1.20 mol dm3 s1 )
d) k = 4.2 10 dm mol s
5 6 2 1
(0.012 mol dm3 )2 (0.002 mol dm3 )
[1] for value, [1] for units
e) Most reactions take place in several steps. Only one of these steps is rate determining. [1] It is
the concentrations of the molecules or ions involved in the rate-determining step that appear
in the rate equation. [1]
f) i) As the temperature rises the value of the rate constant gets larger. [1]
ii) The rate of reaction increases as the temperature rises. This happens because as it gets
hotter the mean kinetic energy of the molecules increases. [1] This is shown by a shift in
the curve of the MaxwellBoltzmann distribution to the right. The consequence is that
there are more molecules with enough energy to react when they collide. [1] The
collisions have enough energy to exceed the activation energy for the reaction. [1] The
rate increases even if the concentrations of reactants stays the same. This is explained,
in the rate equation, by the fact that the value of the rate constant increases. [1]
6 a) The clock procedure measures the initial rate in this case by finding the time taken for a
small, fixed amount of iodine to form. [1] At first the thiosulfate ions immediately turn the
iodine back to iodide ions [1]; but once all the thiosulfate is used up the iodine produces a
deep blue-black colour with the starch indicator. [1]
b) Completion of table as in Figure 16.10 [3]:
Temperature, T/K 288 292.5 299 308 315
Time, t, for the blue 10.0 7.0 5.0 3.5 2.5
colour to appear/s
ln (1/t) 2.30 1.95 1.61 1.25 0.92
1
1/T /K 0.00347 0.00342 0.00334 0.00325 0.00318
Plot of graph of ln (1/t) against 1/T with appropriate scales and accurate linear plot. [3]
E a
Gradient = 4180 K [1] =
R
1
Ea = 35 kJ mol [1]

c) The catalyst provides an alternative reaction pathway with a lower activation energy. [1] One
possible alternative route is that when the catalyst is present, the iron(III) ions oxidise iodide
ions to iodine [1], and that peroxodisulfate(VI) ions then oxidise the resulting iron(II) ions
back to iron(III), thus regenerating the catalyst. [1] Perhaps the negative peroxodisulfate( VI)
ions react more readily with positive iron(II) ions than with negative iodide ions. [1]
7 a) 3ClO (aq) ClO3 (aq) + 2Cl (aq) [1]

Chlorate(I) (+1) is oxidised to chlorate(V) (+5) and reduced to chloride (1). [2]
b) The rate decreases by a factor of 4. [1]
c) The rate-determining step appears to involve two chlorate( I) ions. [1]
Step 1: slow rate-determining [1]
2ClO (aq)

ClO2 (aq) + Cl (aq) [1]
Step 2: fast [1]
ClO2 (aq) + ClO (aq) ClO3 (aq) + Cl (aq)

[1]

d) One possibility is to look for evidence that ClO2 (aq) exists as an intermediate. [1] It might be
detected spectroscopically. [1] This might be hard to do since the second step is fast and so
the intermediate disappears very quickly.
8 a) Reactions happen when molecules collide. Collisions with an energy greater than the
activation energy lead to reaction. [1] Typically the activation energy is to the right-hand end
of the MaxwellBoltzmann distribution, so that only a small proportion of collisions lead
to reaction. [1] Raising the temperature shifts the MaxwellBoltzmann distribution to the
right. [1] The value of the activation energy does not change but the area under the curve of
the distribution representing the number of molecules with enough energy to react can
increase markedly for a small rise in temperature. [1]
b) Raising the temperature increases the speed with which molecules in a gas move so it
increases their kinetic energy. [1] Raising the temperature increases not only the number of
collisions per second, but also the energy of the collisions. [1] So the increase in reaction rate
is the result of two factors: collision rate and the energy per collision. [1]
c) Plot of graph of ln (1/t) against 1/T with appropriate scales and accurate linear plot. [3]
The gradient of the graph = 2.24 10 K [2]
4
Ea = 2.24 10 K 8.31 J K mol [1]

4 1 1
1 1
= 186 000 J mol = 186 kJ mol [1]

17.1 Chirality Answers to Exam practice questions
Page 178
1 a) Two structural isomers with the same functional group [1]; structures of 1-chloropropane and
2-chloropropane. [1]
1-chloropropane 2-chloropropane
b) Six isomers in total: three structural isomers, each of which have E/Z forms.
F and H on the same C atom [2]
Z-1-bromo-1-chloro-2-fluoroethene E-1-bromo-1-chloro-2-fluoroethene
F and Cl on the same C atom [2]
F and Br on the same C atom [2]
c) Structural isomerism (position) and optical isomerism.
1-bromo-2-chloroethane [1] 1-bromo-1-chloroethane [1]

1-Bromo-1-chloroethane exists as a pair of optical isomers:
[1]
2 a) A chiral centre is typically a carbon atom with four different groups around it [1]; in general a
molecule is chiral if it is asymmetric.
b) The mirror-image forms of a chiral molecule cannot be superimposed on one another [1];
they have opposite effects as they rotate the plane of plane-polarised light. [1]
c) Only CH3CHOHCOOH is chiral and can exist as two optical isomers [1]; the other two
compounds both have two hydrogen atoms on the central carbon atom.

d) A racemic mixture contains equal amounts of the two optical isomers [1]; the two isomers
rotate the plane of plane-polarised light equally but in opposite directions, so their effects
cancel. [1]
e) i) C13H21O3N [1]
ii) There is one chiral carbon atom: [1]
3 Stereoisomerism involves molecules with the same molecular formula [1]; and the same
structural formula [1]; but different three-dimensional shapes [1]; in which their atoms occupy
different positions in space. [1]
There are two forms of stereoisomerism.
E/Z (cis/trans) isomerism [1]; which occurs principally in alkenes and other compounds with C=C
double bonds. [1]
In E/Z isomerism, the Z-isomer has atoms, attached to the C atoms of the double bond, with
higher atomic number [1] on the same side of the double bond. [1]
In the E-isomer, atoms attached to the C atoms of the double bond with higher atomic number
are on opposite sides of the double bond. [1] An example of E/Z isomerism is
1,2-dibromoethene.
Named structures of the E- and Z-isomers. [2]
Optical isomerism [1] involves non-superimposable mirror images. [1] In most cases, this requires
the molecules to possess a C atom with four different atoms or groups attached to it. [1]
These mirror images are labelled (+) and () forms. [1]
The (+) form rotates plane-polarised light clockwise [1] and the () form rotates plane-polarised
light anticlockwise. [1]
A named example of optical isomerism [1]; e.g. alanine or bromochlorofluoromethane.
Diagram showing structures of the optical isomers of the example suggested as mirror images. [1]
(Any 15 of these or other legitimate points)
4 a) There is a chiral centre in C2H5CHBrCH3. This means that the molecule is asymmetric and has
distinct mirror-image forms. [1]
b) At a lower temperature the main mechanism for the hydrolysis is S N2. [1] The molecule
inverts in the one continuous step of this process. [1] So an optically active reactant gives rise
to an optically active product. [1]
c) At the higher temperature there is more energy in the collisions between molecules. [1] The
energy is sufficient to break the CBr bond and permit the SN1 mechanism. [1] The first step
of this process gives rise to a planar carbocation intermediate with a positive charge on the
central carbon atom. [1] In the second step, hydroxide ions can attack from either side of the
plane, giving rise to a roughly equal mixture of the two optical isomers. [1] The result is the
optically inactive racemic mixture. [1]

d) H2C=CHCH2CH3; but-1-ene [1]

