CHEMISTRY

MODULE 5
Equilibrium and Acid Reactions
STATIC AND DYNAMIC EQUILIBRIUM

Inquiry question: ​What happens when chemical reactions do not go through to

completion?

Students:

● conduct practical investigations to analyse the reversibility of chemical reactions, for

example: – cobalt(II) chloride hydrated and dehydrated – iron(III) nitrate and potassium
thiocyanate – burning magnesium – burning steel wool (ACSCH090)
● model static and dynamic equilibrium and analyse the differences between open and closed systems
(ACSCH079, ACSCH091)
● analyse examples of non-equilibrium systems in terms of the effect of entropy and enthalpy, for
example: – combustion reactions – photosynthesis
● investigate the relationship between collision theory and reaction rate in order to analyse chemical
equilibrium reactions (ACSCH070, ACSCH094)

FACTORS THAT AFFECT EQUILIBRIUM

Inquiry question: ​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 (ACSCH095)
● explain the overall observations about equilibrium in terms of the collision theory
(ACSCH094)
● examine how activation energy and heat of reaction affect the position of
equilibrium

CALCULATING THE EQUILIBRIUM CONSTANT (​K​EQ)​

Inquiry question: ​How can the position of equilibrium be described and what does the equilibrium
constant represent?

Students:

● deduce the equilibrium expression (in terms of ​K​eq)​ for homogeneous reactions occurring in solution
(ACSCH079, ACSCH096)
● perform calculations to find the value of ​Ke​ 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 (ACSCH096)
● qualitatively analyse the effect of temperature on the value of ​K​eq
(ACSCH093)
● conduct an investigation to determine ​Ke​ q ​of a chemical equilibrium system, for
example: – ​Ke​ q ​of the iron(III) thiocyanate equilibrium (ACSCH096)
● explore the use of ​K​eq f​ or different types of chemical reactions, including but not limited
to: – dissociation of ionic solutions – dissociation of acids and bases (ACSCH098,
ACSCH099)

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 1 OF 29

SOLUTION EQUILIBRIA

Inquiry question: ​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: – potassium chloride and silver nitrate –
potassium iodide and lead nitrate – sodium sulfate and barium nitrate (ACSCH065)
● derive equilibrium expressions for saturated solutions in terms of ​Ks​ p a
​ nd calculate the solubility of an

ionic substance from its ​K​sp ​value

● predict the formation of a precipitate given the standard reference values for
K​sp

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 2 OF 29

REVISION – MODULE 4 – DRIVERS OF

 REACTIONS
ENTHAPLY CHANGE

Enthalpy (H) ​is a measure of the heat content of a system. Absolute enthalpy cannot be measured. However,
the ​change in enthalpy (​∆​H)​: the change in the heat content of system during a process, measured at
constant pressure​.

ΔH = H​products −
​ H​reactants

- H​products ​< H​reactants​, therefore ΔH is ​negative ​and heat energy ​released ​by the system (​exothermic​). -
​ H​reactants​, therefore ΔH is ​positive ​and heat energy ​absorbed ​by the system (​endothermic​).
H​products >

ENERGY PROFILE DIAGRAMS

HESS’S LAW OF HEAT SUMMATION

​ onstant,​ whether the reaction is performed in o

‘​The total enthalpy change in a chemical reaction is c ​ ne
step ​or s
​ everal steps.​’

Hess’s law is a form of the ​law of conversation of energy ​(First law of

Thermodynamics).
 CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 3 OF 29
BOND ENERGIES

Bond energy (or bond enthalpy) is the amount of energy required to ​break one mole ​of a bond in a
gaseous molecule​.

∆H​rxn ​= ∑∆H​reactant bonds broken ​+ ∑∆H​product bonds formed

∆H​rxn ​= ∑∆H​bond enthalpy of reactants ​− ∑∆H​bond enthalpy of products

ENTROPY

Entropy (S) ​is a measure of how ​the available energy is distributed or dispersed ​amount particles in a
system. It is also a measure of energy dispersal (function of temperature). Generally, low entropy → high
entropy. (Chaos)

When energy can be ​distributed in more ways, ​there is a greater

entropy

- Entropy is sometimes referred to as the measure of ​disorder ​or ​randomness​. - A system with ​greater
possible arrangements (microstates Ω)​, or ​greater diversity of movement ​has higher
 entropy.

FACTORS THAT CHANGE

ENTROPY

- Increasing the ​number of particles ​→ Increases microstates → ​Increase ​entropy -

Mixing ​different types of particles → Increases microstates → ​Increase ​entropy -
Increasing the ​volume ​of a container of gas → Increases microstates → ​Increases
entropy
o ​The larger the volume, the more ways there are to distribute the energy -
Increasing the number of particles in ​states with more freedom of movement ​(gas > liquid >
solid) - Molecules becoming ​more complex ​→ Increases microstates → ​Increases ​entropy -
Increase ​temperature ​→ Increases microstates → ​Increases ​entropy

SECOND LAW OF THERMODYNAMICS

The second law of thermodynamics states that the ​entropy of the universe is always
increasing​.

