Chapter 2: Equilibrium

2.1 Chemical systems

Open and closed systems

Open systems exchange ________ and _______ with the surroundings.

Closed systems only exchange ________ with the surroundings.

Irreversible and reversible systems

 An irreversible reaction is a reaction in which the products ______
be converted back to the reactants.
E.g. HCl + NaOH  NaCl + H2O
Non-reversible reactions have a _______ activation energy in the
___________ direction.
 A reversible reaction is a reaction in which the products _______
be converted back to the reactants.

E.g. CH3COOH ↔ CH3COO- + H+

Reversible reactions have a ______ activation energy for _____ forward and reverse reactions.
 Examples of reversible physical changes: ________________________________________

Equilibrium
Many chemical reactions are known to be reversible. In a ________ system, the forward and reverse
reactions will compete preventing the reaction from completing in either direction. Eventually, the
rates of _________ and _________ reactions become equal. The system is said to reach a state of
______________. Equilibrium _________ be achieved in an open system.

2.2 Dynamic equilibrium

At equilibrium, the rate of the forward reaction is __________ to the rate of the reverse reaction
(indicated by double arrows )

Chemical
equilibriums are
____________
because the forward
and reverse reactions
have not ceased.

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Example: See Figure 2.2.7, p.28

During dynamic equilibrium:

• the _______________ properties (e.g. colour) are constant

• the amount & _______________ of reactants and products are constant
• the ______________ and ______________ are constant
• the reaction is ‘incomplete’ - all reactants and products are present in some form
• at molecular level bonds constantly being broken and formed

Example:

Extent vs rate

The extent of a reaction does not give any information about how fast a reaction will proceed. It only
indicates how much product is formed once the system is at equilibrium.
Compare two ionisation equations:

CH3COOH(aq) + H2O(l) ↔ CH3COO-(aq) + H3O+(aq) and HCl (aq) + H2O(l) ↔ Cl-(aq) + H3O+(aq)

________________________________________________________________________________

Practice questions
1. Draw an energy profile diagram for the reaction if P.E. (potential energy) of the reactants is
100 KJ/mole N2O4 and
Ea = 110 KJ/mole N2O4. Energy
(KJ/mole

N2O4 (g) ⇄ 2 NO2 (g)

)

DH= +58KJ

Progress of reaction

2. If a catalyst were added to the reaction, what would happen to the forward and the reverse rate?

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 Forward rate Reverse rate
3. One mole of very cold, colourless N2O4 (g) is placed into a 1.0 L glass container of room
temperature. The reaction proceeds to equilibrium. The concentration of each gas is measured as
a function of time.

N2O4 (g) ⇄ 2 N02 (g) DH= +58 KJ

(colourless) (brown)

Time (s) 0 5 10 15 20 25

[N2O4] (M) 1.0 0.83 0.81 0.80 0.80 0.80

[N02] (M) 0.0 0.34 0.38 0.40 0.40 0.40

a) Plot concentration of N2O4 and N02 against time on the same graph below.
b) After what time interval has equilibrium
been established? ___________
c) Describe the change in the appearance of
the container over 25 seconds (describe the
colour change and when it becomes constant).
_____________________________________
_____________________________________
_____________________________________
_____________________________________
_____________________________________

d) Calculate the rate of N2O4 consumption in (M/s) over the first 5s period and then the second 5s
period. 0-5 sec: rate = _______________M/s, 5-10 sec: rate = _______________M/s
e) Why is the rate greater over the first five minutes compared to the second five minutes (think in
terms of reactant and product concentrations?
____________________________________________________________________________
____________________________________________________________________________
f) Calculate the rate of NO2 production in (M/s) over the first 5s period and then the second 5s
period. 0-5 sec: rate = _______________M/s, 5-10 sec: rate = _______________M/s
g) How does the rate of formation of N02 compare to the rate of consumption of N2O4? Remember, if
you measure the reactants or products, it is still the overall rate.
_____________________________________________________________________________
_____________________________________________________________________________
_____________________________________________________________________________
h) What are the equilibrium concentrations of N2O4 and N02?