CH3CH=CHCH3; but-2-ene [1]; both E- and Z-isomers. [1]
5 a) Electrophilic addition [1]
[4] for the diagram: [1] for each of the three curly arrows and [1] for the structure of the
intermediate ion.
b) HBr can add across the double bond in two ways via different carbocations. [1]
The secondary carbocation is more stable than the primary because of the extra inductive
effect [1], so 2-bromopentane is the major product. [1]
c) In the mechanism, the planar carbocation [1] can be attacked by the bromide ion from above
or below [1] with equal probability [1] so an optically inactive racemic mixture is formed. [1]
6 a)
A B C D
[1] [1] [1] [1]
b) i) Call the isomers A, B, C & D as shown. A possible method is:
Add bromine water to all four [1]: C & D decolourise it [1]; no change with A & B. [1]
Add acidified potassium dichromate(VI) to C & D [1]: D turns it from orange to green [1];
no change with C. [1]
Add acidified potassium dichromate(VI) to A & B. [1]: B turns it from orange to green [1];
no change with A. [1]
1
ii) A absorption at 17201700 cm for a ketone C=O. [1]
1
B absorption at 17401720 cm for an aldehyde C=O. [1]
1
C absorption at 16691645 cm for an alkene C=C but no absorption for an OH
1
alcohol around 37503200 cm . [1]
1
D absorption at 16691645 cm for an alkene C=C and also an absorption for an OH
1
alcohol around 37503200 cm . [1]
c) and
Four-membered ring is strained as the bond angle is 90 [1] compared with the tetrahedral
109.5. [1]
Three-membered ring is even more strained as the bond angle is only 60. [1]
The four-membered ring is likely to be more stable. [1]

7 The final step gives equal amounts of two optical isomers. [1]
The molecules of R must have a chiral centre: CH3CH2CH(CH3)COOH. [1]
The change from P to Q suggests the hydrolysis of the double ethyl ester of a carboxylic acid. [1]
So Q must have two carboxylic acid groups. [1]
Q decomposes to R by losing CO2. [1] Acids with two carboxylic acid groups attached to the same
carbon atom lose a carboxylic acid group relatively easily. [1]
Q: [1]
P: [1]

17.2 Carbonyl compounds Answers to Exam practice questions
Pages 192193
1
Reactant Reagent Organic product
Name Displayed formula
CH3CH2CHO Tollens reagent Propanoic acid [1]
[1]
2 +
CH3CH2CHO Cr2O7 /H [1] Propanoic acid
[1]
CH3CH2CHO LiAlH4 Propan-1-ol [1]
[1]
2 a) C10H16O [1]
b) i) Carboncarbon double bond as in an alkene [1]; aldehyde group. [1]
ii) Ketone group. [1]
c) i) The blue reagent gives an orange-brown precipitate [1] with citral; but not with
-ionone. [1]
ii) The reagent gives a bright orange precipitate [1]; both with citral and with -ionone. [1]
iii) The reagent gives a pale yellow precipitate [1] with -ionone; but not with citral. [1]
d) i) ii)
[1] [1]
e) i) Both compounds have E/Z isomers. [1]

ii) EITHER OR
[1] [1]
Z-citral [1] Z--ionone [1]

iii) Neither compound has a chiral centre and so neither has optical isomers. [1]

3 X must have four separate groups around the central carbon atom [1] including an acid group to
give carbon dioxide with a carbonate [1]: CH3CHOHCOOH. [1]
Oxidation gives a carbonyl compound Y which is a ketone because it does not react with Fehlings
solution [1]: CH3COCOOH. [1]
4 a) W: empirical formula CH2, molecular formula C4H8 [1]; could be but-1-ene or but-2-ene [1];
because both give 2-bromobutane when they add HBr.
X: 2-bromobutane [1]; because it hydrolyses to butan-2-ol. [1]
Y: butan-2-ol [1]; a secondary alcohol because it oxidises to a ketone. [1]
Z: butanone [1]; a ketone because it does not react with Benedicts reagent. [1]
b) CH3CH=CHCH3(l) + HBr(g) CH3CH2CHBrCH3(l) [1]
CH3CH2CHBrCH3(l) + NaOH(aq) CH3CH2CHOHCH3(l) + NaBr(aq) [1]
CH3CH2CHOHCH3(l) + [O] CH3CH2COCH3(l) [1] (oxidation)
c) W: Electrophilic addition [1]
X: Nucleophilic substitution [1]
5 i) a) Tollens [1]: pentanal gives a silver mirror [1]; no reaction with pentan-3-one. [1]
b) Acidified K2Cr2O7 [1]: no reaction with pentan-3-one [1]; solution turns from orange to
green with pentan-3-ol. [1]
c) Iodine and sodium hydroxide [1]: no reaction with pentan-3-ol [1]; yellow precipitate
with pentan-2-ol. [1]
ii) a) Infrared absorptions: pentanal gives an absorption in infrared in the region
1
17401720 cm [1]; pentan-3-one gives an absorption in infrared in the region
1
17201700 cm . [1]
b) Infrared absorptions: pentan-3-one gives an absorption in infrared in the region
1 1
17201700 cm [1]; pentan-3-ol gives an absorption in the region 37503200 cm . [1]
c) Optical activity: pentan-2-ol has a chiral centre so each enantiomer will show optical
activity [1]; pentan-3-ol does not have a chiral centre so does not show any optical
activity. [1]
6) a) CH3CH2CHO + H2O CH3CH2COOH + 2H + 2e
+
[1]
b) CH3CH2CHO + 3OH CH3CH2COO + 2H2O + 2e

[1]
c)
[1]

7 a)
Cyanide ion plus lone pair plus arrow [1]; propanal plus arrow. [1]
Structure of intermediate ion. [1]
Arrow from lone pair on O to HCN and arrow from HCN bond to C of CN. [1]
+
b) If the pH is too high, then [H ] is low [1] (and [HCN] falls), so the second stage becomes slow.
[1]

