Teachers’ Copy

YISHUN INNOVA JUNIOR COLLEGE

2020 JC1 H2 CHEMISTRY
TUTORIAL 11
CHEMICAL EQUILIBRIA

A Dynamic Equilibrium and Equilibrium Constant

[Refer to lecture notes pages 3  7 and 8  11]

1. (a) With the aid of a suitable diagram, define the term ‘dynamic equilibrium’.

Dynamic equilibrium refers to a reversible reaction in which the forward and reverse reactions are
continuing at the same rate.

rate

Rf dynamic equilibrium
Rf = R b ≠ 0

Rb
teqm
time

(b) Write expressions for Kc and Kp (if applicable) for the following reversible reactions at
equilibrium. State the units of the equilibrium constants in each case.
(i) N2(g) + 3H2(g) ⇌ 2NH3(g)

(ii) H2O(g) + C(s) ⇌ CO(g) + H2(g)

(iii) 2HgO(s) ⇌ 2Hg(l) + O2(g)

(iv) NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH(aq)

(v) AgCl(s) ⇌ Ag+(aq) + Cl−(aq)

(vii) CH3COOH(l) + C2H5OH(l) ⇌ CH3COOC2H5(l) + H2O(l)

(i) [NH3 ]2 pNH 2

Kc  units = mol−2 dm6 Kp = 3
units = atm−2 or Pa−2
[N2 ][H2 ]3 pN pH 3
2 2
JC1 H2 Chemistry Tutorial 11: Chemical Equilibria

(ii) [CO][H2 ] pCO pH

2
Kc  units = mol dm−3 Kp = units = atm or Pa
[H2O] pH O
2

(iii) Kc = [O2] units = mol dm−3 Kp = pO2 units = atm or Pa

(iv) [NH4  ][OH ]

Kc  units = mol dm−3
[NH3 ]

(v) Kc = [Ag+][Cl] units = mol2 dm−6

(vi) [CH3CO2CH2CH3   H2O]

Kc = no units
[CH3CH2OH   CH3CO2H]

B Calculating Equilibrium Constants, Kc

[Refer to lecture notes pages 12  13]

2. N10/P3/Q2(b)(iv)
The addition of glucono-delta-lactone, GDL, to soy milk produces soft form of tofu due to a
gradual acidification of the mixture. In aqueous solution the following equilibrium is slowly set
up.

O O OH
HO HO CO2H
+ H2O
HO OH HO OH

OH OH

GDL gluconic acid

When 1.00 g of GDL (Mr = 178) was dissolved in 50.0 cm3 of water and the solution allowed to
reach equilibrium, the concentration of gluconic acid was found to be 0.0670 mol dm-3.
Write an expression of Kc for the equilibrium above, and use the data given to calculate its value.
You can assume that [H2O] = 55.5 mol dm3 throughout.

(0.0266 mol1 dm3)

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[gluconic acid]
Kc =
[GDL][H2 O]

Amount of GDL = 1.00 ÷ 178 = 0.0056179 mol

[GDL] = 0.0056179 ÷ 0.0050 = 0.11235 mol dm−3

GDL + H2O ⇌ gluconic acid

Initial concentration / mol dm3 0.11235 55.5 0

Change in concentration / mol dm3 0.0670  +0.0670

Equilibrium concentration / mol dm3 0.04535 55.5 0.0670

0.0670
Kc = = 0.0266 mol−1 dm3
(0.04535)(55.5)

3. Nitrogen dioxide decomposes on heating according to the following equation:

2NO2(g) ⇌ 2NO(g) + O2(g)
When 4.00 mol of nitrogen dioxide was put into a 2.0 dm3 container and heated, the equilibrium
mixture contained 0.50 mol of oxygen.

(a) Write the equilibrium constant expression, Kc, for this reaction, giving its units.

(b) Use your expression in part (a) to calculate the value for Kc.

(c) Suggest what is the significance of the magnitude of your answer in part (b).

