Queen's College London

Equilibria

Q1.Sulfuric acid is manufactured by the Contact Process.

(a) In this process, sulfur dioxide reacts with oxygen.

The equation for the equilibrium that is established is

SO2(g) + O2(g) SO3(g) ΔH = −98 kJ mol−1

(i) State and explain the effect of a decrease in temperature on the equilibrium
yield of SO3.

Effect of a decrease in temperature on yield .......................................

Explanation ...........................................................................................

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(Extra space) ........................................................................................

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(3)

(ii) Give two features of a reaction at equilibrium.

Feature 1 ...............................................................................................

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Feature 2 ..............................................................................................

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(2)

(b) Write an equation for the reaction of concentrated sulfuric acid with potassium
bromide to form potassium hydrogensulfate and hydrogen bromide.

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

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(c) Bromine is one of the products formed when concentrated sulfuric acid reacts with
hydrogen bromide.

Write an equation for this reaction.

State the role of sulfuric acid in this reaction.

Equation

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

Role of sulfuric acid .......................................................................................

(3)

(d) Concentrated sulfuric acid is used in a two-stage process to convert

2-methylpropene into 2-methylpropan-2-ol.

Stage 1 (CH3)2C=CH2 + H2SO4 (CH3)2C(OSO2OH)CH3

Stage 2 (CH3)2C(OSO2OH)CH3 + H2O (CH3)2C(OH)CH3 + H2SO4

(i) Name and outline a mechanism for Stage 1 of this conversion.

Name of mechanism .........................................................................

Mechanism

(5)

(ii) Deduce the type of reaction in Stage 2 of this conversion.

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(1)

(iii) State the overall role of sulfuric acid in this conversion.

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(1)
(Total 16 marks)

Q2.Ammonia is manufactured by the Haber process in which the following equilibrium is

established.

N2(g) + 3H2(g) 2NH3(g)

(a) Give two features of a reaction at equilibrium.

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Feature 1 .......................................................................................................

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Feature 2 .......................................................................................................

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(2)

(b) Explain why a catalyst has no effect on the position of an equilibrium.

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(Extra space) .................................................................................................

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(2)

(c) The diagram shows how the equilibrium yield of ammonia varies with changes in
pressure and temperature.

(i) Use the diagram to state the effect of an increase in pressure at constant
temperature on the yield of ammonia. Use Le Chatelier’s principle to explain
this effect.

Effect on yield ........................................................................................

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Explanation ............................................................................................

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(Extra space) ........................................................................................

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(3)

(ii) Use the diagram to state the effect of an increase in temperature at constant
pressure on the yield of ammonia. Use Le Chatelier’s principle to explain this
effect.

Effect on yield ........................................................................................

Explanation ............................................................................................

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(Extra space) ........................................................................................

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(3)

(d) At equilibrium, with a pressure of 35 MPa and a temperature of 600 K, the yield of
ammonia is 65%.

(i) State why industry uses a temperature higher than 600 K.

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(1)

(ii) State why industry uses a pressure lower than 35 MPa.

Do not include references to safety.

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(1)
(Total 12 marks)

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Q3. Hydrogen gas is used in the chemical industry.

(a) Tungsten is extracted by passing hydrogen over heated tungsten oxide (WO3).

(i) State the role of the hydrogen in this reaction.

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

(ii) Write an equation for this reaction.

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(1)

(iii) State one risk of using hydrogen gas in metal extractions.

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(1)

(b) Hydrogen is used to convert oleic acid into stearic acid as shown by the following
equation.

+ H2 CH3(CH2)16COOH
oleic acid stearic acid

(i) Use your knowledge of the chemistry of alkenes to deduce the type of
reaction that has occurred in this conversion.

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

(ii) State the type of stereoisomerism shown by oleic acid.

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

(c) Hydrogen reacts with nitrogen in the Haber Process. The equation for the
equilibrium that is established is shown below.

N2(g) + 3H2(g) 2NH3(g)

(i) State Le Chatelier’s principle.

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

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

(ii) Use Le Chatelier’s principle to explain why an increase in the total pressure of
this equilibrium results in an increase in the equilibrium yield of ammonia.