If the pH is too low, then [CN ] is low [1] and the first stage becomes slow. [1]
c) A racemic mixture is formed [1] because attach by the nucleophile can occur from above or
below the plane of the carbonyl group. [1]
8 a) i) C6H12O6 [1]
ii) The formula can be rewritten as C6(H2O)6. So glucose contains carbon with hydrogen and
oxygen in the same proportions as in water. [1] Hence the name carbohydrate.
b) The large number of OH groups means that there is extensive hydrogen bonding between
glucose molecules. [1]
These intermolecular forces are strong enough for the relatively small molecules to form a
solid at room temperature. [1]
Glucose molecules can also form many hydrogen bonds with water molecules [1]. The
interaction with water is strong enough for glucose molecules to break away from the solid
and dissolve. [1]
c) The functional group in open chain glucose is an aldehyde group. Glucose is an aldose. [1]
d) i) Glucose gives an orange precipitate when it reacts with 2,4-dintrophenylhydrazine. [1]
ii) 2,4-Dinitrophenylhydrazine reacts with the aldehyde group in the open chain form. [1]
Only 1% of glucose is in the open chain form in solution. [1]
e) i) As an aldehyde, glucose reacts with Tollens reagent to give a silver mirror. [1]
ii) Glucose is a reducing agent. It reduces silver(I) ions in Tollens solution to metallic silver.
[1] (Glucose similarly reduces copper(II) to copper(I) when it reacts with Fehlings or
Benedicts reagent.)

f) The oxygen on carbon number 5 [1] uses its lone pair to act as a nucleophile [1] to attack the
+ carbon of the carbonyl group on carbon number 1. Nucleophilic addition [1] occurs to
produce the six-membered ring structure. [1] A racemic [1] mixture is formed of and
glucose.
9 Equations to describe the mechanism of addition to C=C and C=O. (2 [2])
Propene with bromine HCN with propanone
Similarities Addition reaction

Heterolytic bond breaking
Two-step process (any 2 for [2])
Differences Electrophilic reagent Nucleophilic reagent
Attacks electron-rich bond Attacks + end of polar C=O bond
Intermediate is a positive ion Intermediate is a negative ion
(any 2 for [2]) (any 2 for [2])
10 a) CH3COCH2CH3 + 2[H] CH3CHOHCH2CH3 [1]

b) i) LiAlH4 effectively contains hydride ions so reacts by nucleophilic addition. [1]
C=O bonds are polar and the nucleophile can attack the + carbon. [1]
C=C bond in alkenes is non-polar so nucleophiles cannot attack
OR The cloud of electrons in alkenes repels the negative hydride ion. [1]
ii) Hydride ions react with + H atoms [1] in water molecules so LiAlH4 is decomposed by
solvents which can donate protons. [1]
c) LiAlH4 is the stronger [1] as it is a better hydride donor.

AlH4 ions contain H ion co-ordinately bonded to Al (using vacant orbital in level 3). [1]

These hydride ions are less strongly held than the H ion co-ordinately bonded to B in BH4
ions, which use vacant orbital in level 2. [1]
11 a) A molecule of P adds two molecules of HCN so P has two aldehyde groups. [1]
P is OHCCH2CH2CHO [1] rather than CH3CH(CHO)2. [1]
Q is HOCH(CN)CH2CH2CH(CN)OH. [1]
Oxidation converts aldehyde groups to acid groups. [1]
R is HOOCCH2CH2COOH. [1]
1.0 g R is 0.00847 mol of the compound. [1]
In the titration this reacts with 0.0169 mol sodium hydroxide [1];
so 1.0 mol of the acid reacts with 2.0 mol of the alkali. [1]
This confirms that there are two acid groups in R.

b) The ratio of amounts in Z is C : H : O = 5.36 : 7.11 : 1.79 [1], which is 3 : 4 : 1.

The simplest (empirical) formula of Z is C3H4O. [1]
The molar mass of Z is 56 and its molecular formula is also C 3H4O. [1]
0.00179 mol Z [1] reacts with 0.00356 mol hydrogen. [1]
So 1 mol Z reacts with 2 H2, showing that there are two double bonds in the molecule. [1]
Z reduces Fehlings solution so one of the double bonds is in an aldehyde group. [1]
Z is CH2=CHCHO. [1]
12 Step 1: Warm 2-bromobutane with aqueous/alcoholic sodium hydroxide [1] to form
butan-2-ol. [1]
Step 2: Heat with acidified potassium dichromate(VI) [1] to form butanone. [1]
Step 3: Add iodine and sodium hydroxide [1] to form propanoate ions [1] (and CHI3).
Step 4: Acidify with dilute hydrochloric acid. [1]

17.3 Carboxylic acids and their
derivatives Answers to Exam practice questions
Pages 209211
1 Butane is non-polar. The only intermolecular forces are weak London forces. It has the lowest
boiling temperature: 273 K. [1]
Methyl methanoate has a polar C=O bond and so there are attractions between permanent
dipoles as well as London forces. It boils at a higher temperature than butane: 305 K. [1]
Hydrogen bonding is the strongest type of intermolecular force. Hydrogen bonding is possible
between the molecules of propan-1-ol and between the molecules of ethanoic acid. [1]
There is greater scope for hydrogen bonding in ethanoic acid with the OH group and O atom in
the carboxylic acid group. Hence both compounds boil at a higher temperature than propanal,
but ethanoic acid boils at a higher temperature (391 K) than propan-1-ol (371 K). [1]
2
a) 1 mark for each complete box. [6]

b) 1 mark for each correctly labelled arrow. [8]
3 a) CH3CHBrCHBrCH2CH2COOCH3 [1]
b) CH3CH2CH2CH2CH2COOCH3 [1]
c) CH3CH=CHCH2CH2COONa and CH3OH [1]

4 a) Possible answers:
Reaction with magnesium [1]; colourless flammable gas given off as metal disappears [1];
reaction much faster with hydrochloric acid. [1]
OR
Reaction with sodium carbonate solution [1]; colourless gas given off which turns limewater
milky [1]; effervescence much more vigorous with hydrochloric acid. [1]
+
b) Acid solutions react in a similar way because they contain H (aq) ions. [1]
Mg(s) + 2H (aq) Mg (aq) + H2(g) [1]
+ 2+
CO3 (s) + 2H (aq) CO2(g) + H2O(l) [1]

2 +
HCl(aq) is a strong acid and so is fully ionised [1]; ethanoic acid is a weak acid and so is only
slightly ionised. [1]
The reactions with HCl(aq) are much faster because of the higher concentration of hydrogen
ions. [1]
5 a) Propanoyl chloride, CH3CH2COCl [1]
b) Butan-1-ol, CH3CH2CH2CH2OH [1]
c) Pentan-1-ol, CH3CH2CH2CH2CH2OH [1]; and sodium ethanoate CH3COONa [1]
d) Calcium ethanoate, (CH3COO)2Ca [1]
e) Methylethyl ethanoate, CH3COOCH(CH3)2 [1]
6 a) C13H18O2 [1]
b) The carboxylic acid group can form hydrogen bonds with water. [1] The hydrocarbon part of
the molecule is non-polar and cannot easily break into the hydrogen-bonded structure of
water. [1] The large hydrocarbon part of the molecule, including a benzene ring, means that
ibuprofen is only likely to be very sparingly soluble in water. [1]
c) i) The same as the structure shown in the question but with the carboxylic acid group
+
turned into a sodium salt: COO Na . [1]
ii) The same as the structure shown in the question but with the carboxylic acid group
turned into an ethyl ester: COOC2H5. [1]
7 a)
Left-hand side structures and reversible arrows [1]; right-hand structures. [1]
b) Sulfuric acid acts as a catalyst in the esterification reaction. [1]
c) The compounds involved, especially ethanol, are volatile [1] and flammable so naked flames
must be kept well away from them. [1]
d) Ethyl ethanoate [1]

e) Ethanoic acid has a pungent smell. [1]