ΔS​universe =
​ ΔS​system +
​ ΔS​surroundings >
​ 0

CALCULATING ENTROPY IN CHEMICAL

REACTIONS

ΔS​rxn ​= ∑ΔS​products ​− ∑ΔS​reactants

GIBBS FREE ENERGY

In any process, the main form of interaction between the ​system ​and the ​surroundings ​is the ​exchange
of heat​.

- In an ​exothermic ​reaction, heat from the system ​enters ​the surrounding and ​increases temperature​,
which
will ​increase ​its ​entropy. ​The reverse will be true for an endothermic reaction. - At a lower
temperature, the same amount of heat will cause a greater proportional change in entropy.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 4 OF 29

ΔS​universe =
​ ΔS​system +
​ ΔS​surroundings >
​ 0
 −ΔH​
​ ​
ΔS​surroundings = system

T
−ΔH​
ΔS​universe = ​ ​
​ ΔS​system − system

>0
T​
−TΔS​universe ​= ΔH​system ​− TΔS​system ​< 0
Josiah Willard Gibbs ​redefined the quantity −TΔS​universe as
​ ​free energy ​or ​Gibbs Free
Energy, ​ΔG​.
ΔG​system =
​ ΔH​system −
​ TΔS​system
The equation allows the ​comparison between the relative contributions ​of the two driving
forces for a reaction, entropy and enthalpy.
​ TΔS​system​), a reaction is ​spontaneous ​- If ΔG > 0 (ΔH​system >
- If ΔG < 0 (ΔH​system < ​ TΔS​system​),
a reaction is ​non-spontaneous ​- If ΔG = 0, a reaction will occur both in the forward and reverse
directions, ​equilibrium​.
EQUATION SUMMARY
q = mc∆T
ΔH = H​products −​ H​reactants
q​
∆H​Combustion ​= −​ n
q​
∆H​Soln =
​ −​ n

∆H​rxn =
​ ∑∆H​bond enthalpy of reactants −
​ ∑∆H​bond enthalpy of products
ΔS​rxn ​= ∑ΔS​products ​− ∑ΔS​reactants
ΔG​system =
​ ΔH​system −
​ TΔS​system
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 5 OF 29

REVERSIBLE
REACTIONS
OUTCOMES COVERED
● model static and dynamic equilibrium and analyse the differences between open and
closed systems (ACSCH079, ACSCH091)
● investigate the relationship between collision theory and reaction rate in order to analyse
chemical equilibrium reactions (ACSCH070, ACSCH094)
● explain the overall observations about equilibrium in terms of the collision theory
(ACSCH094)
EQUILIBRIUM

For reversible reactions, a ​reversible arrow ​is used to indicate that both reactions are capable of
proceeding.

Reactants ​⇋ ​Products

Physical changes ​are generally

reversible

STATIC AND DYNAMIC EQUILIBRIUM

Reactions will proceed until either a ​static ​or ​dynamic equilibrium ​is reached. Equilibrium refers to the
state of a ​closed chemical system ​which:

1) The ​concentrations ​of both reactant and products ​do not change ​with
time 2) The ​rate ​of the forward reaction is ​equal ​to the rate of the reverse
reaction

Irreversible reactions ​(shown with a forward arrow →) that go to completion reach a ​static
equilibrium​.

Reversible reactions ​(shown with a reversible arrow ⇋) do not go to completion. In a closed system,
reversible reactions will instead reach a state known as ​dynamic equilibrium​.

- At equilibrium, the rates of the ​forward ​and ​reverse reactions ​are the ​same​, but ​non-zero. ​- The
equilibrium is dynamic because there are ​changes occurring ​at the ​microscopic level​, even though
the
system undergoes ​no change ​at the m
​ acroscopic
level​.

There are no ​macroscopic changes ​when a closed system is at

equilibrium.

TYPES OF SYSTEMS

- An ​open system ​is a system where matter and energy ​can enter ​and ​leave​. - A ​closed system ​is a
system where matter cannot enter and leave, but energy exchange can take place with
the surrounding (in the form of pressure or heat). - An ​isolated
system ​is a system where neither matter nor energy can leave.
RATES OF REACTION

1) Concentration or Volume/Pressure
2) Surface Area 3) Temperature 4)
Presence of catalyst

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 6 OF 29

5) Reactivity of reactants

COLLISION THEORY

In order for any reaction to proceed, reactants must collide. Particles need to collide with sufficient energy and
in the correct orientation for it to be a successful reaction. A collision with sufficient energy and the correct
orientation is called an effective collision.

The rate of reaction is how rapidly a reaction proceeds. The rate is defined as the change in the
concentration of reactants or products over time. It is dependant on the frequency of effective collisions.