(0.0278 mol dm−3)

(a) 2
[NO] [O2 ]
Kc = mol dm−3
[NO2 ]2

(b) 2NO2(g) ⇌ 2NO(g) + O2(g)

Initial amount / mol 4.00 0 0
Change in amount / mol −1.00 +1.00 +0.50
Equilibrium amount / mol 3.00 1.00 0.50
Concentration at
3.00  2.0 = 1.50 1.00  2.0 = 0.50 0.50  2.0 = 0.25
equilibrium / mol dm−3

(0.50)2 (0.25)
Kc = 2 = 0.0278 mol dm−3
(1.50)

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(c) Since Kc is quite small, this means that equilibrium position lies more to the left, and the
equilibrium concentration of NO and O2 is relatively low, while that of NO2 is relatively high.
This implies that most of the reactant, NO2, still remains (and have not been converted to NO
and O2 yet), and hence the extent of the reaction is quite low.

4. N09/P3/Q1(c) & (d)

(a) One molecule of haemoglobin can bind up to four molecules of oxygen, according to
following equation.

Hb(aq) + 4O2(aq) ⇌ Hb(O2)4(aq)

(i) Write an expression for Kc for this reaction, stating its units.

(ii) Experiments have shown that when the [O2] = 7.6  10−6 mol dm−3, the
concentrations of Hb and Hb(O2)4 are equal.

Use this information to calculate a value of Kc.

(iii) Use your value of Kc to calculate the [O2] necessary for 99% of the Hb to be
converted to Hb(O2)4.

(3.00 × 1020 mol−4 dm12; 2.40 × 10−5 mol dm−3)

(b) Myoglobin, Mb, is an oxygen-carrier protein that occurs in muscle fibres. It has a higher
affinity for O2 than does Hb, but only binds one O2 molecule per Mb molecule.

Mb(aq) + O2(aq) ⇌ MbO2(aq) Kc = 1  106 mol dm3

Calculate the percentage of MbO2 in an Mb-MbO2 mixture when [O2] = 7.6  10−6 mol dm−3.

(88.4%)

(a) (i) [Hb(O2 )4]

Kc =
[Hb][O2 ]4

Units: mol−4 dm12

(ii) Let x = [Hb] = [Hb(O2)4]

x
Kc =
x × (7.6 × 106 )
4

= 3.00 × 1020 mol−4 dm12

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(iii) When 99% of the Hb was converted to Hb(O2)4, [Hb(O2)4] = 0.99 & [Hb] = 0.01.

0.99
Kc = 4
= 3.00 × 1020
0.01 × [O2 ]

[O2] = 2.40 × 10−5 mol dm−3

[MbO2 ] [MbO ]
(b) % of MbO2 in an Mb-MbO2 mixture = [MbO × 100% and Kc = [Mb][O2 ] = 1 × 106
2 ] + [Mb] 2

[MbO2 ] [MbO2 ]
= 1 × 106 & = 7.6 so [MbO2] = 7.6[Mb]
[Mb](7.6 × 10-6 ) [Mb]

7.6[Mb] 7.6
% of MbO2 in an Mb-MbO2 mixture = × 100% = × 100% = 88.4%
7.6[Mb] + [Mb] 8.6

C Calculating Equilibrium Constants, Kp

[Refer to lecture notes pages 14 – 15]

5. (a) Consider the following reaction at 2200 oC,

N2(g) + O2(g) ⇌ 2NO(g)
If the equilibrium partial pressures of N2(g), O2(g) and NO(g) are 0.15 atm, 0.33 atm and
0.05 atm respectively, what is the value of Kp?

(0.0505)

pNO 2 (0.05)2
Kp = = = 0.0505
pN pO (0.15)(0.33)
2 2

(b) N07/P3/Q1(a) & (b)(i)  (ii)

The "OXO" reaction (reaction I in the scheme below) is industrially important for making
alcohols, aldehydes and carboxylic acids. For example, butan-1-ol, butanal and butanoic
acid can all be synthesised from propene, C3H6, according to the following scheme.

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(i) Write an expression for Kp for reaction I, stating its units.

When an equimolar mixture of propene, CO and H2 at an initial total pressure of 120 atm
is allowed to reach equilibrium at 500 K, the partial pressure of butanal is found to be 39.6
atm.

(ii) Calculate the equilibrium partial pressures of propene, CO and H2.

(iii) Hence calculate a value for Kp at 500 K.

