17 E Q U I L I B R I U M ( A H L )

Introduction

This topic examines the equilibrium law and exists with temperature of a reaction and

develops methodology for calculations of the its spontaneity is also examined. This topic

equilibrium constant. The role of Gibbs free highlights the signicance of mathematics in the

energy in describing the relationship that study of chemistry.

17.1 T iii 

Understandings
Applications and skills

➔ Le Châtelier ’s principle for changes in

➔ Solution of homogeneous equilibrium problems

concentration can be explained by the

using the expression for K

c

equilibrium law.

➔ Relationship between ∆G and the equilibrium

➔ The position of equilibrium corresponds to a

constant.

maximum value of entropy and a minimum in

➔ Calculations using the equation ∆G = -RT ln K

the value of the Gibbs free energy.

➔ The Gibbs free energy change of a reaction and

the equilibrium constant can both be used to

measure the position of an equilibrium reaction

and are related by the equation, ∆G = -RT ln K

Nature of science

➔ Employing quantitative reasoning – deduced directly from the stoichiometric

experimentally determined rate expressions equations and allow Le Châtelier ’s principle to

for for ward and backward reactions can be be applied.

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17 E Q U I L I B R I U M ( A H L )

The position of equilibrium

In topic 7 we discussed the characteristics of a reversible reaction

and dynamic equilibrium. We developed an understanding of the

equilibrium constant expression K for a reversible reaction, how the

c

equilibrium constant is determined, why it is signicant, and what

the reaction quotient Q conveys. We began a discussion of how Le

Châtelier’s principle can explain the effect on the equilibrium of changes

in concentration, temperature, and pressure.

The equilibrium law can be used to quantify the equilibrium position

at a given temperature.

Calculating the equilibrium constant using

concentration data

To calculate the equilibrium constant K for a reaction at a given

c

temperature, we follow a series of steps using initial concentrations and

equilibrium concentrations. This chapter will focus on homogeneous

systems: reactions in which all reactants and products are in the same

phase, that is, all gases, all miscible liquids, or all aqueous solutions.

The worked example that follows shows a method that can also be

TOK
applied to calculations involving weak acids and bases (sub-topic 18.2).

A complete understanding of this method is essential.

Natural sciences use

observations of the

ICE method for determining the equilibrium constant

universe to test proposed

1 Deduce the balanced chemical equation for the reaction.

hypotheses. This use of

data and observations is

2 Arrange the data according to the ICE method:

a methodology designed

I: Initial concentration of the reactants. Initially, [products] = 0.

to eliminate human bias.

Empirical inquiry is based C: Change in concentration. This is the amount by which

on perception and deductive [reactants] decrease and [products] increase. These changes

reasoning. must be consistent with the stoichiometric ratios shown by the

coefcients in the balanced equation (sub-topic 1.3).

In ddctiv soning

scientists work from the

E: Equilibrium concentration is the concentration of reactants and

general to the specic.

products when equilibrium is established. E = I +/ C. See the

Indctiv soning works

worked examples that follow for more details.

from specic observations to

3 Substitute the values into the equilibrium constant expression and

broader generalizations and

determine the equilibrium constant.

theories.

The equilibrium law can be

deduced by assuming that

the order of the forward and

Worked example
backward reaction matches

the coecients in the The esterication reaction between ethanol and ethanoic acid produces

chemical equation. How does the ester, ethyl ethanoate, and water. 1.0 mol of ethanol and 1.0 mol

deductive reasoning play a of ethanoic acid are dissolved in an inert organic solvent to produce

role in this phenomenon? 1dm of the solution and heated in the presence of the catalyst sulfuric

What is the role of deductive acid. When equilibrium is reached 0.60 mol of each reactant remains.

reasoning in science? Calculate the equilibrium constant K .

c

390
 1 7. 1 T h e e q u I l I b r I u m l a w

Stdy tip
Solution

H SO
2 4

Have you ever wondered

CH CH OH(l) + CH COOH(l) ⇋ CH COOCH CH (aq) + H O(l)

3 2 3 3 2 3 2

why no units are given for

I 1.0 1.0 0.0 0.0

equilibrium constants?

C α α +α +α
In general no units are included

for the equilibrium constant.

E 1.0 α = 0.60 1.0 α = 0.60 0.0 + α 0.0 + α

The reason for this is that when

● The coefcients for α, the change in concentration, must reect

the equilibrium constant is

the coefcients of the balanced equation. In this reaction the ratios

derived from thermodynamic

of reactants and products are 1 :1:1:1, so the coefcients for α are

measurements, the equilibrium

all 1. We shall develop this in the following examples.

constant is dened in terms

of activities, instead of
● If 0.6 mol of reactants remains at equilibrium, then 1.0 α = 0.60

concentrations (or par tial

and so α = 0.40. We can therefore complete the calculations above

pressures in the case of a

and substitute the values into the equilibrium expression.

gas). For an ideal system, the

● The volume of the reaction mixture is 1 dm so the concentrations

ctivity of a substance is the

in mol dm are the same as the amounts of reactants and

ratio of the concentration, in

products in mol.
3

mol dm (or par tial pressure

[CH COOCH CH ][H O] in Pa) to its standard value

3 2 3 2
___
K =
c
reference, which is taken
[CH CH OH][CH COOH]
3 2 3

3 5

as 1 mol dm (or 10 Pa).