ADDITION/REMOVAL OF A REACTION COMPONENT

If the concentration of one reaction component increases, its rate of reaction will increase as there are more
particles to collide with, thus increasing the frequency of effective collisions. The rate of that reaction will be
relatively greater than that of the rate of the reverse reaction. This means that more products or reactants will
being produced until equilibrium is reached.

Similarly, the reduction in one of the reaction components will reduce its rate of reaction. This occurs as there
are fewer particles to collide with which reduces the frequency of effective collisions. The rate of that reaction
will be relatively less than the rate of the reverse reaction. This means that more products or reactants will
being produced until equilibrium is reached.

CHANGE IN VOLUME OR
PRESSURE

A decrease in the volume of a chemical system involving gasses will result in gasses colliding more often.
The gas particles will also be colliding with more energy as pressure is inversely proportional to volume.
As particles are colliding more frequently and with more energy to overcome the activation energy barrier,
the frequency of effective collision increases. Both the rate of the forward and reverse reaction will
increase, however, the rate of reaction that uses the greatest number of moles will be relatively greater
than the reverse reaction as there are more particles that can collide effectively with each other.
When the volume is increased and pressure is decreased, the partial pressures of all gasses will decrease.
Both the rate of the forward and reverse reaction will decrease. The rate of reaction that produces more
moles will be relatively greater than the reverse as the reaction is more likely to occur because it requires
fewer particles to effectively collide.

Changing the overall pressure of a chemical system does not always cause a disturbance in equilibrium. For
example, the addition of inert gasses.

CHANGE IN TEMPERATURE

By increasing the temperature of a chemical system at equilibrium, particles will possess more kinetic energy,
which means that more particles (both reactants and products) have enough energy to collide and overcome
the activation energy of the forward and reverse reactions.

For an exothermic reaction, the activation energy of the reverse reaction is higher than that of the forward
reaction. An increase in temperature means that proportionally more products will be able to collide with
enough energy in reverse reaction than the reactants. This causes the rate of the reverse reaction to occur at
a faster rate than the forward reaction. Therefore, the concentrations of the reactants will increase whereas
the concentration of the

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 7 OF 29

products will decrease until a new state of equilibrium is
reached.

When the temperature is decreased, all the particles in the system lose energy which decreases both the rate
of the forward and the reverse reaction. However, the rate of the reverse endothermic reaction will be
relatively higher than the rate of the forward reaction.

OUTCOMES COVERED
● analyse examples of non-equilibrium systems in terms of the effect of entropy and
enthalpy, for example: – combustion reactions – photosynthesis

PHOTOSYNTHESIS

Photosynthesis appears to be the ​reverse ​reaction of the combustion of glucose and may seem to be a
reversible reaction. However, in nature, the process involves many individual irreversible steps which
combine to give the overall reaction, hence photosynthesis is irreversible.

6CO​2(g) ​+ 6H​2​O(​ l) ​→ C​6​H​12​O​6(s) ​+

6O​2(g)
 - ∆H > 0 (endothermic) - ∆S > 0 (less moles,
moving to more order) - Non-spontaneous at all
temperatures - Chlorophyll is the catalyst for
photosynthesis. - UV rays drives the
photosynthesis reaction.

SPONTANEITY AND EQUILIBRIUM

Haber Process

N​2(g) ​+ 3H​2(g) ​⇋ 2NH​3(g) ​∆G = −33.3 kJmol​−1

- The Gibbs free energy change for this reaction is negative, therefore we would predict that the
forward
reaction is spontaneous. ​- The Gibbs free energy change for the reverse reaction will be the
negative of this value, ​+33.3 kJmol​−1​, ​so
we would predict that the ​reverse reaction is nonspontaneous​. ​- ​Entropy of mixing ​allows
the reaction to be reversible. - The position with ​lowest free energy ​is somewhere ​in between pure
reactants and pure products. ​This is
the position of equilibrium.

The sign of ∆G indicates whether ​reactants ​or ​products ​will ​dominate the mixture ​with lowest free
energy.

- Since entropy of mixing always exist, ​technically no reaction is strictly

irreversible.
o ​However, if the position of equilibrium lies very close to the products, the reaction is
called
“irreversible” as the reverse reaction will not occur to ​any observable
extent​.
▪ This is when Gibbs free energy is ​very negative​. - Reversibility of a reaction
can also be considered in terms of ​activation energy​.
o ​Reactions are unlikely to be reversible as molecules will not have sufficient energy. ​o
In order for a reaction to be reversible, the forward and reverse reaction must have a
small
activation energy​.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 8 OF 29

 LE CHATELIER’S
PRINCIPLE
OUTCOMES COVERED
● 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 (ACSCH095)
● examine how activation energy and heat of reaction affect the position of equilibrium

RATE OF REACTION (FROM MODULE 3)

- The rate of reaction is the ​speed ​with which reactants are converted to products, or how ​rapidly ​a
reaction
proceeds. - Rate is defined as the ​change in concentration of reactants
or products over time. ​- The rate of reaction depends on the ​frequency of
effective collisions​.