(0.400 atm; 619 atm2)

(i) pCH CH CH CHO

3 2 2
Kp =
pCH CH=CH × pCO × pH
3 2 2

units of Kp = atm−2

(ii)
C3H6(g) + CO(g) + H2(g) ⇌ C4H8O(g)

Initial partial pressure / atm 40 40 40 0

Change in partial pressure / atm −39.6 −39.6 −39.6 +39.6

Equilibrium partial pressure / atm 0.4 0.4 0.4 39.6

Hence the partial pressure of C3H6, CO and H2 = 0.4 atm.

(iii) 39.6
Kp =
0.4 × 0.4 × 0.4

= 619 atm−2

6. Hydrogen gas and iodine vapour exist in equilibrium with hydrogen iodide gas at a constant
temperature according to the following equation:
H2(g) + I2(g) ⇌ 2HI(g)

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(a) In an experiment, 0.040 mol of HI(g) was placed in a 2.00 dm3 stainless steel flask at
430 °C. The equilibrium constant, Kc, for the above reaction is 54.3 at this temperature.
Calculate the equilibrium concentration of each species.
(0.00213 mol dm 3, 0.00213 mol dm 3, 0.0157 mol dm 3)

H2(g) + I2(g) ⇌ 2HI(g)

Initial amount / mol 0 0 0.040
Change in amount / mol x x 2x
Equilibrium amount / mol x x 0.040 2x
Concentration at 𝑥 𝑥 0.040 − 2𝑥
equilibrium / mol dm−3 2.00 2.00 2.00

[HI]2
Kc = = 54.3
[H2 ][I2 ]

0.040 - 2x 2
(
2.00
) (0.040  2x)2
𝑥 𝑥 = = 54.3
(2.00)(2.00) x2

0.040  2x
= √54.3 = 7.3688
x

x = 0.0042694 mol

Equilibrium concentration of H2(g) = 0.0042694  2.00 = 0.00213 mol dm3

Equilibrium concentration of I2(g) = 0.00213 mol dm3
Equilibrium concentration of HI(g) = [0.040 – 2(0.0042694)]  2.00 = 0.0157 mol dm3

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 (b) In another experiment, 0.010 atm of H2(g), 0.005 atm of I2(g) and 0.500 atm of HI(g) were
introduced into a sealed flask at 500 °C. When equilibrium is reached, the partial pressure
of H2(g) is 0.0455 atm.
Calculate the equilibrium partial pressure of HI(g) and I2(g), and hence calculate the
Kp value at this temperature.

(0.429 atm, 0.0405 atm, 99.9)

H2(g) + I2(g) ⇌ 2HI(g)

Initial partial pressure / atm 0.010 0.005 0.500

Change in partial pressure / atm +0.0355 +0.0355 2(0.0355)

Equilibrium partial pressure / atm 0.0455 0.0405 0.429

Hence the equilibrium partial pressure of HI(g) and I2(g) are 0.429 atm and 0.0405 atm respectively.

pHI 2 (0.429)2
Kp = = = 99.9
pH × pI (0.0455)(0.0405)
2 2

7. N16/P3/Q1(f)
One version of the Fischer-Tropsch process for manufacturing methane is the reaction of carbon
monoxide with hydrogen.

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

(a) Write an expression for the equilibrium constant, Kp, for this reaction, and state its units.

A mixture of CO and H2 in a 1 : 3 molar ratio was introduced into a sealed vessel and heated to
1200K. At equilibrium it was found that the total pressure was 32 atm, and the mole fractions of
CO and CH4 were 0.19 and 0.12 respectively.

(b) Calculate the equilibrium partial pressures of the two reactants and the two products.

(c) Use these data to calculate the value of Kp.