It dissolves in water and so does not mask the smell of the ester, which floats on the top. [1]
8 a) A condensation reaction is one in which molecules join together by splitting off a small
molecule, such as water, from two functional groups, such as a carboxylic acid group and an
alcohol group [1]; condensation polymers are produced by a series of condensation reactions
between the functional groups of the monomers, where each monomer has at least two of
the reactive functional groups. [1]
b)
[1] [1]
Benzene-1,4-dicarboxylic acid is a carboxylic acid. [1]
Propane-1,3-diol is an alcohol. [1]
c) Polyesters are used to make fibres and fabrics for clothing and other uses. [1]
Polyesters can be melted and spun into fibres which are strong. The fibres in polyester fabrics
do not stretch or shrink. [1]
9 This question assesses a students ability to show a coherent and logically structured answer with
linkages and fully sustained line of reasoning. Assess the quality of the answer taking into
account both the key points made (up to 4 marks) and the logic and coherence of the discussion
(up to 2 marks).
One mol of acid reacts with 2 mol NaOH therefore each acid contains a benzene ring and two
carboxylic acid groups.
Z has two H and one O less than the formula of its parent acid. Therefore it is an anhydride.
The anhydride forms from heating the compound with two carboxylic acid groups that are
attached to neighbouring carbon atoms in the benzene ring, therefore acid Y is
benzene-1,2-dicarboxylic acid (phthalic acid).
Z is
X forms a linear polymer, therefore it has the carboxylic acid groups on opposite sides of the
benzene ring, so X is benzene-1,4-dicarboxylic acid (terephthalic acid).
W is benzene-1,3-dicarboxylic acid.
10 A an acid liberates CO2 with a carbonate [1], so CH3COOH. [1]
B an aldehyde gives a red ppt with Fehlings [1], so HOCH2CHO. [1]
C an ester is hydrolysed by NaOH(aq) [1], so HCOOCH3. [1]

11 a) Step 1: Heat under reflux with dilute hydrochloric acid. [1]

Step 2: React with PCl5 at room temperature. [1]
b) CH3CH2CH2COCl [1]; butanoyl chloride. [1]
c) Butanamide [1]
[1]
12 a) Amount of H2O = 2 0.27 = 0.54 mol [1]
Amount of A = 0.50 0.27 = 0.23 mol [1]
Amount of CH3CH2OH = 0.80 (2 0.27) = 0.26 mol [1]
[B][H2O]2
b) Kc = [1]
[A][C2H5OH]2
[0.27 / V ][0.54 / V ]2
= [1]
[0.23 / V ][0.26 / V ]2
= 5.1 (no units) [1]

It is not necessary to know the volume, V, because V cancels in the expression for Kc. [1]
c) Exothermic reaction [1]
So, by Le Chateliers principle, the reaction moves to the LHS to oppose an increase in
temperature [1]; so Kc decreases. [1]
d) Diethyl ethanedioate [1]
Any one from:
flammable so keep away from flames
corrosive, so wear protective gloves/eye protection
use in well-ventilated area. [1]
13 a) The four isomeric esters are
1 HCOOCH2CH2CH3 [1]
2 HCOOCH(CH3)2 [1]
3 CH3COOCH2CH3 [1]
4 CH3CH2COOCH3 [1]

b) This question assesses a students ability to show a coherent and logically structured answer
On hydrolysis, the esters form volatile alcohols and carboxylate salts.
Esters 2 and 3 form propan-2-ol and ethanol respectively, which both form CHI3
precipitates with I2/NaOH; but esters 1 and 4 form propan-1-ol and methanol, which do
not give a yellow precipitate.
Therefore esters 2 and 3 are W and X (but not necessarily in that order).
Acidification of the remaining solution in the flask forms carboxylic acids.
Esters 1 and 2 form methanoic acid, which can be oxidised by KMnO 4 and decolourise it
because HCOOH contains the aldehyde group; but ester 3 forms ethanoic acid and ester 4
forms propanoic acid, neither of which have any effect on KMnO4.
Therefore esters 1 and 2 are W and Z (but not necessarily in that order).
Therefore: W = ester 2 X = ester 3 Y = ester 4 Z = ester 1

18.1 Arenes benzene compounds
Answers to Exam practice questions
Pages 230232
1 a) Benzene has a planar molecule [1]; with six carbon atoms in a regular hexagon. [1] Each
carbon atom forms a normal covalent () bond with its two adjacent carbons atoms and a
hydrogen atom. [1] These bonds involve three of the four outer shell electrons on each
carbon atom. The fourth electron on each carbon atom occupies a p orbital [1]; at right
angles to the benzene ring. Sideways overlap [1] of the p orbitals leads to the formation of
bonds [1]; involving rings of delocalised electrons [1] above and below the plane of the
benzene molecule. (maximum 6 marks)
b) The delocalised electron system in benzene is disrupted initially by formation of an
+
intermediate cation [1], but is restored by elimination of H and a reaction involving
substitution. [1]
In ethene, the localised bond is weaker than the delocalised system in benzene. [1]
The breakage of the bond in ethene and the formation of two single bonds by an addition
reaction occurs easily. [1]
So addition is energetically more favourable than substitution [1] (maximum 4 marks)
2 a) An electrophilic substitution is a reaction in which an electron-deficient species, an
electrophile [1], replaces an atom or group of atoms. [1]
b) Methylbenzene [1]
Iron(III) bromide or aluminium bromide or their chlorides. [1]
c)
d) Friedel and Craft [1]

3 a) A is cyclohexane; B is hydrogen; C is aluminium chloride or iron(III) chloride; D is
ethylbenzene; E and F are concentrated nitric acid and concentrated sulfuric acid. [6]
+ +
b) i) CH3C H2 [1]; NO2 [1]
ii) Temperature 5060 C. [1]
HNO3 + H2SO4 H2O + NO2 + HSO4

[1]
[2]
iii) Explosives/further reactions to produce dyes. [1]
c) i) Temperatures >150 C, and high pressure. [1]
ii) As a solvent [1]

d) i)
n
[1]
ii) As an insulator or for packaging. [1]

4 a) i) Aluminium chloride or iron(III) chloride [1]
ii) Bubble chlorine into a boiling benzene and catalyst mixture [1]; under reflux [1];
in a fume cupboard. [1]
b) i) I is 1-chloro-4-methylbenzene. [1]
II is (chloromethyl)benzene. [1]
ii) Formation of I is by electrophilic substitution. [1]
Formation of II is by radical substitution. [1]
c) i) II reacts with sodium hydroxide. [1]

OH can attack the + carbon of the CH2Cl group in II. [1]

The electron cloud of the benzene ring will repel the OH so no reaction will take place
with I. [1]
ii) C6H5CH2OH [1]; nucleophilic substitution. [1]
5 a) Any two from (maximum 2 marks):
limiting the amount of concentrated HNO3 used
adding the nitrating mixture to the methyl benzoate in small amounts
keeping the temperature below 15 C.
b) Methyl 2-nitrobenzoate [1]; methyl 4-nitrobenzoate. [1]
c) To remove any nitric and sulfuric acid. [1]
d) The impurities dissolve in the hot ethanol but there is little present [1] so that none
crystallises out when the ethanol is cooled down [1].
e) i) Some will remain dissolved in the ethanol even when it is cooled in ice. [1]
ii) Taking the minimum volume of ethanol needed to dissolve all the impure solid at the
high temperature. [1]
Cooling the ethanol solution so that more crystallises. [1]
f) Larger crystals form if the solution cools slowly. [1]

g) Methyl benzoate is the limiting reactant.