Rate of Reaction ∝ Frequency of Effective Collisions

FACTORS AFFECTING THE RATE OF

REACTION

- Nature of reactants -
Concentration - Surface
area - Temperature -
Catalysts -
Pressure/volume

NATURE OF REACTANTS

Every reaction has its own rate and its own activation energy, depending on the ​reactivity of the
reactants​.

Aqueous solutions already have dissociated ions. They do not need to collide in any correct orientation and
usually have very low E​a​.
CONCENTRATION

The rate of reaction ​increases ​when the concentration of reactants is

increased​.

- The rate of reaction is directly proportional to the reactant concentration.

- Increasing the concentration increases the number of effective collisions.
- Increases the number of particles in a given space.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 9 OF 29

SURFACE AREA (PARTICLE
SIZE)

The rate of reaction ​increases ​when the surface area of reactants is

increased.

- Exposes more particles to the reactant. This increases the chance of a successful collision which
therefore
increases the rate of reaction.

TEMPERATURE

The rate of reaction ​increases ​when the temperature of the reactants is

increased​.

- The total number of collisions increase.

o ​Increased KE, particles move faster. There is a greater chance of successful collision. ​o
When the temperature increases, the ​average kinetic energy ​of the molecules increase,
thus
molecules move faster which means they ​collide more frequently​. - The ​average energy of the
collisions ​increases. Therefore, a higher fraction of collisions exceed activation
energy. - In general, reaction rate doubles every 10
degrees Celsius.
PRESENCE OF A
CATALYST

A catalyst is a substance that increases the rate of reaction ​without being

consumed​.

Catalysts work by allowing the reaction to take an ​alternative reaction pathway ​with a ​lower activation
energy​.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 10 OF 29

WHAT IS LE CHATELIER’S
PRINCIPLE

In 1888, a French chemist called Henri Le Chatelier (1850-1936) put forth the statement known as ​Le
Chatelier’s Principle:
 ​ isturbed b
“If a system at dynamic equilibrium is d ​ y changing the conditions, the system undergoes a
reaction which ​minimises the effect ​of the disturbance to attain a new e
​ quilibrium​”

A chemical system at equilibrium can be disturbed in the following

ways:

- Change in concentration - Change in pressure → Change in

volume →Change in concentration - Change in temperature

Le Chatelier’s principle is a ​convenient method for predicting ​equilibrium shifts, but ​does not explain
why ​it shifts. Collision theory explains the shift in equilibrium.

THE HABER PROCESS

CHANGE IN CONCENTRATION

N​2(g) ​+ 3H​2(g) ​⇋ 2NH​3(g) ​∆H = −92kJ mol​−1

ADDING A REACTION COMPONENT

Addition of H​2(g) ​increases ​[H​2(g)​]. This will result in the ​rate ​of the ​forward reaction ​to ​increase​, meaning the
forward reaction ​has been ​favoured​.

Since the rate of the forward reaction is different to the rate of the reverse reaction, the ​equilibrium has
been disturbed​.

Generally, the reaction that ​counteracts ​the disturbance will be ​favoured​; in other words, its ​rate will
increase ​relative to the other reaction.

REMOVING A REACTION COMPONENT

Removing N​2(g) ​decreases ​[N​2(g)​]. This will result in the ​rate ​of the ​reverse reaction ​to ​increase​, meaning
the ​reverse reaction ​has been ​favoured​.

The reaction that ​counteracts ​the disturbance will be ​favoured​; in other words, its ​rate will increase
relative to the other reaction.

CHANGE IN VOLUME (OR PRESSURE)

MOLES, VOLUME AND PRESSURE

The pressure exerted by a gas arises from the force of the gas particles colliding with the walls of the
container. Therefore, the ​pressure ​is ​proportional ​to the ​number of gas particles ​present.

Pressure ∝ Moles of gas

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 11 OF 29

Boyle’s Law ​states that ​pressure ​and v
​ olume ​are ​inversely proportional ​to each other.
1
Pressure ∝ ​
Volume
CHANGE IN VOLUME
Doubling the volume ​of the container decreases ​pressure​. To counteract this effect, the
reaction will shift in the direction that ​produces the most amount of moles​. Therefore, the
reverse reaction will be favoured.
CHANGE IN PRESSURE
Doubling the pressure ​of the container ​decreases ​volume. To counteract this effect, the
reaction will shift in the direction that ​produces the least amount of moles. ​Therefore, the
forward reaction will be favoured.
CHANGE IN TEMPERATURE
EXOTHERMIC AND ENDOTHERMIC REACTIONS
The effect of a change in temperature on a reaction at equilibrium depends on whether the
forward reaction is ​exothermic ​or e ​ ndothermic​.
N​2(g) ​+ 3H​2(g) ​⇋ 2NH​3(g) ​∆H = −92kJ mol​−1
If temperature of the system is ​increased​, the reverse reaction will be favoured to counteract
this effect. The reverse reaction is ​endothermic ​and will be favoured.
ADDITION OF A CATALYST
A catalyst ​increases the rate ​of a chemical reaction without being consumed, by providing an
alternate pathway of lower activation energy. The addition of a catalyst reduces the activation
energy of both the ​forward ​and ​reverse ​reaction ​by the same amount​.
- Therefore the addition of a catalyst will not disturb the equilibrium - The concentrations of the
components are not affected, by the system will reach equilibrium faster
ADDITION OF INERT GAS
The addition of an inert gas will increase pressure, but equilibrium will not be disturbed. This is
because the ​concentrations ​of reactants and products ​remain the same​, if the volume of the
container does not change.
DIMERISATION OF NITROGEN DIOXIDE

