MODULE 5: EQUILIBRIUM AND ACID REACTIONS

STATIC AND DYNAMIC EQUILIBRIUM (5.1)

IQ: What happens when chemical reactions do not go through completion?

 Students:
- Model static and dynamic equilibrium and analyse the difference between open and
closed systems
- Analyse examples of non-equilibrium systems in terms of the effect of entropy and
enthalpy (e.g. Combustion reactions and photosynthesis)
- Investigate the relationship between collision theory and reaction rate in order to
analyse chemical equilibrium reactions

OPEN AND CLOSED SYSTEMS (5.1.2)

 Open systems can exchange matter and energy with their surroundings
 Closed systems can exchange only energy with their surroundings
 Isolated systems cannot exchange matter or energy

REVERSIBLE AND IRREVERSIBLE PROCESSES (5.1.2)

IRREVERSIBLE PROCESSES

 Reactants form products and these products cannot be converted back to re-form the reactants
 A unidirectional arrow () to represent an irreversible reaction
 Irreversible processes are said to be in static equilibrium because the rates of forward and
reverse reactions are both zero once the process has finished (i.e. no movement between
reactants and products)
 E.g. Combustion

REVERSIBLE PROCESSES

 Reactants form products and these products can be converted back to re-form reactants
 A bidirectional arrow (⇌) to represent reversible reactions
 Reversible reactions include state changes and the formation of saturated solutions
 If these processes occur in a closed system, dynamic equilibrium can be reached
 This is when opposing reactions occur simultaneously but are in a state of balance (i.e. rate of
forward reaction = rate of backward reaction)
EXPLAINING REVERSIBILITY (5.1.2)

 Energy profile diagrams can be used to represent the energy changes that occur during a
chemical reaction
 It should be noted that the spontaneity and activation energy of a reaction determines whether
it is reversible or irreversible
 If the activation energies are similar = lower change in enthalpy = reversibility
 The activation energies of forward and reverse reactions can be different

THE DEFINITION AND MODELLING OF DYNAMIC AND STATIC EQUILIBRIUM (5.1.2)

EQUILIBRIUM

 Reversible processes reach equilibrium if the forward and reverse reactions occur at a constant
rate, hence resulting in constant concentration of reactants and products (concentrations don't
need to be equal; only constant)
 Although the process appears to stop on a macroscopic scale, the reactants and products would
constantly be forming and re-forming on an atomic scale
 Equilibrium cannot be achieved in an open system

DYNAMIC AND STATIC EQUILIBRIUM

Static Equilibrium Dynamic Equilibrium

- Rate of the reverse reaction = Rate of - Rate of the reverse reaction = Rate of
forward reaction and effectively zero forward reaction and also non-zero
- Applies to irreversible processes - The concentration of reactants and
- No movement of reactant and product products are constant, but don't need to
particles in either forward or reverse be equal
direction - Macroscopic properties are constant
- E.g. The reaction for the conversion of - E.g. The hydration and dehydration of
diamond to graphite would take billions CoCl 2
of years due to its high activation energy
and thus the rates of both forward and
reverse reaction are effectively zero
MODELLING EQUILIBRIUM

 Not all reactions will proceed to the same extent, even if both reach equilibria
 E.g. Dissolving 1 mole of HCl in 1L of H2O and 1 mole of CH3COOH in another litre of H2O:
O The conductivity of HCl will be much higher
O Despite the fact that both reactions reach an equilibrium of dissolution, the HCl dissociates
completely and the CH3COOH only dissociates partially
O Thus, they have different extents of reactions (i.e. amounts of products ≠ reactants)

MODELLING EQUILIBRIUM

 Dynamic and static equilibrium can be represented in a variety of models

 In order to constitute an effective or ineffective model; the following points are considered

Effective model Ineffective model

- Explains many characteristics of a - May be interpreted in many different
phenomena ways
- Simplified enough so that it is - Either oversimplified or too complex
understandable - Inaccurate
- Predictions can be made - Limited or no predictions can be made
- Variables can be changed and the
outcomes can be observed

Q. Models are often used to help explain complex concepts.

a) Outline the procedure used.

The procedure involved using two measuring cylinders of the same diameter, water and a plastic
straw. A measuring cylinder labelled as the ‘reactants’ was filled with 50mL of water. The plastic straw
was used to transfer water from the filled cylinder to the empty cylinder labelled as the ‘products’,
and then repeated the opposite way. The volume of both cylinders was recorded per cycle until the
system has reach equilibrium. This was determined when the final volumes of water within both
cylinders remained unchanged.
b) Describe how this procedure models equilibrium and state a limitation of the model.
The procedure models equilibrium through demonstrating that there is a constant forward and
reverse rate of reaction. This was represented through the consistency of transferring water from the
cylinders using the same straw, thus showing that dynamic equilibrium has been modelled.
Additionally, the procedure demonstrates that dynamic equilibrium involves the exchange of reactant
and product particles in both forward and reverse directions. This is shown through the continuous
transfer of water between the ‘products’ cylinder and the ‘reactants’ cylinder. However, a limitation
of the model is that it does not explain dynamic equilibrium at a molecular level. It does not highlight
that the products and reactants of a reaction are constantly reforming after equilibrium has been
achieved. This limits the model to explaining only macroscopic changes.
EQUILIBRIUM AND COLLISION THEORY (5.1.4)

 The collision theory qualitatively explains chemical reactions and can be used to predict the rate
of reaction
 COLLISION THEORY: A reaction can only occur if, and only if, suitable reactant particles
successfully collide with each other with the correct orientation and a sufficient amount of
energy
 E.g. In a closed system, as the concentration of reactants decreases, the rate of forward
reaction also decreases. The collisions between these reactant molecules occur less frequently.
Once some product starts to form, the reverse reaction occurs and the frequency of collisions
between product molecules increases. At equilibrium, the rates of forward and reverse
reactions are equal and the concentrations of all species don’t change.