(0.0 + 0.40)(0.0 + 0.40) (0.40)

___ _
Hence if the concentration of
= = = 0.44
2

(1.0 0.40)(1.0 0.40) (0.60)

a substance in an equilibrium

3
The equilibrium constant has no units.
was 0.25 mol dm , its activity

would be 0.25 (0.25 mol dm /

1 mol dm ), meaning that

the units cancel. Therefore

TOK

activities have no units and the

numerical value of the activity

Mathematics is an integral par t of the universe. From the symmetry in nature to

is equivalent to the numerical

the presence of geometric shapes in structures and organisms and Fibonacci

value of the concentration.

spirals in plants and animals, mathematics is all around us.

Interestingly in non-ideal

Mathematics can be used to create models that explain the equilibrium

systems (real systems), the

systems that we investigate in chemistry. Do scientists create mathematical

activities will not be precisely

models that mirror what occurs in an equilibrium system or is mathematics a

equal to the concentrations,

par t of the models that we use because reality is intrinsically mathematical?

and notable dierences can

be involved. In this text all

the examples are assumed to

be based on ideal systems.

In the corresponding case of

pure solids and pure liquids,

the activities will be equal

to one. Remember also from

topic 5 that the concentrations

of pure solids and pure liquids

are not included when writing

the equilibrium constant

expression, K
c

▲ Figure 1 The spiral structure of the Nautilus sea shell and its relationship to the

Fibonacci sequence and the golden ratio has been the subject of much debate.

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17 E Q U I L I B R I U M ( A H L )

TOK

Worked example

Many problems in science

Sulfur dioxide, SO is oxidized in the presence of the catalyst

2

involve assumptions that

vanadium(V) oxide, V O . In this reaction 2.0 mol of SO and 1.4mol

2 5 2

simplify the mathematics. In

3

of O are mixed in a 3.0 dm sealed container and the system is

2

solving quantitative problems

allowed to come to equilibrium. At 700K a conversion rate of 15 % is

of equilibrium systems,

achieved. Calculate the equilibrium constant for this reaction.

assumptions are made.

What is the role of intuition in

Solution
problem solving?

2SO (g) + O (g) ⇋ 2SO (g)

2 2 3

I 2.0 1.4 0.0

C 2α α +2α

E 1.7 1.25 0.30

● The change in concentrations reects the coefcients of the

balanced equation. For example for SO the change is 2α

2

● The conversion rate of 15 % means that 15% of SO is converted

2

into product. Hence the equilibrium amount for SO will be:

3

2.0 × 15% = 0.30

α can then be found as follows:

0.30 = +2α

α = 0.15

● Substitute this value into the equilibrium constant expression,

remembering to convert the amounts into concentrations.

[SO ]
3
_
K =
c 2

[SO ] [O ]
2 2

0.30
_

( )
3.0
__ 2

K = = 7.5 × 10
c 2

1.7 1.25
_ _

( ) ( )
3.0 3.0

Gis f ngy nd iii

The Gibbs free energy G describes the spontaneity and temperature

dependence of a reaction (sub-topic 15.2). The free energy will

change as reactants are converted into products. The reaction will be

spontaneous in the direction that results in a decrease in free energy (or

the direction in which the free energy value becomes more negative).

During this discussion we shall explore the relationship between the free

energy, entropy, and position of the equilibrium.

When the equilibrium constant K is determined for a given reaction,

its value indicates whether products or reactants are favoured at

equilibrium. The Gibbs free energy change ∆G for a given reaction is an

indication of whether the forward or reverse reaction is favoured. The

392
 1 7. 1 T h e e q u I l I b r I u m l a w

relationship between Gibbs free energy and the equilibrium constant K is

summarized in table 1.

eiii constnt Dsciption Gis f ngy cng

at equilibrium, neither
K = 1 ∆G = 0

reactants nor products

favoured

K > 1 products favoured ∆G < 0 (negative value)

K < 1 reactants favoured ∆G > 0 (positive value)

▲ Table 1 The relationship between the equilibrium constant and the Gibbs free energy change

At a given temperature, a negative ∆G value for a reaction indicates that

Stdy tip

the reaction is spontaneous and the equilibrium concentrations of the

The expression ∆G = -RT ln K

products are larger than the equilibrium concentrations of the reactants.