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 [N2O4]= ______M [NO2] = ______M Are they equal? ______!
4. The equation to produce ammonia from hydrogen gas and nitrogen gas is: N2(g) + 3H2(g) ↔ 2NH3(g)
1 mol of N2 gas and 3 mol of H2 gas are mixed in 1L sealed container. The system is allowed to
reach the equilibrium. Draw the following graphs:

a) changes in reaction rates over time

b) changes in concentrations of N2, H2 and NH3 over time

Complete: 2.1 and 2.2 Key Questions (p.24 and 31) and Chapter review Q1, 2, 6 (p.56)

2.3 & 2.4 Equilibrium law and equilibrium constants

Equilibrium position

During equilibrium the concentrations of reactants and products are _____________.

However, the relative concentrations of reactants and products are ____________ for different
systems.
Some systems favour a high concentration of ___________, other favour _____________.

Equilibrium law

Equilibrium constant Kc is
________

E.g. aA + bB ↔ cC + dD K c = _________________

Equilibrium constant

• Only __________ and __________ species are included (solids and liquids have a fixed conc. of 1)
• Kc has ___________
• Kc varies with _______________.
Equilibrium quotient

Qc = Qc has the same mathematical expression as the Kc. It can be calculated for any
stage of a chemical reaction (non-equilibrium stage).

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Practice question
Write the equilibrium law expression for each of the following reactions.

Equation Equilibrium constant

HCN(aq) H+(aq) + CN-(aq)

CaCO(s) + 2H+(aq) H2O(l) + CO2(g) + Ca2+(aq)

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

Pb2+(aq) + 2Cl-(aq) PbCl2(s)

Value of Kc
• Large values – equilibrium favours ____________
• Small values – equilibrium favours ____________
• Close to 1 – implies significant _____________________ of both reactants and products

Equilibrium yield
The amount of ________________ present at equilibrium

Kc Extent of reaction Equilibrium yield

>104 Almost complete reaction occurs. The concentrations of

___________ are much higher than the concentrations of
(very large) ___________ at equilibrium.

10-4 – 104 The extent of reaction is significant. _____________

concentrations of reactants and products are present at
equilibrium.

<10-4 Negligible reaction occurs. The concentration of

_____________ are considerably higher that the
(very small) concentration of ___________ at equilibrium.

The equilibrium constant changes with temperature

Reaction Temperature Kc

Exothermic Increase

Endothermic Increase

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Practice questions

1. Use your knowledge of the equilibrium constant, Kc to answer the following

a. Which species are favoured in the following equilibrium systems? Answer reactants,
products or neither.

i. 2CO (g) + O2(g) 2CO2 (g) Kc = 2.2 x 1022 ________________

ii. NH4+(aq) NH3(aq) + H+(aq) Kc = 5.8 x 10-10 ________________

iii. N2O4(g) 2NO2(g) Kc = 0.21 ________________

b. Which of the two acids, nitric acid or nitrous acid is likely to be the strongest acid? Explain
your choice with reference to Kc.

HNO2(aq) H+(aq) + NO2- (aq) Kc = 5.1x10-4

HNO3(aq) H+(aq) + NO3-(aq) Kc = 23

___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________

2. What does the Kc for the dissociation of lead iodide indicate about its solubility in water?

PbI2 (s) Pb2+(aq) + 2I-(aq) Kc = 8 x 10-9

___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
3.
1.00 mol each of H2(g) and I2(g) were placed in a closed 1.00 L flask and heated to 425oC. When
chemical equilibrium was established the remaining concentrations of H2(g) and I2(g) were
0.21 molL-1, the rest having been converted to HI(g) according to the equation,
H2(g) + I2(g) ↔ 2HI(g)
a) Calculate the equilibrium concentration of HI(g).

b) Calculate the equilibrium constant K for this reaction at 425oC.