POSSIBLE QUESTION

1. The production of ammonia is an equilibrium reaction:

N2(g) + 3H2(g) ⇌ 2NH3(g)

1 mol of nitrogen and 3 mol of hydrogen was mixed at 773K, in a closed reaction vessel of 1L, and left alone
until equilibrium was reached. In terms of collision theory, explain what would happen to the amount of each
molecule. (4 marks)

Initially at the start of the reaction, there is a high concentration of both hydrogen and nitrogen gas. As a result
of this, there is a high chance of a successful collision between hydrogen and nitrogen gas, resulting in the
formation of ammonia. Additionally, the rate of reverse reaction is zero due to having no product. Overtime,
the rate of reverse reaction increases as a result of the formation of ammonia, thus resulting in a higher
production and chance of successful collisions between hydrogen and nitrogen gas. Eventually, the rate of
forward reaction will decrease and the rate of reverse reaction will increase due to the subsequent decrease in
the amount of reactants and increase in amount of products. As a result, equilibrium will eventually be
reached due to the constant concentrations of the decreased moles of nitrogen and hydrogen gas and
increased amount of ammonia.

NON-EQUILIBRIUM SYSTEMS (5.1.3)

 Non-equilibrium systems are irreversible and will never reach an equilibrium state (e.g. combustion
reactions and photosynthesis)
 NB: Some irreversible reactions can still undergo static equilibrium

COMBUSTION

 The combustion of octane is a spontaneous non-equilibrium system

2C8H18(g) + 25O2(g)  16CO2(g) +18H2O(g) H = -5114 kJ mol-1

 The enthalpy of the reaction is negative as heat energy is released to the surroundings; and its
entropy is positive due to the increase in the number of gas molecules; therefore resulting in Gibbs
free energy being negative and thus the reaction being spontaneous
 The products of the reaction are stable and don't react with each other to re-form octane and oxygen
gas – the reaction is irreversible and can’t reach equilibrium
PHOTOSYNTHESIS

 During photosynthesis, heat energy is also produced and released to the surroundings, increasing the
entropy of surroundings and thus causing the reaction to be irreversible  Respiration can’t happen
simultaneously because of the positive entropy change  It is unfavourable  Strong force towards
completion
CO2(g) + 6H20(l) → C6H12O6(aq) + 6O2(g) H = +2803 kJ mol-1

 The enthalpy of the reaction is positive as energy is being absorbed during the reaction, and the
enthalpy is negative due to the decrease in molecules produced by the reaction, thus resulting in
Gibbs free energy being positive and thus the reaction being not spontaneous

NB: When there is no further change in free energy (when G = 0), then the reaction is at equilibrium, as
neither the forward nor the reverse reaction is favoured and thus enthalpy and entropy no longer need to be
considered.

PRACTICALS FROM IQ1 (5.1.1)

HYDRATED AND DEHYDRATED COBALT (II) CHLORIDE

 Solid dehydrated cobalt (II) chloride is coloured blue, and when hydrated with water turns pink
 This reaction is reversible as the cobalt (II) chloride can return blue once the water has been
evaporated

CoCl2(s) + 6H2O(l) ⇌ CoCl2(s) . 6H2O(l)

 Cobalt (II) chloride is used as a humidity or moisture indicator

IRON (III) NITRATE AND POTASSIUM THIOCYANATE

 Solutions of iron (III) nitrate are pale yellow and solutions of potassium thiocyanate are
colourless
 When mixed, they form the red-coloured complex ion iron thiocyanate

Fe3+(aq) + SCN-(aq) ⇌ FeSCN2+(aq)

 This reaction is reversible and forms an equilibrium

BURNING MAGNESIUM AND STEEL WOOL

 As stated before; combustion is a spontaneous non-equilibrium system and is thus irreversible

FACTORS THAT AFFECT EQUILIBRIUM (5.2)

IQ: What factors affect equilibrium and how?

 Students:
- Investigate the effects of temperature, concentration, volume and/or pressure on a
system at equilibrium and explain how Le Chatelier’s principle can be used to predict
such effects, for example:
- Heating cobalt (II) chloride hydrate
- Interaction between nitrogen dioxide and dinitrogen tetroxide
- Iron (III) thiocyanate and varying concentration of ions
- Explain the overall observations about equilibrium in terms of collision theory
- Examine how the activation energy and heat of reaction affect the position of
equilibrium

LE CHATELIER’S PRINCIPLE (5.2.1)

 The effect of changes in conditions of temperature, concentration (also impacted by dilution for an
equilibrium in solution) and volume (or pressure) to an equilibrium system, can be predicted through
Le Chatelier’s principle [i.e. increase/decrease in products/reactants]
 Le Chatelier’s principle states that:
If a closed system at equilibrium is subject to changes in conditions, the system will behave in a way to
partially counteract the change and re-establish equilibrium.

NB: The system will try to oppose the change but does not necessarily restore its original conditions.