When colourless dinitrogen tetroxide gas (N​ O​ ) is enclosed in a vessel, a brown colour will
2​ 4​
 appear indicating the formation
​ of nitrogen dioxide (NO​ ). The intensity of the brown colour
2​

indicates the amount of nitrogen dioxide present

​ in the vessel. The dimerization of nitrogen
dioxide is an exothermic process
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 12 OF 29
NOTES

- A shift in the ​forward ​direction is called a shift ​towards the right side. ​- A shift in the
reverse ​direction is called a shift ​towards the left side. ​- Equilibrium will shift to remove
an added component (away from component) - Equilibrium will shift to replace a removed
component (towards the component) - An ​increase in volume ​will cause equilibrium to
shift towards the side with ​more gas moles. ​- A ​decrease in volume ​will cause
equilibrium to shift towards the side with ​fewer gas moles.

ANSWERING LE CHATELIER’S PRINCIPLE

QUESTIONS

Clearly explain the effect of changes in conditions on the yield of equilibrium

reactions.

1) State that the change in reaction conditions ​disturbs the equilibrium. ​2)
“According to Le Chatelier’s principle, the ​position of equilibrium shifts ​left/right”
3) ​Justify ​the shift:
a. ​“​To replace/remove” b. ​“​To the side with more/less gas moles, to increase/reduce pressure” c. ​“​In
the exothermic/endothermic direction, to replace/remove heat” 4) ​... and minimise the disturbance ​5)
State the effect of the shift, “Therefore, the ​concentrations of the reactants/products
increase/decrease”
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 13 OF 29

QUALITATIVE ANALYSIS OF
EQUILIBRIUM
OUTCOMES
● 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 (ACSCH095)
CONCENTRATION PROFILE DIAGRAMS

The changes occurring in a system can be identified by examining the shape of the line in a concentration
profile diagram during a particular time period.

- The ​x-axis ​is time or reaction progress - The

y-axis ​is concentration or partial pressure

Graph Feature Disturbance

Decrease volume → Increase pressure →
Concentration of one component spikes up, then Increase [concentrations] of components
all concentrations change
Increase [concentration] of a component Concentrations of all components spike down, then
all concentrations change
Increase volume → Decrease pressure →
Concentration of one component spikes down, then Decrease [concentrations] of components
all concentrations change
Decrease [concentration] of a component There are no spikes in the graph, then
all concentrations change
Change in temperature
Concentrations of all components spike up, then
all concentrations change

Concentrations are flat Nothing, at equilibrium

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 14 OF 29

EQUILIBRIUM CONSTANT
OUTCOMES
● deduce the equilibrium expression (in terms of ​K​eq​) for homogeneous reactions occurring in
solution (ACSCH079, ACSCH096)
● explore the use of ​Ke​ q ​for different types of chemical reactions, including but not limited to: –
dissociation of ionic solutions
EQUILIBRIUM CONSTANT EXPRESSION
A quantitative way of describing the position of equilibrium is the ​equilibrium constant ​(K​eq​).
aA + bB ⇋ cC + dD
- ​Capital ​letters represent ​chemical substances ​- Lower case letters represent the
stoichiometric coefficients ​of the balanced equation
[products]
K​eq ​= K​c ​= K = ​
= [C]​c​ d ​ a​ b
[reactants] ​ [D]​ [A]​ [B]​
In an ideal system, the value of K is ​constant at constant temperature​.
PURE, LIQUIDS AND SOLIDS
In ​heterogeneous ​systems, some of the components are in different phases:

CaCO​3(s) ​⇋ CaO​(s) ​+ CO​2(g)