(6.08 atm, 18.2 atm, 3.84 atm, 3.84 atm; 4.00 × 10−4 atm−2)

(a) pCH × pH O
Kp = p 4 2
3 units: atm−2
CO × pH 2

(b) mole fraction of H2 = 3 × 0.19 = 0.57

mole fraction of H2O = 0.12 = mole fraction of CH4

JC1 H2 Chemistry Tutorial 11: Chemical Equilibria

equilibrium partial pressure of CO = 0.19 × 32 = 6.08 atm

equilibrium partial pressure of H2 = 0.57 × 32 = 18.24 = 18.2 atm

equilibrium partial pressure of CH4 = equilibrium partial pressure of H2O = 0.12 × 32 = 3.84 atm

(c) 3.84 × 3.84

Kp = = 4.00 × 10−4 atm−2
6.08 ×18.243

D Position of Equilibrium and ∆Go

[Refer to lecture notes pages 15 – 16]

8. The Haber process is an important chemical reaction as it synthesise ammonia, NH3(g). The
equation below describes the equilibrium between NH3, N2 and H2.
3H2(g) + N2(g) ⇌ 2NH3(g)
thermodynamic data:
 Ho = −45.8 kJ mol−1
 So = −198.3 J mol−1 K−1

(a) Calculate Go for the Haber Process.

(b) Suggest what is the significance of your answer in (a) in terms of the position of the
equilibrium, and hence the equilibrium composition.

(+13.3 kJ mol−1)

(a) Go = Ho − TSo

= −45.8 − (298) (−198.3  1000)
= +13.3 kJ mol−1

(b) Since Go > 0, reaction is spontaneous in the backward direction. The position of equilibrium
lies to the left. Hence the equilibrium mixture would contain a higher concentration of the
reactants, N2(g) and H2(g), than the product, NH3(g).

E Le Chatelier’s Principle
[Refer to lecture notes pages 16 – 24]

9. (a) State Le Chatelier’s Principle.

(b) Each of the following established equilibrium is subjected to a change.

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Explain how each change will affect the position of the equilibrium and the value of the
equilibrium constant.

(i) CO2(g) + H2(g) ⇌ H2O(g) + CO(g)

silica gel (a drying agent) is added to the air column.

(ii) N2(g) + 3H2(g) ⇌ 2NH3(g)

iron is added to the reaction.

(iii) CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g) H > 0

temperature is increased.

(iv) CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)

pressure is increased.

(c) Consider the following equilibrium,

PCl3(g) + Cl2(g) ⇌ PCl5(g)

The figure below shows how the percentage of PCl5(g) in the vessel varies with pressure
at temperatures 400 °C and 600 °C respectively.

% PCl5

By using Le Chatelier’s principle, explain if the reaction is exothermic or endothermic.

(a) Le Chatelier’s Principle states that when a system in equilibrium is disturbed, the system will
shift the equilibrium position to counteract the change imposed to re-establish the equilibrium.

(b) (i) The silica gel removes H2O(g). Thus, the concentration of H2O(g) decreases.
The position of equilibrium will shift to the right to produce more H2O(g).

There is no change in the value of Kc.

(ii) Iron is the catalyst used in the Haber Process. Equilibrium is attained faster as it increases
the rate of both forward and reverse reactions equally.

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There is no change in the position of equilibrium.

There is no change in the value of Kc.

(iii) The position of equilibrium will shift to the right to absorb the heat added, as the forward
reaction is endothermic.

The value of Kc will be increased.

(iv) The position of equilibrium will shift to the left to reduce the pressure, as the backward
reaction involves a decrease in the total number of gas molecules.

There is no change in the value of Kc.

(c) From the graph, as the temperature increases, the percentage PCl5 decreases. This implies the
position of equilibrium has shifted to the left.

By Le Chatelier’s principle, as temperature increases, the position of equilibrium will shift to

favour the endothermic reaction and absorb the excess heat.

Reverse reaction is endothermic i.e. forward reaction is exothermic.

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10. The reaction between NO and F2 was studied by mixing the two gases. At different times during
the experiment, various single changes was made to the conditions inside the reaction vessel.

2NO(g) + F2(g) ⇌ 2ONF(g)

The change in concentrations of the three compounds in the equilibrium mixture with time is
given by the graph below.

1.4

1.3

1.2 F2

1.1

1
Concentration / mol dm-3

0.9

0.8

0.7
NO
0.6

0.5 ONF

0.4

0.3

0.2

0.1

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Time / min

(a) (i) Write an expression for the equilibrium constant, Kc, for the reaction.