CHANGES IN CONCENTRATION

QQ: The equation below shows a reversible reaction:

N2O4(g) ⇌ 2NO2(g)

State what happens if the concentration of:

a) N2O4(g) is increased.
The increase in concentration of N2O4(g) will disturb the equilibrium. By applying Le Chatelier’s
principle, the closed system at equilibrium will attempt to partially counteract the disturbance by
decreasing the concentration of N2O4(g, and thus favouring the forward reaction to re-establish
equilibrium. This results in the reaction mixture becoming darker brown in colour.

b) NO2(g) is increased.
The increase in concentration of NO 2(g) will disturb the equilibrium. By applying Le Chatelier’s
principle, the closed system at equilibrium will attempt to partially counteract the disturbance by
decreasing the concentration of NO2(g). Hence, the reverse reaction is favoured to re-establish
equilibrium, and thus the reaction mixture will be lighter brown in colour.
DILUTION

 Dilution by adding water reduces the number of particles per volume. This results in a shift in
the position of equilibrium towards the side that produces the greater number of dissolved
particles.

EXAMPLE:

Fe3+(aq) + SCN-(aq) ⇌ FeSCN2+(aq)

2 particles in solution 1 particle in solution

The addition of water immediately lowers the concentration of each species since the volume is
increased. In terms of Le Chatelier’s Principle, the reverse reaction will be favoured, hence increasing
the total concentration of particles in solution.

Effect of dilution on the equilibrium:

Fe3+(aq) + SCN-(aq) ⇌ FeSCN2+(aq)

Although the equilibrium position shifts to the

left, the concentrations of Fe3+ and SCN− at the
new equilibrium are lower than their
concentrations before dilution, because the
equilibrium shift only partially opposes the
change.

CHANGES IN PRESSURE AND VOLUME

 Whenever there is a change in pressure within a system; then there is always a change in volume and
vice versa
 It must be noted that changes in pressure and volume only affect gaseous species within a reversible
reaction
 Increase in pressure = Decrease in volume
 Decrease in pressure = Increase in volume
 Whenever there is a question involving changes in pressure or volume; both conditions must be
mentioned in the response

QQ: The equation below shows a reversible reaction:

3H2(g) + N2(g) ⇌ 2NH3(g)

State what happens if:

a) pressure is decreased.
The decrease in pressure of the reactants disturbs the equilibrium. By applying Le Chatelier’s
principle, the closed system at equilibrium will partially counteract the disturbance by favouring the
reverse reaction. This will produce less moles of gas than the forward reaction and thus allow the
system to re-establish equilibrium.

b) volume is decreased.
When volume is decreased, the pressure will increase and disturb the equilibrium. By applying Le
Chatelier’s principle, the closed system at equilibrium will partially counteract the disturbance by
 favouring the forward reaction. This will produce more moles of gas than the reverse reaction and
thus decrease the pressure of reactants to allow the system to re-establish equilibrium.

NB:

Direction of forward reaction Volume change System

No change (1) Increase H2(g) + I2(g) ⇌ 2HI (g)

No change (2) Decrease N2(g) + O2(g) ⇌ 2NO(g)

Reverse (3) Decrease CaCO3(s) ⇌ CaO(s) + CO2(g)

(1) + (2): There are no changes in reaction rate despite the volume change because there are the same mole of
gas on each side of the reaction.

(3): Changes in pressure and volume only apply to gaseous species, and so only apply to CO2(g).

CHANGES PRESSURE BY ADDING AN INERT GAS

 The total pressure of an equilibrium mixture of gases may also be changed, without changing the
volume of the container, by adding an inert gas such as helium, neon or argon
 However, the presence of an additional inert gas does not change the concentrations of
reactants and products. Hence, there is no effect on the position of equilibrium or the value of
the equilibrium constant. Additionally, the inert gas is not part of the reaction, and hence no net
reaction will occur.

CHANGES IN TEMPERATURE

 Temperature is the only condition that will affect Keq if it is changed

Exothermic Reactions
A + B ⇌ AB + heat

- Decrease in temperature = Equilibrium shifts right + Increase in Keq

- Increase in temperature = Equilibrium shifts left + Decrease in Keq

Endothermic Reactions

AB + heat ⇌ A + B

- Decrease in temperature = Equilibrium shifts left + Decrease in Keq

- Increase in temperature = Equilibrium shifts right + Increase in Keq

QQ: The equation below shows a reversible reaction:

N2O4(g) ⇌ 2NO2(g) H = +57 kJ mol-1

State what happens if:

a) temperature is increased.
When the above reaction is heated, the equilibrium is disturbed. According to Le Chatelier’s principle,
the closed system at equilibrium will partially counteract the disturbance by decreasing the
temperature. Since the reaction is endothermic, the forward reaction is favoured in order for the
absorption of heat to occur to cool the system. As a result, there is an increase in the formation of
NO2(g), resulting in the reaction mixture becoming darker brown.

b) temperature is decreased.
When the above reaction is cooled, the equilibrium is disturbed. According to Le Chatelier’s principle,
the closed system at equilibrium will partially counteract the disturbance by increasing the
temperature. Since the reaction is endothermic, the reverse reaction is favoured in order for the
release of heat to occur to heat the system. As a result, there is a decrease in the formation of NO2(g),
resulting in the reaction mixture becoming lighter brown.

CATALYSTS

 Adding a catalyst to an equilibrium system provides an alternative pathway with a lower

activation energy for both forward and reverse reactions
  This does not affect the proportions of reactants and products, but will increase both the
forward and reverse rates of reaction

 Within a concentration-time graph, there will be no evident changes when a catalyst is involved,
with the exception that equilibrium will be reached at a faster rate. As seen in the above energy
diagram, catalysts provide an alternative pathway with a lower activation energy for equilibrium
to reached. It does not, in any way, lower the activation energy and does not react within the
system.