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

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

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

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(2)

(d) Hydrogen reacts with oxygen in an exothermic reaction as shown by the following
equation.

H2(g) + O2(g) → H2O(g) ∆H = –242 kJ mol–1

Use the information in the equation and the data in the following table to calculate a
value for the bond enthalpy of the H–H bond.

O–H O=O

Mean bond enthalpy / kJ mol–1 + 463 + 496

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(3)
(Total 11 marks)

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M1.(a) (i) M1 (Yield) increases / goes up / gets more

If M1 is blank, mark on and seek to credit the correct
information in the explanation.
If M1 is incorrect CE=0 for the clip.

M2
The (forward) reaction / to the right is exothermic or gives out /
releases heat
OR
The reverse reaction / to the left is endothermic or takes in /
absorbs heat
M3 depends on a correct statement for M2

M3 depends on correct M2 and must refer to temperature / heat

The (position of ) equilibrium shifts / moves left to right to oppose
the
decrease in temperature
For M3, the equilibrium shifts / moves
to release heat OR
to raise the temperature OR
to heat up the reaction.
3

(ii) M1 Concentration(s) (of reactants and products) remain or stay

constant /
the same
For M1 credit [ ] for concentration.

M2 Forward rate = reverse / backward rate

Not “equal concentrations”.
Not “concentrations is / are the same”.
Not “amount”.
Ignore “dynamic” and ignore “speed”.
Ignore “closed system”.
It is possible to score both marks under the heading of a
single feature.
2

(b) KBr + H2SO4 KHSO4 + HBr

Credit this equation in its ionic form.
Ignore state symbols.
Credit multiples.
1

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(c) M1 SO2 identified

M2 correctly balanced equation (would also gain M1)

Credit M2 equation in its ionic form.
Ignore state symbols.

2HBr + H2SO4 Br2 + SO2 + 2H2O

Credit multiples.
Not H2SO3 on the right-hand side.

Mark M3 independently
M3 Oxidising agent OR electron acceptor OR oxidant
OR to oxidise the bromide (ion) / HBr
M3 Not “electron pair acceptor”.
3

(d) (i) M1 Electrophilic addition

M1 both words required.

For the mechanism
M3 Penalise incorrect partial charges on O − H bond and
penalise formal charges
Ignore partial negative charge on the double bond.
M5 Not HSO4 –
For M5, credit as shown or −:OSO3H ONLY with the negative
charge anywhere on this ion
OR correctly drawn out with the negative charge placed
correctly on oxygen.

M2 must show an arrow from the double bond towards the H atom of the H −
O bond / HO on a compound with molecular formula for H2SO4
M2 could be to an H+ ion and M3 an independent O − H bond break on a
compound with molecular formula for H2SO4
Max any 3 of 4 marks for a correct mechanism using the
wrong organic reactant or wrong organic product (if shown)
or a primary carbocation.

M3 must show the breaking of the O − H bond on H2SO4

Penalise once only in any part of the mechanism for a line
and two dots to show a bond.

M5 must show an arrow from the lone pair of electrons on the correct oxygen
of the negatively charged ion towards the positively charged carbon atom on

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their carbocation
Credit the correct use of “sticks”.
For M5, credit attack on a partially positively charged
carbocation structure, but penalise M4

NB The arrows here are double-headed

5

(ii) Hydrolysis
Credit “(nucleophilic) substitution” but do not accept any
other prefix.
Credit phonetic spelling.
1

(iii) Catalyst
1
[16]

M2.(a) In either order

For M1 accept [ ] for concentration

M1 Concentrations (of reactants and products) remain or stay constant / the same
NOT “equal concentrations” and NOT “concentration(s) is /
are the same”

M2 Forward rate = Reverse / backward rate

NOT “amount”
Ignore “dynamic” and ignore “speed”
Ignore “closed system”
It is possible to score both marks under the heading of a
single feature
2

(b) M1 Catalysts increase rate of / speed up both forward and reverse / backward
reactions
If M1 is given as “no effect” / “no change” then CE= 0 for clip

M2 increase in rate / affect on rate / speed is equal / the same

Ignore references to “decrease in rate”
2

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(c) (i) M1 (The yield) increases / goes up / gets more
If M1 is given as “decreases” / “no effect” / “no change” then
CE= 0 for clip, but mark on from a blank.