The concentrations of ​pure solids ​and ​pure liquids cannot change ​at a constant
temperature.
- Because the equilibrium constant is only concerned with concentrations that change as they
approach
equilibrium, ​eliminate the terms for pure solids or liquids​. - The concentrations disappear
from the equilibrium constant expression. - Only ​gases ​and ​aqueous ​species appear in the
equilibrium, ​except ​if all the reactant and products are ​all
liquids​.
OUTCOMES
● perform calculations to find the value of ​K​eq a
​ nd concentrations of substances within an

equilibrium system, and use these values to make predictions on the direction in which a
reaction may proceed (ACSCH096)
INTERPRETING THE EQUILIBRIUM CONSTANT
The ​larger ​the value of K, the further the equilibrium lies towards the ​RHS. ​A reaction with a
very large ​K, proceeds ​almost to completion​.
The ​smaller ​the value of K, the further the equilibrium lies towards the ​LHS​. A reaction with a
very small ​K, proceeds ​barely at all​.
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 15 OF 29
K AND THE DIRECTION OF REACTION
If concentrations are substituted into the expression at any point, the value is called ​Q, ​the
reaction quotient​.
[C]​
Q = ​ c​[D]​d ​[A]​a​[B]​b
The relative values of Q and K determines which way the reaction will proceed to reach
equilibrium.
- If Q = K, then the system is at ​equilibrium ​- If Q > K, then the ​backwards ​reaction will be
favoured - If Q < K, then the ​forwards ​reaction will be favoured
RICE CALCULATIONS
Ratio ​The stoichiometric molar ratio of reactants and products.
[Initial] ​The initial concentrations of all components. The initial concentrations of the products
are zero if not
explicitly stated.
Change ​The change in concentration. Work one entry out from being given one equilibrium
concentration and
fill in the rest of the row according to the molar ratio.
[End] ​The concentrations of the components at equilibrium.
CALCULATIONS WITH QUADRATIC EQUATIONS
In some calculations, it will be required to solve a ​quadratic equation ​to determine x.
In these calculations, ​simplification ​can be used to make the calculation less complicated to
solve:
- If K is very small, then x will be very small, and the calculation can be simplified by using the
following
​ x ≈ [reactant]​initial -​ However, the ​assumption must be checked
approximation: [reactant]​initial −
to be ​valid​. The calculated value of x must be ​less than 5% ​of
the reactant’s initial concentration.
If the assumption is invalid, the quadratic formula has to be used: x = −b±√b​
​ 2​
−4ac
2a
OUTCOMES
● qualitatively analyse the effect of temperature on the value of ​K​eq ​(ACSCH093)
EFFECT OF TEMPERATURE ON ​K​eq
When temperature is ​increased​, equilibrium shifts so that the ​endothermic ​reaction is
favoured, whether it is the forward or the reverse reaction. Therefore, unlike changes in
concentration and pressure, a change in temperature is ​the only factor ​that will change the
value of K.
For ​exothermic ​reactions, K ​increases ​with ​lower ​temperatures and ​decreases ​with ​higher
temperatures.
For ​endothermic ​reactions, K ​decreases ​with ​lower ​temperatures and ​increases ​with ​higher
temperatures.
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 16 OF 29

IRON(III)
THIOCYANATE
OUTCOMES
● conduct an investigation to determine ​Ke​ q ​of a chemical equilibrium system, for
example: – ​K​eq ​of the iron(III) thiocyanate equilibrium (ACSCH096)

IRON (III) THIOCYANATE EQUILIBRIUM REACTION

When mixed together, aqueous solutions of ​iron(III) nitrate ​(Fe(NO​3​)​3​) and ​potassium thiocyanate ​(KSCN)
combine, in a ​reversible exothermic ​process, to form the aqueous i​ ron(III) thiocyanate ​complex
([Fe(SCN)]​2+​(aq)​).

+ SCN​−​ ⇌ ​[Fe(SCN)]​2+​
Fe​3+​(aq) ​ (aq) ​ (aq)

Iron(III) ions are very ​pale yellow ​colour, while iron(III) thiocyanate complex is an ​intense deep red
colour. When diluted and at equilibrium, the colour of the mixture containing all three species is amber.

EQUILIBRIUM SHIFTS

A shift to the RHS, increase concentration of [Fe(SCN)]​2+ ​→ More

intense

- Cool down system: ice water bath - Increase [Fe​3+​]

and [SCN​-​]: Add more FeCl​3 ​and KSCN

A shift to the LHS, decreases concentration of [Fe(SCN)]​2+ ​→ Less

intense

- Heat system: Hot water bath (Approx. 70 degrees Celsius)

- Decrease [Fe​3+​] and [SCN​-​]: Add NaOH and AgNO​3

NOTES

Since thiocyanate ions bind to iron via the nitrogen atom, the formula of the iron(III) thiocyanate
complex is sometimes written as [Fe(NCS)]​2+​.

WHAT IS SPECTROPHOTOMETRY

Spectrophotometry is an ​analytical technique ​that is used to determine the ​concentration ​of a

substance in a solution.
 - Iron(III) thiocyanate strongly ​absorbs light ​at
a wavelength of ​447 nm ​and reflects light that is
mostly ​orange-red​, hence we see it as
orange-red ​in colour. - Iron(III) thiocyanate
absorbs light blue light. - When it absorbs the
light, electrons are
transitioning from lower to higher quantised
energy levels. The energy gap between the
levels is equal to the energy of the 447 nm
wavelength light.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 17 OF 29

A ​UV/Vis spectrophotometer ​like the one shown measure the ​intensity ​of light passing through a sample
solution in a cuvette.