OBSERVATIONS ABOUT EQUILIBRIUM IN TERMS OF COLLISION THEORY (5.2.2)

E.g. A sealed reaction vessel hydrogen and nitrogen gases as a particular temperature will establish an
equilibrium with ammonia gas, according to the equation: 3H2(g) + N2(g) ⇌ 2NH3(g) By referring to the
collision theory and reaction rates, explain what would happen if the concentration of N 2(g) was to
increase and how equilibrium would be re-established. Supply an annotated rate-time graph and a
concentration time graph with your answer.

When the concentration of N 2(g) molecules increases, the equilibrium of the system is disturbed.
According to Le Chatelier’s Principle, the closed system will attempt to partially counteract this change
by favouring the forward reaction in order to reduce the concentration of N 2(g). This is because, as a
result of the increase in N 2(g) molecules, the rate of the forward reaction will be initially greater than the
rate of the reverse reaction due to an increased likelihood of successful particle collisions. This is in
accordance to the collision theory, which states that a chemical reaction can only occur if suitable
reaction particles were to successfully collide with the correct orientation and a sufficient amount of
energy. However, as the reaction proceeds, the concentration of N 2(g) and H 2(g) begins to decrease and
the concentration of NH 3(g) begins to increase. This will eventually result in the forward reaction
decreasing and the rate of reverse reaction increasing until their rate of reaction becomes equal to each
other. Hence, a new equilibrium has been established.

GRAPHING AND EQUILIBRIUM

 Chemical systems involving equilibrium can be studied by either considering:

Rate of reaction (y) over time (x) Concentration over time

- Two lines are present (forward reaction and - Any number of lines depending on the
reverse reaction) number of substances present in the
- Depicts the system reaching equilibrium system
when the two lines meet - Depicts the system reaching equilibrium
when the lines become horizontal
(indicating that the concentrations have
become constant) but not necessarily equal

The system has reached equilibrium (purple

dashed line)
Change since the rate of forward reaction
to system Feature on graph
is equal to the rate of reverse reaction.
Increase in concentration/partial pressure of a Sudden increase in one substance
substance
Decrease in concentration/partial pressure of a Sudden decrease in one substance
substance
 Increase in volume/decrease in pressure of system Sudden decrease in all gaseous species

Decrease in volume/increase in pressure of system Sudden increase in all gaseous species

Increase in temperature No sudden changes

Decrease in temperature No sudden changes

Addition of catalyst Reaches the same equilibrium position in a shorter

time

HSC Question (2009)

Whilst the system was being observed, three changes have occurred. At t=4s, a change in the conditions of the
closed system at equilibrium resulted in the system being disturbed. Thus, the closed system will partially
counteract the change, according to Le Chatelier's principle. Therefore, the forward reaction was favoured in
order to re-establish equilibrium, as evident at t=8s when the concentrations of Cl2(g), CO(g) and COCl2(g)
remain the same at 0.11M, 0.085M and 0.04M respectively for another two seconds. The sharp, downward
spike of CO(g) at t=10s indicates the removal of CO(g) from the system, as shown through the 0.035M
decrease in concentration. According to Le Chatelier's principle, the closed system will partially counteract the
change by increasing the concentration of CO(g). As a result, the forward reaction is favoured as indicated by
the graph, which shows an increase in the concentration of Cl2(g) and CO(g) and a decrease in concentration of
COCl2(g). Due to this, equilibrium was re-established at approximately t=11.5s, with the constant
concentrations of Cl2(g), CO(g) and COCl2(g) being 0.12M, 0.06M and 0.03M respectively. The sharp,
downward spike of Cl2(g) and CO(g) at t=14s indicates the increase in volume or decrease in pressure of the
system which disturbs the equilibrium. According to Le Chatelier's principle, the closed system will partially
counteract this change by increasing the pressure or decreasing the volume of the system, thus favouring the
forward reaction. This is indicated by the subsequent decrease in concentration of COCl2(g) from 0.03M to
0.02M, and an increase in Cl2(g) and CO(g). Due to this, equilibrium is once again re-established at t=15s, when
the concentrations of Cl2(g), CO(g) and COCl2(g) remain the same at 0.085M, 0.045M and 0.015M respectively.

PRACTICALS FROM IQ2 (5.2.1)

HEATING COBALT (II) CHLORIDE HYDRATE

THE IMPACT OF ACTIVATION ENERGY AND HEAT OF REACTION ON THE POSITION OF

EQUILIBRIUM

CALCULATING THE EQUILIBRIUM CONSTANT (K EQ ) (5.3)

IQ: How can the position of equilibrium be described and what does the equilibrium constant represent?

 Students:
 - Deduce the equilibrium expression (in terms of K e q ) for homogenous reactions
occurring in solution
- Perform calculations to find the value of K e q and concentrations of substances within
an equilibrium system, and use these values to make predictions on the direction in
which a reaction may proceed
- Qualitatively analyse the effect of temperature on the value of K e q
- Conduct an investigation to determine K e q of a chemical equilibrium system, for
example the K e q of the iron (III) thiocyanate equilibrium
- Explore the use of K e q for different types of chemical reactions, including but not
limited to: the dissociation of ionic solutions; the dissociation of acids and bases

THE EQUILIBRIUM EXPRESSION (5.3.1)

 In an equilibrium system, the relationship between the concentrations of products and reactants is
known as the equilibrium constant (Keq)
 The equilibrium constant is based on the ratio between the products and reactants for a particular
reaction at equilibrium
 The equilibrium expression:

Keq =
[ products ]
[reactants]
c d
[C] [D]
 E.g. For the reaction aA + bB ⇌ cC + dD; Keq = a b
[ A ] [ B]
 Remember PORK  Products Over Reactants K
 Homogenous reactions are when all reactants and products are in the same phase; any states in
homogenous reactions can be written in the equilibrium expression

NB: Liquids are not usually included within the equilibrium expression unless all the species within the
reaction are also liquids. Solids and inert gases are never included.