M2 There are more moles / molecules (of gas) on the left / of reactants
Ignore “volumes”, “articles” “atoms” and “species” for M2

OR fewer moles / molecules (of gas) on the right / products

OR there are 4 moles / molecules (of gas) on the left and 2 moles
/ molecules on the right.

OR (equilibrium) shifts / moves to the side with less moles / molecules

M3 Can only score M3 if M2 is correct

The equilibrium shifts / moves (from left to right) to oppose the increase
in pressure
For M3, not simply “to oppose the change”
For M3 credit the equilibrium shifts / moves to lower /
decrease the pressure
(There must be a specific reference to the change that is
opposed)
3

(ii) M1 The yield decreases / goes down / gets less

If M1 is given as “increase” / “no effect” / “no change” then
CE= 0 for clip, but mark on from a blank.

M2 (Forward) reaction is exothermic OR gives out / releases heat

OR

reverse reaction is endothermic OR takes in / absorbs heat

Can only score M3 if M2 is correct

The equilibrium shifts / moves (from right to left) to oppose the increase in
temperature
For M3, not simply “to oppose the change”
For M3 credit the equilibrium shifts / moves
to absorb the heat OR
to cool the reaction OR
to lower the temperature
(There must be a specific reference to the change that is
opposed)
3

(d) (i) Must be comparative

Credit correct reference to rate being too (s)low / (s)lower at

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temperatures less than 600 K

Higher rate of reaction

OR increase / speed up the rate (of reaction)

Ignore statements about the “yield of ammonia”

OR Gets to equilibrium faster/ quicker

OR faster or quicker rate / speed of attainment of equilibrium

1

(ii) Less electrical pumping cost

Not just “less expensive” alone

OR
Not just “less energy or saves energy” alone

Use lower pressure equipment / valves / gaskets / piping etc.

Credit correct qualified references to higher pressures

OR

Uses less expensive equipment

Ignore references to safety
1
[12]

M3. (a) (i) Reducing agent

OR

Reduce(s) (WO3/tungsten oxide)

OR

electron donor

OR

to remove oxygen (from WO3/tungsten oxide or to form water);

1

(ii) WO3 + 3H2 → W + 3H2O

Or multiples

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1

(iii) One from

H2 is

• explosive

• flammable or inflammable

• easily ignited
Ignore reference to pressure or temperature
1

(b) (i) Addition

Ignore “electrophilic”
Penalise “nucleophilic addition”

OR

(catalytic) hydrogenation

OR

Reduction
1

(ii) Geometric(al)

OR

cis/trans OR E Z OR E/Z
1

(c) (i) (If any factor is changed which affects an equilibrium), the
position of equilibrium will shift/move/change/respond/act
so as to oppose the change.

OR

(When a system/reaction in equilibrium is disturbed), the

equilibrium shifts/moves in a direction which tends to
reduce the disturbance
A variety of wording will be seen here and the key part is the
last phrase and must refer to movement of the equilibrium.
QoL
1

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(ii) M1 – Statement of number of moles/molecules

There are more moles/molecules (of gas) on the left/of reactants

OR

fewer moles/molecules (of gas) on the right./products

OR

there are 4 moles/molecules (of gas) on the left and 2 moles/

molecules on the right.
Ignore “volumes” for M1
Mark independently

M2 – Explanation of response/movement in terms of pressure

Increase in pressure is opposed (or words to that effect)

OR

pressure is lowered by a shift in the equilibrium (from left) to

right/favours forward reaction.
2

(d) ΣB(reactants) – ΣB(products) = ΔH (M1)

OR

Sum of bonds broken – Sum of bonds formed = ΔH (M1)

B(H–H) + ½B(O=O) – 2B(O–H) = – 242 (M1)

B(H–H) = – 242 – ½(+496) + 2(+463) (this scores M1 and M2)

B(H–H) = (+)436 (kJ mol–1) (M3)

Award 1 mark for – 436

Candidates may use a cycle and gain full marks.

M1 could stand alone
Award full marks for correct answer.
Ignore units.
Two marks can score with an arithmetic error in the working.
3
[11]

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