3
Volume of methyl benzoate used = 5 cm
Mass of methyl benzoate used = 5.5 g [1]
5.5 g
Moles of methyl benzoate used = = 0.0404 mol [1]
136.0 g mol1
From the equation: 1 mol methyl benzoate 1 mol methyl 3-nitrobenzoate

0.0404 mol methyl benzoate 0.0404 mol methyl 3-nitrobenzoate
Theoretical yield of methyl 3-nitrobenzoate = 0.0404 mol 181.0 g mol [1] = 7.3 g [1]
1
3.5
h) Percentage yield = 100% = 48% (2 s.f.) [1]
7.3
6 a) A is dilute nitric acid. [1]
b) B C
[1] [1]
c) i) EITHER warming [1] with dilute nitric acid [1]
OR conc. nitric acid [1] at room temperature. [1]
ii) 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 3,4-dinitrophenol,
3,5-dinitrophenol.
All 5 correct [3]; 3 or 4 correct [2]; 1 or 2 correct [1]. (Subtract [1] for any incorrect
isomers to a minimum of 0.)
7 a) i) CH3CH2COCl [1]; catalyst AlCl3 [1]
CH3CH2COCl + AlCl3 CH3CH2C O + AlCl4
+
ii) [1]
[1] [1]
b) LiAlH4 [1]; nucleophilic addition. [1]
c) Conc. phosphoric or conc. sulfuric acid [1]; dehydration or elimination. [1]
d) Step 2: Optical isomerism occurs as product has four groups attached to central C. [1]
Racemic mixture of optical isomers formed. [1]

H can attack from either side of planar C=O. [1]
Step 3: E/Z isomerism. [1]
No rotation about C=C. [1]
Two different groups on each end of the C=C. [1]

8 a) i)
[1]
ii)
[1]
b)
[1]
c) A lone pair of electrons on each of the OH groups in L-dopa interacts with the delocalised
electrons in the benzene ring [1], releasing electrons into the ring and making it more
susceptible to electrophilic attack. [1]
d) i) Primary amines are organic compounds containing the NH2 group.
ii)
9 a)
H1 = 6 atH(carbon) + 6 atH(hydrogen) [1]

H1 = 6(+715) + 6(+218) [1]
1
H1 = +5598 kJ mol [1]
For Kekul benzene:
H2 involves formation of 3 CC bonds + 3 C=C bonds + 6 CH bonds. [1]
1
H2 = 3(347) + 3(612) + 6(413) kJ mol [1]
1
H2 = 5355 kJ mol [1]
1
fH = H1 + H2 = +5598 5355 kJ mol
1
= +243 kJ mol [1]
1
b) Experimental value is +82 kJ mol .
1
Difference is 161 kJ mol . [1]
1
So actual benzene is 161 kJ mol lower in energy than the Kekul structure. [1]
Delocalisation of electron density gives extra stability to benzene. [1]

10 a) This question assesses a students ability to show a coherent and logically structured answer
Ethanol is much weaker acid than phenol.
Dissociation of alcohols is according to ROH(aq) RO (aq) + H (aq).
+
For phenol, the negative charge is delocalised into benzene ring.

Therefore the anion is stabilised and proton loss is easier.
For ethanol, the inductive effect of the ethyl group pushes electrons towards the oxygen
so its electron density is increased.
Therefore the anion is more likely to bond to H to reform the OH bond.
+
b) Ethanol forms CH3COOCH2CH3; ethyl ethanoate [1]

Phenol forms CH3COOC6H5; phenyl ethanoate [1]

18.2 Amines, amides, amino acids
and proteins Answers to Exam practice questions
Pages 255258
1 a) D b) C c) E d) B e) A f) D [1] for each
2 a) Proton acceptor [1] lone pair which can be donated. [1]
+ 2
b) (CH3CH2CH2CH2NH3 )2 SO4 [1]
c) Bases are lone pair donors. [1] Inductive effect of alkyl group increases electron density on N
in butylamine so better lone pair donor. [1] Lone pair is delocalised into aromatic ring in
phenylamine so poorer lone pair donor. [1]
2+
d) Deep blue solution [1]; acts as a ligand [1]; [Cu(C4H9NH2)4(H2O)2] (aq). [1]
3 a) i) Insertion of to give:
[2] (wrong way around gets [1])

ii) All four chiral centres circled [3]; three chiral centres circled [2]; two chiral centres
circled [1].
b) The compound has at least one carbon atom with four different atoms or groups attached to
it. [1] Molecules of the compound are asymmetric. [1] The compound has optical isomers. [1]
c)
[1] [1]

4 a) The NH2 group in amino acids can act as a base accepting H ions and the COOH group can
+
+
act as an acid, donating H ions. [1] Therefore, in solution, amino acids, like glycine, can exist
as zwitterions such as H3 NCH2COO (aq). [1]
+
At one particular pH, the glycine particles will form zwitterions with an overall net charge of
zero and this pH is the isoelectric point of the amino acid. [1]
b) The isoelectric point of the amino acid will be dictated by the relative abilities of the COOH
group to donate H ions and the NH2 group to accept them. [1] These relative abilities are
+
not equal, so the isoelectric point is not at pH = 7. [1]

As the isoelectric point of glycine is at pH = 6; this suggests that the COOH group loses
H ions to form COO ions more readily than the NH2 group accepts them to form
+
NH3 ions. [1]

+
However, at pH = 6 (i.e. [H ] > [OH ]), the dissociation of COOH is suppressed and the
+
acquisition of H by NH2 is raised so that the two processes are equally likely. [1] At this pH,
+
the zwitterions are most stable and the average net charge on glycine particles is zero. [1]
c) Glutamic acid has two COOH groups and only one NH2 group. This will mean that COO

anions form more readily than NH3 cations. [1] In order to suppress the formation of COO
+
groups and promote the formation of NH3 groups relative to the glycine situation, the pH
+
must be more acidic. [1] Therefore, the isoelectric point of glutamic acid will be less than
pH = 6. [1]
5 a) i) CH3CH2Br + NH3 CH3CH2NH2 + HBr [1]
Note that the HBr formed will react with NH3 to form the salt NH4Br, so strictly the
equation should be:
CH3CH2Br + 2NH3 CH3CH2NH2 + NH4Br
ii) Nucleophilic substitution [1]
iii) (CH3CH2)2NH and (CH3CH2)3N [2]
iv) The ethylamine which forms is a better nucleophile than ammonia [1] and may react
with any unreacted bromoethane forming diethylamine. [1]
CH3CH2Br + CH3CH2NH2 (CH3CH2)2NH + HBr
diethylamine
The diethylamine can also react as a nucleophile [1] with any excess bromoethane to
form triethylamine.
CH3CH2Br + (CH3CH2)2NH (CH3CH2)3N + HBr
triethylamine
Note that the HBr formed in each of these reactions will react with the amines in the
reaction mixture to form substituted ammonium salts.