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c) Plot qualitative graphs showing the following.
i) The changes in concentration of H2(g), I2(g) and HI(g).
ii) The rates of the forward and reverse reactions from the start of the reaction until equilibrium
was reached. Mark on the graphs the time when equilibrium was reached.

d) What would be the characteristics of the system once equilibrium was established?
_____________________________________________________________________________

Complete: 2.3 & 2.4 Key Questions (p.36 and 39) and Chapter review Q7-9, 11-13 (p.56)

2.5 & 2.6 Le Châtelier’s principle and its applications

Le Châtelier’s principle predicts how a system will respond to imposed changes in concentration,
pressure and temperature.

“If a system is at equilibrium and a change in conditions is imposed on the system then the
system will readjust to establish a new equilibrium that _______________________________
the imposed change”

Le Châtelier’s principle is used to ____________ the effect of various changes on the

equilibrium systems. Collision theory is used to _____________ the changes.

The position of the equilibrium may be changed by:

• changing ______________/ pressure
 adding or removing a reactant or product
 changing the _____________ (gases)
 _____________ (solutions)
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• changing _______________

Increasing the concentration of one of the reactants or products

Example 1: Increasing the concentration by adding extra reactant

3H2(g) + N2(g) ↔ 2NH3(g) Change: adding N2(g) to the system

The ____________/partial pressure of N2 changes, the system will therefore be out of ___________.

Predicting the effect of a change using Le Châtelier’s principle

When N2 is added to an equilibrium system, the concentration (partial pressure) of N2 ___________.

The system will adjust to partially counteract this change and ____________ the concentration of the
added N2. To do this the system will favour the ________ reaction shifting the equilibrium to the ____.

The equilibrium will re-establish, however the

concentrations will ____________ to the original.
The value of K remains _____________ as the temp.
has not changed.

Explaining the effect of a change using collision theory and reaction rates

Follow this example to

answer similar questions.

Also, refer to How to

answer equilibrium
questions template
available on Connect.

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Increasing the concentration of one of the products – See Fig. 2.5.5 on page 42.

Decreasing the concentration of one of the reactants or products

Example 2: Decreasing the concentration of one of the reactants

2−¿¿ 2−¿¿
2CrO 4 (aq) + 2H+(aq) ↔ Cr2O 7 (aq) + H2O(l)
yellow orange

What will happen when a few drops of NaOH solution are added to
the equilibrium mixture? _____________________________________________________________
_________________________________________________________________________________
_________________________________________________________________________________

Use Le Châtelier’s principle to predict the effect on the position of equilibrium.

_________________________________________________________________________________
_________________________________________________________________________________
_________________________________________________________________________________
_________________________________________________________________________________

Observation: _______________________________________

Draw a graph showing how the concentration of the substances change when some H+ is removed
from the equilibrium reaction.

Explain the effect of a change using collision theory and reaction rates.

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 (1)_______________________________________________
_________________________________________________

(2)_______________________________________________
_________________________________________________
_________________________________________________
_________________________________________________

(3)_______________________________________________
_________________________________________________
________________________________________________________________________________

(4)______________________________________________________________________________
________________________________________________________________________________
________________________________________________________________________________

(5)______________________________________________________________________________
________________________________________________________________________________

Practice question

1. CO gas is added to the following equilibrium system: H2(g) + CO2(g) ↔ H2O(g) + CO(g)
(a) Draw graphs showing the following:
i) The changes in concentrations of all species over time
ii) The rates of the forward and reverse reactions from the start of the reaction until equilibrium
was reached.

(b) Predict the effect of this change on the system.

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 ___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
(c) Explain the effect of the change on this system.
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________
___________________________________________________________________________

Complete 2.5 Key Questions (p.45) and Chapter review Q14-16 (p.57)

Changing pressure by changing volume

What happens to the pressure of gases when the volume is changed?