(ii) To determine the concentrations of the substances at equilibrium at the 7th minute,
the reaction was quenched* rapidly by cooling. Explain why the cooling must be
done rapidly.
* note: quench is to stop the reaction

(iii) Calculate the value of Kc at the 7th minute, including its units.

(b) The change in the concentration of each substance observed in the period from 7.5
minutes to 10 minutes results from heating the system. Deduce, with reasoning, if the
forward reaction is exothermic or endothermic.

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(c) (i) Suggest what disturbance has been effected at the 10th minute to cause the
changes in concentrations observed after the 10th minute.

(ii) Based on your answer in (c)(i), account fully for the change in concentration of
each of the substance.

(d) On the graph above, sketch the changes that would be observed when the concentration
of ONF is increased at the 15th minute.

(0.123 mol1 dm3)

(a) (i) [ONF]2

Kc =
[NO]2 [F2 ]

(ii) When the reaction mixture is cooled, the equilibrium position shifts and the concentrations
of the substances change. Hence, the cooling is done quickly to minimise any change in
the concentrations of the substances.
or
It takes time for shifting of equilibrium to occur, hence cooling fast leaves little time for
equilibrium to shift.

(iii) (0.2)2
Kc = = 0.123 mol1 dm3
(0.6)2 × (0.9)

(b) When the system is heated, [ONF] increases, while [NO] and [F2] decrease.
This indicates that the equilibrium position has shifted to the right when temperature increases.
Hence, the forward reaction is endothermic.

(c) (i) Increase in the pressure of the system or a decrease in the volume of the system.

(ii) The forward reaction is accompanied by a decrease in the number of moles of gaseous
molecules.
When pressure increases, the equilibrium position shifts to the right to reduce the pressure
by decreasing the number of moles of gaseous molecules.
Hence, [ONF] increases while [NO] and [F2] decrease.

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(d)

F Application of Chemical Equilibria to Industrial Processes

[Refer to lecture notes pages 25]

11. Modified from N02/P3/Q3(either)

The key stage in the Contact Process for the manufacture of sulfuric acid is the reaction between
sulfur dioxide and oxygen.

2SO2(g) + O2(g) ⇌ 2SO3(g), H = 197 kJ mol1

(a) Describe and explain the effect of the position of this equilibrium of increasing

(i) the pressure,

(ii) the temperature.

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(b) In the industrial process, the reaction is carried out at a pressure of 5 atm and a
temperature of 500 °C.

(i) In what respects are these conditions not what you might have expected?

(ii) Suggest why these particular conditions are used.

(c) (i) Write an expression for Kp for this reaction, giving its units.

(ii) When a 2 : 1 mixture of SO2 and O2 was allowed to reach equilibrium at 500 °C
and a total of 5.00 atm, the partial pressure of SO3 was found to be 4.70 atm.
Use your expression in (c)(i) to calculate the value for Kp.

(5520 atm1)

(a) (i) Equilibrium position will shift to the right to decrease the total pressure, as the forward
reaction involves a decrease in the total number of gas molecules.

(ii) Equilibrium position will shift to the left to absorb the heat added, as the reverse reaction
is endothermic.

(b) (i) I would have expected that a pressure higher than 5 atm and a temperature lower than
500 °C should have been used, so as to increase the yield of SO3(g) in the industrial
process (or to shift the equilibrium position to the right).

(ii) A lower pressure (than expected) was used so that the cost of building and maintenance
of the reactor and storage facility will be lower (the walls do not need to be very thick so
as to be able to withstand the high pressure), and it is also safer (lower risk of explosion).

A higher temperature (than expected) was used so that an optimal (reasonably high) rate
of reaction will be obtained.
Note: a lower operating temperature could be used if a catalyst is employed in this
industrial process - in fact, the catalyst commonly used is vanadium(V) oxide, V2O5.