E.g. Construct an equilibrium constant expression for the reaction 2SO2(g) + O2(g) ⇌ 2SO3(g).

2
[SO 3]
Keq = 2
[SO 2] [O 2]

 In heterogeneous reactions, reactants and products are in different phases

 The species is only included in the equilibrium expression if it is in a state where its concentration can
vary:
o Species in aqueous or gaseous states are included
o Species in solid or liquid states are not included

NB: The concentration of a pure liquid or solid is assigned a value 1

E.g. Construct an equilibrium constant expression for the reaction C(s) + O2(g) ⇌ CO2(g).

[CO 2]
Keq =
[O 2]
  The equilibrium constant predicts the relative concentrations of products and reactants, as well as the
position of equilibrium at any given temperature

K < 10-3 10-3 ≤ K ≤ 103 K > 103

Mostly reactants Significant amounts of Mostly products

reactants and products

 Only changing the temperature can change the Keq

THE REACTION QUOTIENT (5.3.2)

 The equilibrium constant (Keq) is only used when a system is at equilibrium

 A reaction quotient (Q) is used to determine whether a reaction is at equilibrium by comparing it to
the known K value.

If:

o Q = Keq then the reaction has reached equilibrium

o Q < Keq then the products need to be increased; the forward reaction will be favoured
o Q > Keq then the products need to be decreased; the reverse reaction will be favoured

E.g. For the reaction:

H2(g) + I2(g) ⇌ 2HI(g)

At 425˚C, Keq = 57. For the following three systems, calculate Q and describe how the system will respond to
reach equilibrium.

[H2] [I2] [HI]

System 1 0.020 0.020 0.18
System 2 0.030 0.015 0.16
System 3 0.040 0.035 0.24
2
[ HI ]
Q1 =
[ H 2][i 2]
2
=
0.18
0.020 ×0.020
= 81

Since Q1 > Keq, the reverse reaction will be favoured to reduce the concentration of the products.

2
Q2 =
0.16
0.030 ×0.010
= 57
Since Q1 = Keq, the reaction has reached equilibrium.

2
Q3 =
0.24
0.040 ×0.035
= 41

Since Q1 < Keq, the forward reaction will be favoured to increase the concentration of products.

CALCULATIONS INVOLVING EQUILIBRIUM CONSTANTS (5.3.2)

To answer Keq questions:

1. Write out a balanced chemical equation.

2. Write out the general expression for the Keq of the system.
3. Write out the ICE table (Initial, Change, Equilibrium).
4. Fill in the table, find all the values and solve for the desired quantity.

E.g. Consider the following reaction:

HSO4-(aq) + H2O(l) ⇌ H3O+(aq) + SO42-(aq)

The initial concentrations are given, where [HSO4-]= 0.40 molL-1, [H3O+] = 0.010 molL-1 and [SO42-] = 0.070
molL-1. Calculate the equilibrium concentrations of the reactants and products if K eq = 0.12.

HSO4- H 2O H 3O + SO42-  MOLARITY/CONCENTRATION NOT

I 0.4 0.010 0.070 MOLES
C -x +x +x
 ADHERE TO MOLE RATIO
E 0.4 - x 0.010 + x 0.070 + x

Q = ¿¿ 0.048 – 0.12x = 0.0007 + 0.010x + 0.070x + x2

0.020 ×0.010 x2 + 0.2x – 0.0473 = 0

=
0.40
−0.2 ± √ 0.22−4 ×1 ×(−0.0473)
= 0.00175 x=
2
 Q < Keq x = 0.139 or -0.339

 The forward reaction is favoured However mole values can’t be negative; so x =

0.139
Keq = ¿ ¿
 [HSO4-]= 0.26 molL-1
0.12 = ¿ ¿
[H3O+] = 0.15 molL-1
(0.010+ x )(0.070+ x )
0.12 =
( 0.4−x ) [SO42-] = 0.21 molL-1

THE EFFECT OF TEMPERATURE ON K E Q (5.3.3)

  Changing the temperature of the equilibrium affects both the position of the equilibrium and the
equilibrium constant. This is in contrast to other conditions such as concentration, which does not
affect the equilibrium constant.
 The effect of increasing the temperature on the equilibrium constant of an:
o Exothermic reaction: The equilibrium constant will decrease since the reverse reaction is
favoured, resulting in Q < Keq
o Endothermic reaction: The equilibrium constant will increase since the forward reaction is
favoured, resulting in Q > Keq
 The effect of decreasing the temperature on the equilibrium constant of an:
o Exothermic reaction: The equilibrium constant will increase since the forward reaction is
favoured, and thus Q > Keq
o Endothermic reaction: The equilibrium constant will decrease since the reverse reaction is
favoured, and thus Q < Keq

K E Q FOR DIFFERENT TYPES OF CHEMICAL REACTIONS (5.3.5)

EQUILIBRIUM OF IONIC DISSOCIATION

 The dissociation of solids into ions can occur as an equilibrium; with the equilibrium constant
being known as the solubility product (K sp)

AB (s) ⇌ aA+(aq) + bB -(aq)