b) Ethylamine vapour and hydrogen chloride gas will diffuse away from the cotton wool plugs
along the tube [1]. The relative molecular mass of HCl (Mr = 36.5) is marginally less than that
of ethylamine (Mr = 45.0) so it will diffuse slightly faster along the tube. [1]
When the vapours meet (approximately midway along the tube, but slightly closer to the
ethylamine end [1]), a white smoke will form, eventually settling on the bottom of the tube as
a white powder [1]. This is ethylammonium chloride.
CH3CH2NH2(g) + HCl(g) CH3CH2NH3 Cl (s) [1]
+
6 a) i) Fishy smell [1]

ii) 1,5-Diaminopentane [1]
+ +
iii) Cl H3NCH2CH2CH2CH2CH2NH3 Cl [1]
+
iv) NH4 Cl [1]; ammonium chloride [1]
v) NaCl [1]; H2O [1]
b) i) Primary amines have one alkyl or aryl group attached to an NH2 group. [1]
Secondary amines have two alkyl or aryl groups attached to an NH group. [1]
Tertiary amines have three alkyl or aryl groups attached to a nitrogen atom. [1]
ii) Cadaverine is a primary amine [1]; piperidine is a secondary amine. [1]
c) Their infrared spectra will be very similar [1]; because they have exactly the same types of
bonds. [1]
7 a)
[1]
[1]
b) CH3CH=CHCH3 [1]; but-2-ene [1]

c) i)
[1] [1]
ii) 1,4-Dihydroxybenzene (4-hydroxyphenol) or pentanedioic acid [1]

d) Ester links in the condensation polymer can be hydrolysed by water [1]; and this process will
be catalysed if the conditions are acidic or alkaline. [1]
[1]
The CC and CH bonds in polymer A are strong and non-polar, so are not degraded by
sunlight, water, acids, alkalis or microorganisms. [1]
8 a) i) Mass C : H : N = 61.0 : 15.3 : 23.7 [1]
61.0 15.3 23.7
Moles C : H : N = : :
12.0 1.0 14.0
= 5.08 : 15.30 : 1.69 [1]
= 3 : 9 : 1 [1]
Empirical formula = C3H9N
ii) Its relative molecular mass (or molar mass). [1]
iii)
[1] for each.

b) The alkyl groups provide an inductive effect towards the nitrogen atom. This increases the
electron density on the nitrogen atom and also its basic character. [1]
Therefore, the predicted order of basic strength from the strongest to the weakest should be:
trimethylamine (3 alkyl groups ) > ethylmethylamine and 2-aminopropane
(2 alkyl groups) > propylamine (1 alkyl group). [1]
c) In water, the amines are protonated by the water:
+
R2NH + H2O R2NH2 + OH
+
R3N + H2O R3NH + OH (Both equations needed for [1].)
Because of the extra NH bonds in the protonated secondary amines there is more hydrogen
+
bonding possible. [1] This stabilises these ions more than the equivalent R 3NH . [1]

9 a) i)
ethenol [1] repeat unit [1]
ii)
[1]
iii) Relative mass of one poly(ethenol) unit = 44.0 [1]

Relative mass of one poly(ethenyl ethanoate) unit = 86.0 [1]
Relative molecular mass of polymer
= relative mass of 1800 poly(ethenol) units
+ relative mass of 200 poly(ethenyl ethanoate) units
= (1800 44.0) + (200 86.0) [1]
= 79 200 + 17 200 = 96 400 [1]
iv) Almost every monomer unit contains an OH group which can hydrogen bond with
water. [1] The extensive hydration of the OH groups by water molecules results in a
soluble polymer. [1]
b) i) Because there are fewer OH groups on the polymer which can form hydrogen bonds
with water molecules. [1] (Water molecules can, of course, still form hydrogen bonds
with the O atoms in the C=O bonds of the ethanoate groups, but the larger size of the
ethanoate group relative to the OH group will reduce its solubility.)
ii) Because the OH groups on the poly(ethenol) molecules will form hydrogen bonds with
each other rather than with water molecules. [1]
iii) The poly(ethenol) forms a crystalline solid in which extensive hydrogen bonding
between OH groups along the polymer chain holds the molecule firmly together. [1]
Few, if any, OH bonds are available for hydrogen bonding with water and the
poly(ethenol) is insoluble. [1]
(Allow credit for any sensible suggestions.)

10 a) i) Induced dipole attractions [1]

ii) Low density polythene has short side chains attached to the main CC chain. [1] This
means that its molecules cannot pack as closely as those in high density polythene. [1]
iii) High density polythene has the higher melting temperature. [1] Molecules in high
density polythene can pack closer than those in low density polythene. [1] This results in
more and stronger induced dipole attractions. More energy is therefore needed to
overcome the stronger forces in high density polythene, [1] so its melting temperature is
higher.
b) i) A polyamide is a polymer with amide links between monomer units. [1]
ii)
[1]
iii) Hydrogen bonds [1]

iv) Hydrogen bonds between the H atom of an NH group on one chain and the N atom on
another chain. [1]
Hydrogen bonds between the H atom of an NH group and the O atom of a C=O group
on another chain. [1]
c) i) In the crystalline regions, the chains of different molecules are packed in a regular,
parallel fashion, but in the non-crystalline regions, the molecules are more randomly
placed. [1]
ii) In the crystalline regions, more hydrogen bonds can form between the parallel chains
making the total intermolecular forces stronger. [1]
11 a) To prevent loss of nitrobenzene if the flask gets hot. [1]
b) The reaction is too slow if the temperature is too low. [1]
c) To allow unreacted nitrobenzene to evaporate. [1]
d) To neutralise the HCl so oily phenylamine forms from the water-soluble salt. [1]
To convert the tin compounds into soluble hydroxy complex ions. [1]
e) To saturate the aqueous layer and reduce the solubility of phenylamine in the water. [1]
f) Although the densities are similar, the salt increases the density of water so the phenylamine
floats [1]; it is the upper layer. [1]
g) To absorb water. [1] (Other drying agents react with the phenylamine.)
3
h) 4.2 cm nitrobenzene have mass 4.2 1.20 = 5.04 g [1]
5.04
Amount nitrobenzene = mol = amount phenylamine [1]
123.0
5.04
Max. mass phenylamine expected = 93.0 = 3.81 g [1]
123.0

i) C6H5NO2(aq) + 7H (aq) + 6e C6H5NH3 (aq) + 2H2O(l) [1]