(c) (i) pSO 2

3
Kp = atm1
pSO 2 × pO
2 2

(ii) Let the initial partial pressure for O2(g) be x, and for SO2(g) is 2x

2SO2(g) + O2(g) ⇌ 2SO3(g)

Initial partial pressure / atm 2x x 0

Change in partial pressure / atm 4.70 ½(4.70) +4.70

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Equilibrium partial pressure / atm 2x4.70 x  2.35 4.70

total pressure = (2 x – 4.70) + (x – 2.35) + 4.70 = 3x – 2.35 = 5.00

x = 2.45 atm

pSO2 = 2(2.45) – 4.70 = 0.20 atm

pO = 2.45 – 2.35 = 0.10 atm

2

pSO 2 (4.70)2
3
Kp = = = 5520 atm1
pSO 2 × pO (0.20)2 × (0.10)
2 2

G Additional Questions

12. The equilibrium constant, Kc for the decomposition of ammonia is 1.54 at 200 oC.

2NH3(g) ⇌ N2(g) + 3H2(g) Kc = 1.54 mol2 dm6

(a) Write the equilibrium constant expression, Kc, for the reaction above.

(b) (i) Write the equilibrium constant expression, Kc’, for the reverse reaction.

(ii) Express Kc’ in terms of Kc and hence find the value of Kc’.

(c) The reaction can also be written in 2 different ways:

1 3
 NH3(g) ⇌ N2(g) + H2(g)
2 2
2 1
 NH3(g) ⇌ N2(g) + H2(g)
3 3

Write the equilibrium constant expressions, Kc’’ and Kc’’’ for both the reactions and express
them in terms of Kc.

(0.649)

(a) [N2 ][H2 ]3

Kc =
[NH3 ]2

(b) (i) [NH3 ]2

Kc’ =
[N2 ][H2 ]3

(ii) 1
Kc’ =
Kc
1
= = 0.649 mol2 dm6
1.54

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(c) 1 3 1
[N2 ]2 [H2 ]2 [N2 ][H2 ]3 2 1
 Kc’’ = =( 2 ) = Kc 2
[NH3 ] [NH3 ]

1 1
[N2 ]3 [H2 ] [N2 ][H2 ]3 3 1
 Kc’’’ = 2 =( 2 ) = Kc 3
[NH3 ]
[NH3 ]3

13. A mixture of 0.50 mole of ethanoic acid and 1.00 mole of ethanol was shaken for a long time to
reach equilibrium. The whole mixture was titrated quickly with 1.00 mol dm −3 sodium hydroxide
and 80 cm3 of alkali were required.

The reaction between ethanoic acid and ethanol is shown below.

CH3COOH(l) + C2H5OH(l) ⇌ CH3COOC2H5 (l ) + H2O(l)

(a) Calculate how many moles of ethanoic acid remained at equilibrium.

(b) Write an expression for the equilibrium constant, Kc, for the equation you have given in (a)
and calculate its value.

(0.0800 mol; 3.80)

(a) No. of moles of ethanoic acid at equilibrium = Amount of NaOH reacted

80
= 1.00 ´ = 0.0800 mole
1000

(b) [CH3CO2CH2CH3   H2O]

Kc =
[CH3CH2OH   CH3CO2H]

CH3COOH(l) + C2H5OH(l) ⇌ CH3COOC2H5 (l ) + H2O(l)

Initial amount / mol 0.50 1.00 0 0
Change in amount / mol 0.42 0.42 +0.42 +0.42
Equilibrium amount / mol 0.08 0.58 0.42 0.42

Let V = total volume,

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0.42 0.42
( )( )
V V
Kc = 0.08 0.58 = 3.80
( )( )
V V

14. The equilibrium mixture in a 2 dm3 vessel at 773 K and 1.3 atm contains 0.60 mol sulfur dioxide,
0.20 mol oxygen and 4.80 mol sulfur trioxide.

2SO2(g) + O2(g) ⇌ 2SO3(g)

(a) Calculate the partial pressures of the three gases in the flask.

(b) Calculate the equilibrium constants

(i) Kp, and

(ii) Kc.