Solubility product: Ksp = [A+]a x [B-]b

 The solubility product constant is used when the system is at equilibrium

 SMALLER SOLUBILITY PRODUCT = LOWER SOLUBILITY
 For a system not at equilibrium, the expression represents the ionic product. If:
O Ionic product = K sp then the system is at equilibrium
O Ionic product < K sp the forward reaction is favoured; the solid would dissolve for each
equilibrium
O Ionic product > K sp the reverse reaction is favoured; more precipitate would form to
reach equilibrium

EQUILIBRIUM OF ACID DISSOCIATION

 Weak acids partially ionise in water to form H + ions and the anion of the acid, therefore forming
an equilibrium
 The equilibrium constant is known as the acid dissociation constant (K a)

HA(aq) + H 2O(l) ⇌ H3O+(aq) + A -(aq)

Acid dissociation constant: Ka = ¿ ¿

 This does not strictly apply to strong acids as they fully dissolve in water to form ions, and hence
there is no equilibrium (the reaction is irreversible)
 The equilibrium constants can be used to determine the relative strengths of the acid:
 o Higher K a value (due to higher concentration of ions formed), more acid dissociates 
STRONGER acid
o Lower K a value (due to lower concentration of ions formed), less acid dissociates 
WEAKER acid

EQUILIBRIUM OF BASE DISSOCIATION

 Weak acids partially dissociate and react with water to produce hydroxide ions
 The equilibrium constant is known as the base dissociation constant (Kb)

B(aq) + H 2O(l) ⇌ BH+(aq) + OH-(aq)

Base dissociation constant: Ka = ¿ ¿

USING COLORIMETRY TO DETERMINE K E Q (5.3.4)

Explanation

Within the equilibrium reaction Fe3+(aq) + SCN-(aq) ⇌ FeSCN2+(aq), the colour of the solution is directly proportional
to the concentration of FeSCN2+ ions present. The spectroscopic technique, known as colorimetry, is used to
determine the concentration of coloured species in an aqueous sample. The absorption of light causes
electrons in ions or molecules to jump from a lower energy level to a higher one. The amount of light energy
absorbed is directly proportional to the concentration of the coloured species.

In this experiment, a colorimeter will be used to measure the absorbance of a standard solution with a known
concentration of FeSCN2+. The concentration of FeSCN2+ ions in other equilibrium mixtures can then be found
by measuring the absorbance and comparing the absorbance with the absorbance of the standard. Knowing
the initial concentration of Fe3+ and SCN- in each mixture, the equilibrium concentration of both ions can be
calculated and a value for the equilibrium constant, Keq, for the reaction can be determined.

Equipment

- 20mL of 0.0020M KSCN solution - Test-tube rack

- 30mL of 0.0020M Fe(NO3)3 solution - Stirring rod
- 2+
15mL of 0.00020M FeSCN solution - Colorimeter and data collection device
- 15mL deionised water - Colorimeter cell
- Graduated pipette - Marking pen
- Pipette filler - Tissues
- 5 x 100mL beakers - Safety gloves
- 4 test-tubes

Method

1. Label the test-tubes A-D.

2. Using a graduated pipette, place volumes of 0.0020M Fe(NO3)3 solution, 0.0020M KSCN solution and
water into each test-tube as indicated in the table below. Mix each solution thoroughly with a stirring
rod. Be careful to clean and dry the stirring rod after each mixing.
 Test-tube Fe(NO3)3(aq) (mL) KSCN(aq) (mL) H2O (mL)
A 5.0 2.0 3.0
B 5.0 3.0 2.0
C 5.0 4.0 1.0
D 5.0 5.0 0.0

3. Prepare a reference cell or ‘blank’ by filling the colorimeter cell to three-quarters of its volume with
deionised water. Following the manufacturer’s instructions, calibrate the colorimeter to read zero
transmittance when no lights passes through the cell and 100% transmittance when blue light
(470nm) passes through the blank. Use blue light for the remainder of this experiment.
4. Discard the deionised water from the cell, rinse the cell twice with the standard 0.00020M FeSCN2+
solution and fill the cell to three-quarters of its volume. Measure the absorbance and record the
results.
5. Repeat step 4 to measure the absorbance of the solutions in each of the test-tubes A-D.

SOLUTION EQUILIBRIA (5.4)

IQ: How does solubility relate to chemical equilibrium?

 Students:
- Describe and analyse the processes involved in the dissolution of ionic compounds in
water
- Investigate the use of solubility equilibria by Aboriginal and Torres Strait Islander
Peoples when removing toxicity from foods, for example toxins in cycad fruit
- Conduct an investigation to determine solubility rules, and predict and analyse the
composition of substances when two ionic solutions are mixed, for example KCl and
AgNO 3
- Derive equilibrium expressions for saturated solutions in terms of K s p and calculate
the solubility of an ionic substance from its K s p value
- Predict the formation of a precipitate given the standard reference values for K s p

DISSOLUTION OF IONIC COMPOUNDS (5.4.1)

 When an ionic substance is added to water, the hydrogen atoms of the water molecules are attracted
to the negatively charged ions and the oxygen atoms of the water molecules are attracted to the
positively charged ions. This is because water is polar, and hence it is made of ions.
 The attraction between the water molecules and the ions is known as ion-dipole attraction.
 When these ion-dipole attractions are strong enough, the ions are removed from the ionic lattice and
enter the solution (dissociation). When an ion is surrounded by water molecules, it is said to be
hydrated.
E.g. When sodium chloride dissolves in water:

 ionic bonds within the sodium chloride lattice are broken

 hydrogen bonds between water molecules are broken
 ion–dipole attractions form between ions and polar water
molecules.