+ +
Sn(s) + 6Cl (aq) [SnCl6] (aq) + 4e [1]

2
2C6H5NO2(aq) + 14H (aq) + 3Sn(s) + 18Cl (aq) 2C6H5NH3 (aq) + 3[SnCl6] (aq) + 4H2O(l) [1]
+ + 2
12 This question assesses a students ability to show a coherent and logically structured answer with
linkages and fully sustained line of reasoning. Assess the quality of the answer taking into
account both the key points made (up to 4 marks) and the logic and coherence of the discussion
(up to 2 marks).
C=O bond in ethanamide.
Lone pair on N in propylamine accepts protons, so is basic.
C=O withdraws electrons from lone pair on N, therefore ethanamide is not basic.
Hydrogen bonding in propylamine, therefore liquid at room temperature.
Delocalisation of lone pair from N onto C=O
leads to a separation of charge and therefore stronger electrostatic forces in ethanamide.

18.3 Organic synthesis Answers to Exam practice questions
Pages 280282
1 a) i) A is immiscible with water. This suggests that part or all of the molecule is non-polar. [1]
ii) The cream precipitate is silver bromide [1]; so, A contains bromine. [1]

A might be a bromoalkane which has reacted with OH ions in NaOH(aq) to form an

alcohol and Br ions. [1] (Maximum 2 marks)
b) i) Charring is the formation of carbon [1]; the vapour produced on heating is water [1];
this suggests that B may be hydrated/contain water of crystallisation. [1] (Maximum 2
marks)
ii) B is acidic. [1]
iii) B is sufficiently acidic to produce CO2 [1] from Na2CO3(aq). So the acid group present is
not a phenol. [1]
iv) The sweet-smelling product is probably an ester [1], which has been formed by reaction
of a carboxylic acid [1] with ethanol plus concentrated H2SO4 as catalyst.
c) i) The very smoky flame suggests C has an aryl group/high C : H ratio. [1]
ii) C is not acidic/a carboxylic acid. [1]
iii) C contains an OH group [1]; which reacts with sodium to produce hydrogen. [1]
2 a) The diagram for refluxing should show:
liquids heated in a round-bottomed or pear-shaped flask [1]
Liebig (water) condenser arranged vertically [1]
water in at the bottom, out at the top. [1]
Subtract [1] if condenser is closed at the top.
b) A Refluxing for 45 minutes as the reaction is slow [1]; the reflux condenser prevents
escape of volatile reagents such as ethanol. [1] Conc. H2SO4 is the catalyst. [1]
B Collecting all the distillate below 84 C ensures that all the ethyl ethanoate is collected.
[1]
C Sodium carbonate neutralises any acid impurity in the distillate. [1]
D Anhydrous sodium sulfate or anhydrous calcium chloride are added to remove
water [1] from the organic product.
E Collecting liquid that boils between 75 and 79 C ensures that most of the ethyl
ethanoate is collected [1], but other impurities with boiling temperatures above or
below this range are not collected. [1]
(Total 8 marks)

3 a) Phenol [1]; carboxylic acid [1]

b) C7H6O3 [1]
c) i) ii)
(Allow one or two Br atoms

at any positions on the ring.)
iii)
4 a) To spread the heat from the Bunsen over the bottom of the flask. [1]
b) So that a larger surface area of the rind is exposed to hot water and steam. [1]
c) Steam distillation [1] Use a dropping pipette to remove the upper oily layer or use a
separating funnel [1]
d) Leave the limonene in a specimen tube with a suitable drying agent such as anhydrous
calcium chloride, anhydrous sodium sulfate, anhydrous magnesium sulfate or silica gel. [1]
e) Because the temperature required to vaporise the limonene would char the peel and
decompose the limonene. [1]
f) The alkene group. [1] Show that the limonene will decolourise yellow/orange bromine water
[1] and will also decolourise dilute acidified purple potassium manganate(VII). [1]
5 a) C13H20O3 [1]
b) Alkene [1]; carbonyl [1]; ester [1]
c) i) and ii)
[2] [2]
iii) The stereoisomers with the skeletal formula shown will all be Z isomers. [1]
There will be (+) and () isomers at both the chiral centres [1]; therefore four
stereoisomers [1]; with the skeletal formula shown.

6 a) F is CH3CH2CH2OH [1]; propan-1-ol. [1]

G is CH3CHOHCH3 [1]; propan-2-ol. [1]
H is CH3CH2CHO [1]; propanal [1]
J is CH3COCH3 [1]; propanone [1]
b) i) The orange [1]; mixture turns green. [1]
The products are propanoic acid [1]
3+
and chromium(III) ions Cr /chromium(III) sulfate. [1]
ii) Reduction half-equation:
2 + 3+
Oxidation half-equation:
CH3CH2CHO(aq) + H2O(l) CH3CH2COOH(aq) + 2H (aq) + 2e [1]
+
Overall ionic equation:

Cr2O7 (aq) + 8H (aq) + 3CH3CH2CHO(aq) 2Cr (aq) + 3CH3CH2COOH(aq) + 4H2O(l) [1]
2 + 3+
(Accept CH3CH2CHO + [O] CH3CH2COOH for [1])

12.0
7 a) Mass of C in 0.36 g of the compound = 0.88 g = 0.24 g [1]
44.0
2.0
Mass of H in 0.36 g of the compound = 0.36 g = 0.04 g [1]
18.0
Mass of O in 0.36 g of the compound = (0.36 0.28) g = 0.08 g
0.24 0.04 0.08
Ratio of moles of C : H : O = : : [1]
12.0 1.0 16.0
= 4 : 8 : 1
Empirical formula of X = C4H8O [1]
Relative molecular mass of X 70
Relative molecular mass of empirical formula = 72
Molecular formula of X = C4H8O [1]
b) X contains a carbonyl group. [1]
c) CH3CH2CH2CHO butanal [1]
2 methylpropanal [1]
CH3CH2COCH3 butanone [1]

d) Butanal and butanone have four different types of carbon so either could be X. [1]
Take the melting temperature of X [1] and compare with values on the data sheet of melting
temperatures of 2,4-dinitrophenylhydrazine derivatives of carbonyl compounds. [1]