________________________________________________________________________________

If the volume of a gaseous equilibrium system is changed, then the _______________ of the
substances making up the system will also change. The system will therefore be _____ of equilibrium.

According to Le Chatelier’s principle, when the total pressure of a gaseous equilibrium system is
__________ (by decreasing its volume), the system will adjust to partially counteract this change by
_____________ the total pressure. This is done by decreasing the overall _____________________
in the system. For this to happen, the equilibrium shifts towards the side of the reaction with the
_______ number of particles.

What will happen if the volume is increased? According to Le Chatelier’s principle, when the total
pressure of a gaseous equilibrium system is _____________________________________________
_________________________________________________________________________________
_________________________________________________________________________________
_________________________________________________________________________________

Example: Decreasing the volume of a gaseous system

N2(g) + 3H2(g) ↔ 2NH3(g)

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 How will the system react?

_________________________________

Notes:

• When the reaction contains equal number of particles on both side of the equation
(e.g. H2 + Cl2 ↔ 2HCl), then the system will _____ be put out of equilibrium.
• The addition of an inert gas has _______ effect on the position of equilibrium.
Practice question
State what will happen and draw a graph to show the effect of increasing the volume in these
scenarios.
• CaCO3(s) CaO(s) + CO2(g)
__________________________________________________
__________________________________________________
__________________________________________________

• I2(g) + H2(g) 2HI(g)

__________________________________________________
__________________________________________________
__________________________________________________

Dilution

For equilibria in solutions, dilution has a similar effect to the one with volume and gases.

Example: Fe3+(aq) + SCN-(aq) ↔ FeSCN2+(aq) See Fig. 2.6.6, p.49

• Adding water reduces the concentration of ______ aqueous species instantaneously

• Equilibrium will shift to __________ the number of aqueous species in solution (shift to the _____)

Changing temperature

Le Châtelier’s principle

Increasing temperature of the system

• The system will convert some added energy into chemical potential energy, ____________ the
temperature of the system
• favours the _______________ reaction
Decreasing temperature of the system

• The system will convert chemical potential energy into kinetic energy, ____________ the
temperature of the system
• favours the _______________ reaction

Example: Draw a concentration vs time graph to represent the changes when temperature is raised
and when it is lowered. C(s) + H2O(g) + 131 kJ ↔ CO(g) +H2(g)
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Temperature and the collision theory

 When the temperature is increased the average Ek ___________, particles move faster and
there are more frequent and energetic collisions.
 The rates of ________ forward and reverse reactions ____________.
 However, the rate of the endothermic reaction increases more.
The reason for that is that for the endothermic reaction, the proportion of reactant molecules,
which can collide with enough energy to overcome the Ea increases more for an endothermic
reaction than for the corresponding exothermic reaction when the temperature is increased.
 For a ___________ in temperature, the rate of endothermic reaction drops ___________ than
the exothermic reaction does.

Temperature and Kc

Changing the temperature of an equilibrium affects the value of the

equilibrium constant (Kc)
As you increase temperature:
• Exothermic reactions will favour the __________ (_____Kc value)
• Endothermic reactions will favour the _________ (______ Kc value)

Effect of a catalyst on equilibrium

The addition of a catalyst has _____________ on the position of equilibrium, only how quickly
equilibrium is attained.

STAWA Exp. 3 and 4 For both experiments:

• Read information on page 27-31
• Start your experiment report (Refer to A guide to writing practical reports points 1-4)
• Set up a table to record your observations.
• Use Le Chatelier’s principle to predict your observations.