An equation can be written to represent the dissociation

process:

H2O(l) + −
NaCl(s) →Na (aq)+Cl (aq)

Note that the formula of water sits above the arrow. This is
because there is no direct reaction between the water and
the sodium chloride. No chemical change occurs; only the
state symbol for sodium chloride is altered from solid (s) to
aqueous (aq), indicating it is now dissolved in water.
SOLUBILITY (5.4.3)

DEFINTION

 The solubility of a solute refers to the maximum mass that can dissolve in 100mL of water or a solvent
at a particular temperature
 Some ionic salts dissolve more easily than others. Insoluble ionic compounds don't dissolve in water
because the energy required to separate the ions from the lattice is greater than the energy released
when the ions are hydrated.
 By convention if:
o > 1.0g/0.1mol can be dissolved in 100mL of water, it is considered soluble
o 0.1 to 1.0g or 0.01 to 0.1mol can be dissolved in 100mL of water, it is considered slightly
soluble
o < 0.1g/0.1mol can be dissolved in 100mL of water, it is considered insoluble
 The solubility of a solute is dependent on temperature and a variety of other factors

SATURATED SOLUTIONS

 Unsaturated: A solution that contains less than the maximum amount of solute dissolved.
Hence, the solute completely dissolves into the solvent.
 Saturated: A solution that contains the maximum amount of solute dissolved at a given
temperature and amount of solvent.
 Supersaturated: more of the solute is dissolved than could be dissolved under normal
circumstances.
 Saturated solutions are actually in dynamic equilibrium as some ions can break free from their
ionic compound’s lattice and are hydrated while some hydrated ions re-join the lattice
SOLUBILITY CURVES

 A solubility curve shows how much of a solute can be dissolved over a range of temperatures
 Through using one it is also possible to deduce the level of saturation that the solution is

E.g.

1. Determine which of K2Crr2O7, CaCl2 and NaNO3 is most soluble in water at 25˚C. NaNO3
2. Sketch a solubility curve to indicate regions where a solution is unsaturated, saturated and
supersaturated.
SOLUBILITY RULES

 Precipitation reactions occur when two solutions react to form an insoluble solid
 Remember SNAAP  SODIUM (Na+) NITRATE (NO3-) ACETATE (CH3COO-) AMMONIUM (NH4+)
POTASSIUM (K+)  These anions and cations never form precipitates; hence they are spectator
ions

E.g.
SOLUBILITY AND K S P (5.4.4)

COMMON ION EFFECT

 Adding ions already present in a solution causes the equilibrium to shift in order to use up the
excess ions (Le Chatelier’s principle). This is called the common ion effect, and greatly
decreases the solubility of ionic compounds.
 Adding common ions to a solution shifts the equilibrium, however, adding a different salt with
no common ions has no effect on the original equilibrium.

Calculating the effect of a common ion on the molar solubility of an ionic compound

Q. Lead(II) chloride has a Ksp value of 1.70 × 10−5 at 25°C. Calculate its molar solubility in a 0.20molL−1
solution of NaCl.
PbCl2(s) ⇌ Pb2+(aq) + 2Cl -(aq)
Let s = molar solubility of lead (II) chloride
For 1.0L of solution:

PbCl2 Pb2+ Cl-

I 0 0.20 (from the NaCl)
C +s +2s
E s 0.20 + 2s

Since the amount of chloride ions contributed from dissolving lead(II) chloride is so small, it can be assumed
that all of the chloride ions come from the NaCl solution, hence this value is used for the equilibrium
concentration of Cl−.

PbCl2 Pb2+ Cl-

I 0 0.20
C +s 0
E s 0.20

K 2+][Cl−]2
sp = [Pb
1.70 × 10−5 = (s ) (0.20)2
s = 1.70 x 10-5 (0.20)2
= 4.3 × 10−4molL−1
The molar solubility of lead(II) chloride in 0.20molL−1 NaCl is 4.3 × 10−4 mol L−1.
Note that this is lower than the molar solubility of lead(II) chloride in water calculated later on (1.62 × 10 −2
mol L−1).

MOLAR SOLUBILITY

 The molar solubility of an ionic salt is the number of moles that will dissolve in water to form 1L of
saturated solution. It provides a relationship between the Ksp and concentration of its ions. This only
occurs if there is only one type of ionic compound dissolved in water.
  If the molar solubility of a salt is known, the Ksp can be calculated

Calculating Ksp from molar solubility/solubility data

 Note that some Ksp values can be found on the data sheet!

Q. Silver chloride is a sparingly soluble salt. At a certain temperature, 1L of water can dissolve 1.33 × 10 −5
mol of AgCl. Calculate Ksp for silver chloride at this temperature.
AgCl(s) ⇌ Ag+(aq) + Cl -(aq)

AgCl Ag+ Cl-

I 0 0
C +1.33 × 10−5mol +1.33 × 10−5mol
E 1.33 × 10−5mol 1.33 × 10−5mol

Since there is 1L of solution:

[Ag+] = 1.33 × 10−5 mol L−1
[Cl−] = 1.33 × 10−5 mol L−1

Ksp = [Ag+][Cl−]
= (1.33 × 10−5)(1.33 × 10−5)
= 1.77 × 10−10 at the given conditions

Calculating molar solubility from Ksp

Q. Lead(II) chloride has a Ksp value of 1.70 × 10−5 at 25°C. Calculate the molar solubility of lead(II) chloride at this
temperature.
PbCl2(s) ⇌ Pb2+(aq) + 2Cl -(aq)
Let s = molar solubility of lead (II) chloride

PbCl2 Pb2+ Cl-

I 0 0
C +s +2s
E s 2s

Ksp = [Pb2+][Cl−]2 1.70×10−5 =(s)(2s)2

1.70×10−5 =4s3

4.25×10−6 =s3
Take the cube root of both sides:
s =1.62×10−2
The molar solubility of lead(II) chloride is 1.62 × 10−2 mol L−1 at 25˚C

Calculating the concentration of ions from Ksp

Q. Copper (II) phosphate was placed in water at 25˚C to be dissolved. Calculate the concentration of the
copper (II) phosphate ions in a saturated aqueous solution of copper (II) phosphate.