- A ​lamp ​provides white light (continuous source, which is narrowed and aligned into a beam using a
slit​. - A ​prism ​splits the light into different wavelengths and is rotated so the desired wavelength of light
passes
through the ​monochromator ​(exit slit). - The light beam passes through the sample,
which ​absorbs ​a fraction of the light. The greater the
concentration of iron(III) thiocyanate, the greater the absorption of 447 nm light. - The ​remaining
light ​is ​transmitted ​through the sample and reaches a ​detector​, which converts the amount
of light to an electrical signal.

A spectrophotometer expresses the intensity of light in absorbance

(A).

A = log​10 ​I​0​I

- ​A: ​Absorbance, a number typically between 0.3 – 2.5. It is dimensionless but often expressed in
absorbance
units (AU) - ​I​0​: ​The intensity of light passing through the ​blank
(reference) sample. - ​I: ​The intensity of light passing through the
analyte ​sample.

Absorbance ​is ​proportional ​to both ​concentration a

​ nd the ​length ​of the sample, according to the
Beer-Lambert Law.

A = εlc
 - ε​: ​Extinction coefficient (also known as molar absorptivity), a constant that relates absorbance
with
concentration and path length, with the units L cm​−1
mol​−1 ​- l: Path length of sample in cm - c: Concentration of the
substance in the sample in mol L​−1

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 18 OF 29

SOLUBILIT
Y
OUTCOMES
● describe and analyse the processes involved in the dissolution of ionic compounds in water

PROPERTIES OF IONIC COMPOUNDS

A process where equilibrium is often established is in the ​dissolution of ionic compounds ​in
water.

- Ionic compounds contain both ​cations ​and ​anions​. - They have an

electrostatic attraction ​between oppositely charged ions. - They are:
o ​Brittle ​o ​High MP, BP ​o ​Solids at room
temperature ​o ​Molten and aqueous state
conducts electricity

SOLUTIONS OF IONIC COMPOUINDS

Soluble ionic compounds will dissolve in water to form ​aqueous solutions. ​When a soluble ionic compound
is added to water, the ions at the surface of the crystal become ​surrounded ​by water molecules.

- Some molecules of water separate from one another and are able to pack closer to the cations and
anions of
the ionic salt.
o ​They form ion-dipole forces between the
molecules. - Solute: Ionic salt - Solvent: Water

When the ion-dipole forces between the ions and the permanent dipoles of the water molecules (​adhesive
forces​) become stronger than the ionic bonds between the ions and the hydrogen bonding within the water
(​cohesive forces​), the ions are dislodged from their position in the crystal.

- The ionic compound ​dissociates ​into its component ions.

- The ions become ​solvated.

The solvated or hydrated ions are surrounded by a shell of water molecules known as a ​solvation
layer.
 CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 19 OF 29
- The solvation layer acts as a cushion and prevents a solvated anion from colliding directly with a
solvated
cation, and therefore keeps the ions in the
solution.

Many ionic compounds are soluble in water and will dissociate to form aqueous
solutions.

- However not all ionic compounds are soluble in water. For example, AgCl and Ca​3​(PO​4​)​2 ​are insoluble.
- The ​insolubility ​of these ionic compounds is due to their ​strong ionic bonds ​which cannot be
disrupted by
the ​adhesive ion-dipole ​forces between solute ions and water molecules. Hence the ions do not
become dislodged from their positions in the crystal.

Entropy can also contribute to solubility. Most dissolutions are ​entropically favourable ​(∆S > 0), but
some dissolutions are unfavourable.

- The solution consists of the solute and the solvent, so the change in entropy of each part can be
considered
separately to determine the overall change in entropy for the dissolution
process:

∆S​solute ​+ ∆S​solvent =
​ overall ∆S

- Depending on the relative magnitude of the effects, total entropy can increase or decrease for the
overall
system when dissolution occurs, although in majority of cases ​overall entropy will increase​. - An
overall decrease in entropy sometimes occurs for ions with ​high charge density ​as they interact strongly
with water molecules, so the water molecules are ​held tightly ​around the solvated
ions.

INCREASE IN ENTROPY

Solute in a solid state has a ​fixed ordered arrangement​. Dissolved solute has ​free mobile ions​. Therefore,
there is an increase in entropy as the number of possible arrangement increases.

DECREASE IN ENTROPY

Pure water molecules are in ​random arrangements ​and are also ​mobile. ​When water becomes a solvent,
molecules solvate the solute and has ​less possible arrangements ​decreasing entropy.

NOTES

“Clear” means that light can pass through the substance without being
scattered.

“Colourless” means the substance is not coloured. Solutions are clear, but not necessarily
colourless.”