(0.139 atm, 0.0464 atm, 1.11 atm; 1380 atm 1, 640 mol1 dm3)

(a) 2SO2(g) + O2(g) ⇌ 2SO3(g)

Equilibrium amount / mol 0.60 0.20 4.80

Total pressure, ptotal at equilibrium = 1.3 atm

Total number of moles of gases at equilibrium = 0.60 + 0.20 + 4.80 = 5.60 mol

0.60
pSO = × 1.3 = 0.139 atm
2 5.60

0.20
pO2 = 5.60 × 1.3 = 0.0464 atm

4.80
pSO3 = 5.60 × 1.3 = 1.11 atm

(b) (i) pSO 2 (1.11)2

3
Kp = = = 1380 atm1
pSO 2 × pO (0.139)2 × (0.0464)
2 2

(ii) 2SO2(g) + O2(g) ⇌ 2SO3(g)

Equilibrium amount / mol 0.60 0.20 4.80
Equilibrium concentration / mol dm3 0.60  2 = 0.20  2 = 4.80  2
0.30 0.10 = 2.40

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[SO3 ]2 (2.40)2
Kc = = = 640 mol1 dm3
[SO2 ]2 [O2 ] (0.30)2 × (0.10)

15. N12/P3/Q1(b)
The following equilibrium exists in a sample of aluminium chloride vapour.

Al2Cl6(g) ⇌ 2AlCl3(g) ΔH = +63 kJ mol−1

(a) Draw a ‘dot-&-cross” diagram of Al2Cl6 molecule including its co-ordinate (dative covalent)
bonds

(b) Suggest the shape of the AlCl3 molecule.

(c) Predict the effect of increasing the temperature on the above equilibrium. Explain your
answer.

When 1.50 g of aluminium chloride was introduced into an evacuated flask of 250 cm 3 capacity
and heated to 500 K, the pressure inside the flask rose to 1.16  105 Pa.

(d) Assuming the gaseous mixture behaves ideally, use the general gas equation to calculate
the average Mr of the mixture.

(e) Using the following relationships, calculate the mole fraction of Al2Cl6, x, and the mole
fraction of AlCl3, y, in the mixture.

x+y=1
Mr(average) = 267x + 133.5y

(f) Hence calculate the partial pressure of Al2Cl6 and AlCl3 in the mixture.

(g) Write an expression for Kp for the reaction, and calculate its value. Include units in your
answer.

(214.9; 0.610, 0.390; 7.07  104, 4.53  104, 2.90  104)

(a)

(b) trigonal planar

(Note that the question is asking for the shape of AlCl3 and not Al2Cl6)

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(c) Since the forward reaction is endothermic, when the temperature increases, the position
of the equilibrium will shift to the right to absorb some of the heat. Hence some of the
Al2Cl6 molecules will dissociate to form AlCl3 molecules.

(d) 1.50 × 8.31 × 500

Mr = = 214.9
1.16 × 105 × 250 × 106

(e) x=1–y
Mr(average) = 267(1 – y) + 133.5y = 214.9
y = 0.390, x = 0.610

(f) partial pressure of Al2Cl6 = 0.60974 × 1.16 × 105 = 7.07 × 104 Pa

partial pressure of AlCl3 = 0.39026 × 1.16 × 105 = 4.53 × 104 Pa

2
(g) pAlCl 2 (4.5270 × 104 )
3
Kp = = = 2.90 × 104 Pa
pAl Cl 7.0730 × 104
2 6

16. N13/P3/Q1(d)(i),(ii)
Iodine and iodide ions undergo the following equilibrium in aqueous solution.
I2(aq) + I−(aq) ⇌ I3−(aq)

(a) Write an expression for the equilibrium constant for this reaction, Kc, stating its units.

When 2.54 g of solid iodine is dissolved in 100 cm3 of 1.00 mol dm−3 KI, and allowed to reach
equilibrium, the resulting [I3−(aq)] = 9.98  10−2 mol dm−3.

(b) Calculate the equilibrium values of [I2(aq)] and [I−(aq)] in this solution and hence calculate
a value for Kc.

(2.80  104, 0.9002, 396)

(a) [I3  ]
Kc = dm3 mol−1
[I2 ][I ]

(b) Initial amount of I2 added = 2.54 ÷ (2 × 126.9) = 0.010007 mol

Initial [I2] = 0.010007 ÷ 0.1 = 0.10007 mol dm−3

I2(aq) + I−(aq) ⇌ I3−(aq)

Initial concentration / mol dm3 0.10007 1.00 0

Change in concentration / mol dm3 −9.98  10−2 −9.98  10−2 +9.98  10−2

Equilibrium concentration / mol dm3 2.70  10−4 0.9002 9.98  10−2

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(9.98 × 102 )
Kc = = 396 dm3 mol−1
(2.8 × 104 )(0.9002)

17. N11/P2/Q2(a),3(a)-(c)
Phorsphorus(V) chloride, PCl5, is a white solid which sublimes at 160 oC.

When gaseous phorsphorus(V) chloride is heated in a closed container, the following equilibrium
is established.