Practice Questions
1. Describe the changes that occur after each stress is applied to the equilibrium.
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 4HCl (g) + O2 (g) ⇄ 2H2O(g) + 2Cl2 (g) + 98 KJ

Equilibrium concentrations Shifts Shifts to Favour the

Stress [O2] [H2O] [HCl] Right or Left Reactants or Products
a) [HCl] is increased

b) [H2O] is increased ____________

c) [O2] is increased

d) Temp is increased ______

e) [H2O] is decreased ______

f) [HCl ] is decreased ______

g) [O2] is decreased ______

h) Temp is decreased ____________

i) A catalyst is added

2. The oxidation of ammonia is a reversible exothermic reaction that proceeds as follows:

4 NH3 (g) + 5 O2 (g) ⇄ 4 NO (g) + 6 H2O (g)
For each situation described in the table, indicate an increase, or decrease in overall concentration
from before to after a new equilibrium has been established.

Component Stress Equilibrium Concentrations

[NH3] [O2] [NO] [H2O]
NH3 addition
removal

O2 addition
removal

NO addition
removal

H2O addition
removal
[NH3] [O2] [NO] [H2O]
Increase in temperature
Decrease in temperature
Increase in pressure
Decrease in pressure
Addition of a catalyst
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An Inert gas is added

3. State the direction in which each of the following equilibrium systems would be shifted upon the
application of the following stress listed beside the equation.

a) 2 SO2 (g) + O2 (g) ⇄ 2 SO3 (g) + energy decrease temperature

b) C (s) + CO2 (g) + energy ⇄ 2 CO (g) increase temperature

c) N2O4 (g) ⇄ 2 NO2 (g) increase total pressure

d) CO (g) + H2O (g) ⇄ CO2 (g) + H2 (g) decrease total pressure

e) 2 NOBr (g) ⇄ 2 NO (g) + Br2 (g) decrease total pressure

f) 3 Fe (s) + 4 H2O (g) ⇄ Fe3O4 (s) + 4 H2 (g) add Fe(s)

g) 2 SO2 (g) + O2 (g ) ⇄ 2 SO3 (g) add catalyst

h) CaCO3 (s) ⇄ CaO (s) + CO2 (g) remove CO2 (g)

i) N2 (g) + 3 H2 (g) ⇄ 2 NH3 (g) He is added

4. Consider the equilibrium that follows: Cu+ (aq) + Cl-(aq) ⇄ CuCl (s) ΔH = + 98 kJ
(green)
Describe how the above equilibrium will shift after each stress below:

shift colour of solution change

Increase in temperature
Increase [HCl]
Add NaCl
Decrease temperature
Add NaOH (aq) ____________
(check your solubility table for a possible reaction)

Add CuCl(s)

Add AgNO3 (aq)

(check your solubility table for a possible reaction)

Add CuNO3 (aq)

Add Cu(NO3)2 (aq)

5. Describe ways of increasing the yield of for the reactions below.

a) N2O4(g) + 59 KJ ⇄ 2 NO2(g)
___________________________________________________________________________
b) 2SO3(g) ⇄ 2SO2(g) + O2(g) + 215 KJ

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 ___________________________________________________________________________

c) H2O(g) ⇄ H2O(l) DH = -150 KJ

_________________________________________________________________________

6. In the Haber reaction: 3H2(g) + N2(g) ⇌ 2NH3(g) + energy

Explain why each condition is used in the process to make ammonia.

A High pressure of 50 MP ________

The presence of Ur or Os ________
Condensing NH3 to a liquid ________
o
A relatively high temperature 500 C ______________

Complete: 2.6 Key Questions (p.55) and Chapter review Q17,18 (p.57)

Interpreting concentration vs time graphs

Suggest what could have caused the change to the equilibrium in the systems below.

1. H2(g) + I2(g)  2HI(g) 2. 3H2(g) + N2(g)  2NH3(g) H= -92.4 kJmol-1

3. 2SO2(g) + O2(g)  2SO3(g) H = -197 kJmol-1 4. 2CrO42-(aq) + 2H+(aq)  Cr2O72-(aq) + H2O(l)

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5. 3H2(g) + N2(g)  2NH3(g) H= -92.4 kJmol-1

Answers:

1. More iodine is
added to the system
2. Volume doubles
3. System is heated
4. Dilution (water
added)
5. System is cooled

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