Cu3(PO4)2(s) ⇌ 3Cu2+(aq) + 2PO43-(aq) Ksp = [Cu2+]3 [PO43-]2

Let 3s = [Cu2+] and 2s = [PO43-]

From the solubility product data sheet: Ksp of s = 1.67 x 10-8
copper (II) phosphate = 1.40 x 10-37
 [Cu2+] = 5.01 x 10-8M and [PO43-] = 3.34 x 10-8M
-37
1.40 x 10 = (3s) x (2s) 3 2
at 25˚

= 108s2

USING K S P TO PREDICT THE FORMATION OF A PRECIPITATE AMD THE IONIC PRODUCT (5.4.5)

THE IONIC PRODUCT/ PREDICTIING THE FORMATION OF A PRECIPITATE

 The solubility constant (K sp) is only used for ‘sparingly soluble’ or ‘insoluble’ salts in systems at
equilibrium

 For ‘sparingly soluble’ salts where the system may not be at equilibrium, the reaction quotient
called the ionic product (Q sp) is used instead

If:

O Qsp = Ksp  The

reaction is a
saturated solution

O Qsp < Ksp  No

precipitate is formed Predicting the formation of a precipitate given Ksp

O Qsp > Ksp  It is a

Q. supersaturated Barium sulfate has a Ksp value of 1.08 × 10−10 at 25°C. If 1.0 ×
10−3 g solution and a of barium sulfate is added to 1L of water at 25°C, predict
precipitate will form whether a precipitate will form.

= 4.3 x 10−6 molL−1

There is 1.0 × 10−3 g of barium sulfate.

m Assume that each mole of barium sulfate (BaSO4)

n(BaSO4) =
MM dissociates to form 1mol of barium ions and 1mol
of sulfate ions.
−3
=
1.0× 10 Qsp = [Ba2+][SO42-]
233.43
= (4.3 × 10−6 )(4.3 × 10−6 )
= 4.3×10−6 mol
= 1.8 × 10−11
n
c=
v
 As Ksp = 1.08 x 10-10, Qsp < Ksp, no precipitate will
−6
form at 25˚C  Make sure to specify the
=
4.3 ×10 conditions!
1

Predicting the formation of a precipitate when solutions are mixed

Q. 10.0mL of 0.00200 mol L-1 Na2SO4 is added to 100 mL of 3.20 x 10-4 mol L-1 BaCl2. Determine whether a
precipitate will form, if Ksp = 1.08 x 10-10 for barium sulfate.
Na2SO4(aq) + BaCl2(aq) ⇌ NaCl(aq) + BaSO4(s) n
[BaSO4] =
v
n(Na2SO4) = cV
−5
= 0.0100(0.00200) 2.00 ×10
= −3
(100+10.0)×10
= 2.00 x 10-5 mol
= 1.81 x 10-4 mol L-1
n(BaCl2) = 0.100(3.20 x 10 ) -4

Qsp = [Ba2+][ SO42-]

-5
= 3.20 x 10 mol
= (1.81 x 10-4)(1.81 x 10-4)
 Na2SO4 is the limiting reagent
= 3.31 x 10-8
Since n(Na2SO4): n(BaCl2) = 1:1, n(BaSO4) = 2.00 x
10-5 mol  As Ksp = 1.08 x 10-10, Qsp > Ksp, a precipitate
BaSO4(s) will form at the given conditions
BaSO4(s) ⇌ Ba2+(aq) + SO42-(aq)

DETOXIFYING FOOD USING SOLUBILITY EQUILIBRIA (5.4.2)

DETOXIFYING CYCAD SEEDS

1. The cycad nuts are ground into a powder to increase the surface area of the nuts.

2. The nuts are placed under running water. This leaches the toxins (known as cycasin) from the cycads
since the toxins are soluble in water (leaching). This occurs because of solubility equilibria (this
principle must be mentioned when answering questions relating to this topic!).

3. The running water, when removing the toxins, ensures that equilibrium is never established, and
pushes the reaction to always be in favour of dissolving the toxins.

 Aboriginal people in New South Wales used two leaching methods to detoxify cycads. Briefly roasting
the seeds and then leaching them in water for a short period of time yielded cycad seeds that,
although free of poison, did not keep well and had to be eaten quickly. Leaching the fruit for longer
periods meant that the seeds did not need prior roasting and lasted longer. Another technique is
ageing, where seeds that have lain underneath the trees for some months are collected, or the seeds
are dried and stored or buried for several months.

DETOXIFYING THE BITTER YAM

 The bitter yam (Dioscorea bulbifera) contains oxalates that would be toxic if consumed. In the Tiwi
islands the kulama ceremony ritualises the detoxification of the yam. The yams are placed in running
water to remove the oxalates by leaching. While this is taking place, an earth oven is prepared. When
the oven is ready, the yams are roasted.