is provided in section 1 of the

The equilibrium constant is greater than 1. The more negative the value

Data booklet
of ∆G, the more the forward reaction is favoured and the larger the

value of K. The gas constant (R) has

the value and units of

The quantitative relationship between standard Gibbs free energy

1 1

8.31 J K mol . This is

change, temperature, and the equilibrium constant is described in the

provided in section 2 of the

equation:

Data booklet. The standard

∆G = -RT ln K
Gibbs free energy, ΔG°, has

units of kJ mol . When using

By rearranging this equation it is possible to calculate the equilibrium

this expression, as shown in

constant, and hence deduce the position of equilibrium for the reaction.

the worked example below,

∆G
_
ln K = -
either R has to be changed to
RT

1 1

0.00831 kJ K mol or ΔG°

The standard Gibbs free energy change can be calculated using the

conver ted to J mol .

methods described in sub-topic 15.2.

Worked example

Calculate the equilibrium constant at 300 K for Rearranging the equation to solve for K,

the oxidation of iron:

∆G = -RT ln K

2Fe(s) + O (g) ⇋ Fe O (s)

2 2 2 3 ∆G
_
ln K = -

RT
1

∆H = -824.2 kJ mol
3 1

743.1 × 10 J mol
___
ln K = - = 298
1 1 1 1

∆S = -270.5 J K mol 8.31 J K mol × 300 K

298 129

K = e = 2.6 × 10

Solution
The very large value of K demonstrates that the

First nd ∆G :
oxidation of iron at room temperature is highly

favoured. Reactions of this nature are said to be

∆G = ∆H - T∆S

irreversible.

= -824.2 - (300 × -0.2705) kJ mol

= -743.1 kJ mol

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17 E Q U I L I B R I U M ( A H L )

Questions

1 Consider the following equilibrium reaction. A. 0.64

Cl (g) + SO (g) ⇋ SO Cl (g) ∆H = -84.5 kJ B. 1.3

2 2 2 2

In a 1.00 dm closed container, at 375 °C, C. 2.6

3 3

8.60× 10 mol of SO and 8.60 × 10 mol

2
D. 64 [1]

of Cl were introduced. At equilibrium, 7.65 ×

2

4
IB, May 2010
10 mol of SO Cl was formed.
2 2

a) Deduce the equilibrium constant

expressionK for the reaction. [1]

c 4. a) The production of ammonia is an important

b) Determine the value of the equilibrium

industrial process.

constant K . [3]
c

N (g) + 3H (g) ⇋ 2NH (g)

2 2 3

c) If the temperature of the reaction is

i) Using the average bond enthalpy

changedto 300 °C, predict, stating a reason

values in Table 10 of the Data Booklet,

in each case, whether the equilibrium

determine the standard enthalpy

concentration of SO Cl and the value of
2 2

change for this reaction. [3]

K will increase ordecrease. [3]
c

d) If the volume of the container is changed ii) The standard entropy values, S, at 298

to1.50 dm , predict, stating a reason K for N (g), H (g) and NH (g) are 193,
2 2 3

1 1

in eachcase, how this will affect the 131 and 192 JK mol respectively.

equilibrium concentration of SO Cl and Calculate ∆S for the reaction and with

2 2

thevalue of K . [3] reference to the equation above, explain

c

the sign of ∆S . [4]

e) Suggest, stating a reason, how the

additionof a catalyst at constant

iii) Calculate ∆G for the reaction

pressure and temperature will affect the

at 298 K. [1]

equilibriumconcentrationof SO Cl . [2]
2 2

iv) Describe and explain the effect

IB, November 2009

of increasing temperature on the

spontaneity of the reaction. [2]

2 When a mixture of 0.100 mol NO, 0.051 mol b) The reaction used in the production of

H and 0.100 mol H O were placed in a 1.0 dm ammonia is an equilibrium reaction.

2 2

ask at 300 K, the following equilibrium was Outline the characteristics of a system at

established. equilibrium. [2]

2NO(g) + 2H (g) ⇋ N (g) + H O(g) c) Deduce the equilibrium constant expression,

2 2 2

K , for the production of ammonia. [1]

c

At equilibrium, the concentration of NO was

found to be 0.062 mol dm . Determine the d) i) 0.20 mol of N (g) and 0.20 mol of H (g)
2 2

equilibrium constant, K , of the reaction at this were allowed to reach equilibrium

c

temperature. in a 1 dm closed container. At

equilibrium the concentration of NH (g)

3

IB, May 2009

3

was 0.060 mol dm . Determine the

equilibrium concentrations of N (g)

2

and H (g) and calculate the value

2
3. 0.50 mol of I (g) and 0.50 mol of Br (g)
2 2

of K . [3]
c
are placed in a closed ask. The following

equilibrium is established.
ii) Predict and explain how increasing

the temperature will affect the

I (g) + Br (g) ⇋ IBr(g)

2 2

value of K . [2]
c

The equilibrium mixture contains 0.80 mol of

IB, May 2010

IBr(g). What is the value of K ?

c

394