8 a) Warm (reflux) with aqueous NaOH. [1] Acidify with HNO3(aq) and then add AgNO3(aq). [1]
Cl white precipitate [1], I yellow precipitate. [1]
b) Iodine and aqueous sodium hydroxide. [1] Pentan-2-one will give a pale yellow precipitate of
CHI3. [1] There will be no precipitate with pentan-3-one. [1]
c) Add 2,4-dinitrophenylhydrazine at room temperature. [1]
Ketone phenylhydrazone, yellow solid [1]
Ester no reaction [1]
d) Acidified potassium dichromate(VI). [1]
Phenol no reaction. [1]
Primary alcohol solution turns from orange to green. [1]
e) Dip a glass rod into concentrated hydrochloric acid and hold over open bottles of the
compounds. [1]
Amide no effect. [1]
+
Amine clouds of white smoke formed as CH3CH2CH2CH2NH3 Cl (s) forms. [1]
12.0
9 a) Mass of carbon = 7.92 = 2.16 g [1]
44.0
2.0
Mass of oxygen = 1.44 = 0.16 g [1]
18.0
Mass of oxygen in Y = (2.64 2.16 0.16) g = 0.32 g [1]
In Y, ratio of masses C : H : O = 2.16 : 0.16 : 0.32
2.16 0.16 0.32
Ratio of moles C : H : O = : : [1]
12.0 1.0 16.0
= 0.18 : 0.16 : 0.02
= 9 : 8 : 1
Empirical formula of Y = C9H8O [1]
Relative molecular mass of Y = 132
Relative molecular mass of C9H8O = 132
Molecular formula of Y = C9H8O [1]
b) Observations Inferences
Burns with a smoky flame Y is probably aromatic and contains a
benzene ring [1]
The yellow/orange colour of Y is probably an alkene [1]
bromine water is decolourised
A yellow/orange precipitate is Y probably contains a carbonyl group [1]
produced
A silver mirror or dirty grey solid Y is probably an aldehyde [1]
appears

c) Possible structures for Y would be
or 1,2 or 1,3 isomers [1]

10 a) Assess the quality of the answers taking into account both the key points made (up to 4
marks) and the logic and coherence of the discussion (up to 2 marks).
Key points to make in an answer:
Weigh a sample of D.
Heat (reflux) with NaOH(aq).
Cool and add HNO3 to neutralise excess NaOH.
Add an excess of AgNO3(aq).
Filter the cream precipitate of AgBr.
Wash, dry and weigh.
b) Reaction with NaOH(aq) converts the halogenoalkane to an alcohol + sodium bromide. [1]
[1]
HNO3 neutralises excess NaOH and the AgNO3 precipitates Br(aq) ions in the aqueous
solution as cream-coloured AgBr(s). [1]
Ar [Br]
Mass of Br in D = mass of AgBr [1]
Ar [AgBr]
mass of Br in D
% of Br in D = 100% [1]
mass of D
11 a) Step 1 CH3CH2CH2Br with KCN in ethanol [1] forms CH3CH2CH2CN. [1]
Step 2 CH3CH2CH2CN with Ni/H2 [1] forms CH3CH2CH2CH2NH2. [1]
Step 3 CH3CH2CH2CH2NH2 with CH3COCl [1] forms CH3CONHCH2CH2CH2CH3. [1]
b) Step 1 C2H4 with HBr [1] forms CH3CH2Br. [1]
Step 2 CH3CH2Br with NaOH(aq) [1] forms CH3CH2OH. [1]
Step 3 CH3CH2OH with acidified K2Cr2O7 [1] and distil off the product CH3CHO immediately it
forms. [1]
Step 4 CH3CH2Br with Mg in ethoxyethane [1] forms CH3CH2MgBr. [1]
Step 5 CH3CH2MgBr with CH3CHO [1] then hydrolysis [1] forms CH3CH2CH(OH)CH3. [1]
Step 6 CH3CH2CH(OH)CH3 with conc. H2SO4 [1] forms CH3CH=CHCH3. [1]

12 a) Ratio of masses C : H : Al = 50 : 12.5 : 37.5

50 12.5 37.5
Ratio of moles C : H : Al = : : [1]
12.0 1.0 27.0
= 4.17 : 12.5 : 1.39
=3:9:1
Empirical formula of A = C3H9Al [1]
b)
[1]
3
c) 0.24 dm of B has a mass of 0.16 g
24 dm of B has a mass of 16 g
3
Molecular mass of B = 16 g mol

1
[1]
d) B is methane, CH4. [1] C is aluminium hydroxide, Al(OH)3. [1]
e) i) 3CH3Cl(g) + Al/3Na(s) Al(CH3)3(l) + 3NaCl(s) [1]
3
ii) 0.24 g of A produce 0.24 dm of B (CH4)
24 g of A produce 24 dm of B (CH4), i.e. 1 mole of CH4 [1]
3
1 mole of C3H9Al (72.0 g) produces 3 moles of CH4. [1]

Al(CH3)3(l) + 3H2O(l) Al(OH)3(s) + 3CH4(g) [1]
iii) Al(OH)3(s) + 3HCl(aq) AlCl3(aq) + 3H2O(l) [1]
iv) Al(OH)3(s) + NaOH(aq) NaAl(OH)4(aq)
or
Al(OH)3(s) + OH(aq) Al(OH)4 (aq) [1]


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11 Equilibrium Answers to Exam practice questions

Pages 1719 Exam practice questions

= 3.20 10 [1]; atm [1]

Andrew Hunt, Graham Curtis 2015

c) [PCl3(g)] = [Cl2(g)] = x [1]

Andrew Hunt, Graham Curtis 2015

b) i) Kp does not change [1]

b) i) = 1.4 103 (working [1], answer [1])

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

3 x (0.01 x)2 (0.01 x)2

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

c) Total entropy of reactants = 50.9 J mol K + (3 5.7 J mol K ) = 68 J mol K [1]

Total entropy of products = (2 28.3 J mol K + (3 198 J mol K )

Labelled axes and appropriate

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

= 0.000 097 mol [1]

= 0.5 0.000 097 mol [1]

Andrew Hunt, Graham Curtis 2015

d) Ecell = 0.34 V + 0.80 V [1] = +0.46 V [1]

Andrew Hunt, Graham Curtis 2015

5 mol C2O4 2 mol MnO4 [1]

5 mol Fe 1 mol MnO4 [1]

5 mol Fe 1 mol MnO4

Zinc reduces iron(III) to iron(II): Zn Zn + 2e [1]

In the first titration:

Andrew Hunt, Graham Curtis 2015

Amount of copper ions in the pipette volume of solution

I2(aq) + 2S2O3 aq) 2I aq) + S4O6 aq)

2 mol S2O3 1 mol I2 2 mol Cu [1]

Fe(s) + I2(aq) Fe (aq) + 2I (aq) or Cd(s) + I2(aq) Cd (aq) + 2I (aq) [1]

salt bridge. [1]

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

(accept Cu (aq) + 2OH (aq) Cu(OH)2(s))

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

3 a) Axes [1]; plot and curve. [1]

Half-life from 12 10 mol dm : 7.6 10 s [1]

Lower starting concentration higher half-life. [1]

d) Rate-determining step involves two Y molecules. [1]

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

Ea = 2.24 10 K 8.31 J K mol [1]

Andrew Hunt, Graham Curtis 2015

1-bromo-2-chloroethane [1] 1-bromo-1-chloroethane [1]

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

d) H2C=CHCH2CH3; but-1-ene [1]

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

e) i) Both compounds have E/Z isomers. [1]

Z-citral [1] Z--ionone [1]

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

Andrew Hunt, Graham Curtis 2015

Propene with bromine HCN with propanone

Similarities Addition reaction