PCl5(g) ⇌ PCl3(g) + Cl2(g)

(a) Write an expression for Kc for this equilibrium, stating the units.

In an experiment, 1.00 mol of PCl5 vapour was heated in a closed 5.00 dm3 flask at 500 K until
equilibrium had been established.
The gases in the flask were then rapidly cooled, causing the formation of crystals of PC l5 and
liquid PCl3. The chlorine gas present was pumped away and collected.
The amount of chlorine collected was x mol.
An excess of water was then very carefully added to the two remaining compounds, under
suitable conditions, causing the following reactions to occur.

PCl5 + 4H2O  5HCl + H3PO4

PCl3 + 3H2O  3HCl + H3PO3

You may assume that both H3PO4 and H3PO3 behave as dibasic(diprotic) strong acids i.e. the
mole ratio of the acid to H+ produced is 1:2.

(b) Determine, in terms of x, the number of moles of H+ that will be formed after the addition
of water to the mixture of PCl5 and PCl3.

The resulting solution was made up to 1.00 dm3 in a standard flask. 25.0 cm3 of this solution was
titrated with 4.00 mol dm−3 NaOH and required 37.4 cm3 for neutralisation.

(c) (i) Calculation the total amount, in moles, of H+ ions present in the 1.00 dm3 standard
flask.

(ii) Use your answers to (a) and (c)(i) to calculate the amounts, in moles, of PCl5, PCl3
and Cl2 in the original equilibrium at 500 K.

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(d) Use your answers to part (a) and (c)(ii) to calculate a value for Kc for the equilibrium.

(7.00 – 2x; 5.98; 0.492 mol, 0.508 mol, 0.508 mol; 0.105 mol dm3)

(a) [PCl3 ][Cl2 ]

Kc =
[PCl5 ]

units: mol dm−3

(b) PCl5(g) ⇌ PCl3(g) + Cl2(g)

Initial amount / mol 1.00 0 0
Change in amount / mol −x +x +x
Equilibrium amount / mol 1.00 − x x x

From PCl5 + 4H2O  5HCl + H3PO4

Amount of HCl formed from PCl5 = 5(1.00 – x)
Amount of H+ formed from HCl = 5(1.00 – x)
Amount of H3PO4 formed from PCl5 = (1.00 – x)
Amount of H+ formed from H3PO4 = 2(1.00 – x)
Amount of H+ from PCl5 = 5(1.00 – x) + 2(1.00 – x) = 7(1.00 – x) = 7.00 – x

From PCl3 + 3H2O  3HCl + H3PO3

Amount of HCl formed from PCl3 = 3x
Amount of H+ formed from HCl = 3x
Amount of H3PO3 formed from PCl3 = x
Amount of H+ formed from H3PO3 = 2x
Amount of H+ from PCl5 = 3x + 2x = 5x

Total amount of H+ produced = (7.00 – x) + 5x = (7.00  2x) mol

(c) (i) Amount of NaOH used in 25.0 cm3 = 4.00 × 0.0374 = 0.1496 mol
Amount of NaOH used in 1.00 dm3 = 40 × 0.1496 = 5.98 mol

H+ + OH−  H2O

Amount of H+ in 1.00 dm3 = 5.98 mol

(ii) Total amount of H+ = 7.00  2x = 5.98

x = 0.508

Amount of PCl5 = 1.00 – 0.508 = 0.492 mol

Amount of PCl3 = 0.508 mol
Amount of Cl2 = 0.508 mol

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(d) [PCl3] = [Cl2] = 0.508 ÷ 5 = 0.1016 mol dm−3

[PCl5] = 0.49 ÷ 5 = 0.098 mol dm−3

(0.1016)(0.1016)
Kc = = 0.105 mol dm−3
0.098

CHEM~IS~TRY

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