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 20 OF 29

OUTCOMES
● conduct an investigation to determine solubility rules, and predict and analyse the
composition of substances when two ionic solutions are mixed, for example: – potassium chloride and
silver nitrate – potassium iodide and lead nitrate – sodium sulfate and barium nitrate (ACSCH065)

PRECIPITATION

The production of an insoluble compound, usually by reacting two soluble

compounds.

NaCl​(aq) ​+ AgNO​3(aq) ​→ AgCl​(s) ​+

NaNO​3(aq)

When two clear solutions are mixed together, an insoluble compound is formed. This is called a ​precipitate
reaction​. Precipitation reactions are used to remove minerals from drinking water, to remove heavy metals
from wastewater and in purification plants of reservoirs.

SOLUBILITY RULES
 Rule Exceptions
NONE
+​ +​ +​ +​ +​
All Group 1 (Li​ Na​ K​ Rb​ Cs​ ) and
ammonium (NH​+​) salts are soluble
NONE All chloride (Cl​-​), bromide (Br​-​) and iodide
(I​-​) salts are soluble
Ag​+​, Pb​2+ ​and Hg​2+ ​halides are
All nitrate (NO​3-​​ ), acetate (CH​3​COO​-​) insoluble
and bicarbonate (HCO​3​-​) salts are
soluble

All sulfate (SO​42-​ +​ 2+​ 2+​ 2+​ 2+​

​ ) salts are soluble Ag​ , Pb​ , Hg​ , Ba​ , Ca​ , Sr​
2+

sulfates are insoluble

All hydroxides (OH​-​) salts are insoluble Group 1 and NH​4+​ ​hydroxides
are soluble,

Ba​2+ ​and Ca​2+ ​are slightly soluble

Group 1 and NH​4+​ ​carbonates
All carbonate (CO​32-​​ ) and phosphate are soluble
3-​
(PO​4​ ) salts are insoluble

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 21 OF 29

OUTCOMES
● derive equilibrium expressions for saturated solutions in terms of ​K​sp a
​ nd calculate the

solubility of an ionic substance from its ​K​sp ​value

SOLUBILITY
The ​solubility ​of a compound is the ​maximum amount of solute that can dissolve ​in a specific volume of
solvent at a certain temperature.

- Solubility is a physical constant, like melting point or boiling point

Term Solubility Range in Water (​g L​−1​)

Very soluble ≥ 1000

Freely soluble 100 – 1000

Soluble 33 – 100

Sparingly soluble 10 – 33

Slightly soluble 1 – 10

Very slightly soluble 0.1 – 1

Insoluble < 0.1

EQUILIBRIA IN SATURATED SOLUTIONS

When a solvent has dissolved all the solute it can at a given temperature, the resulting solution is
saturated​.

- Any solution containing less solute than this is ​unsaturated​. - If

more solute is added to a saturated solution, no more will dissolve.

In a saturated solution, the system is ​in dynamic

equilibrium​:

- All of the species – the ionic solid and dissolved ions – are present in the final mixture. - The
forward reaction is occurring at the ​same rate ​as the reverse reaction. In other words, when an ion
dissolves, another ion is precipitating at ​the same
time​.

The equilibrium constant for these solution equilibria is called the ​solubility product constant
(K​sp​).

- The equilibrium constant is for the equation written in ​the direction of the
 dissolution​.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 22 OF 29

UNITS OF CONCENTRATION
MOLARITY
Molarity ​is the main unit of ​concentration u
​ sed in chemistry:
moles of solute (n)
molarity (c) = ​
volume of solution (V)
- The volume of solution is expressed in ​litres (L)​.
o ​The volume of the total solution (​solute + solvent​) is used calculate concentration.
PERCENTAGE BY MASS OR WEIGHT (% M/M OR % W/W)
- Percentages by mass and weight are both extensively used in industry. - ​% m/m ​is an
abbreviation for the ​percentage mass ​of a s ​ ubstance ​relative to the ​total mass​. This is the
same as ​percentage weight (% w/w)​.
o ​Percentage is given by the formula: % by mass = mass ​ of solute

× 100 ​
mass of solution ​ o ​% w/w or m/m can be interpreted as ​grams of solute ​per ​100g. ​o ​Note:
the formula requires the total mass of the ​solution​, not solvent.
PERCENTAGE BY VOLUME (% V/V)
- Percentages by mass and weight are both extensively used in industry. - The Percentage by
volume is given by the formula: % of volume = volume
​ of solute

× 100
volume of solution ​

MASS PER VOLUME (M/V)

- Mass per volume is used in pharmacy and medicine. - Mass per volume is used to measure
the ​blood alcohol level of drivers​. o​ ​A blood alcohol level of 0.01 refers to 0.010/g / 100mL of
blood
PARTS PER MILLION & PARTS PER BILLION
- ​Parts per million ​and ​parts per billion ​(ppm and ppb) are useful when describing ​very
dilute ​solutions.
o ​concentration (ppm) = mass
​ of solute (mg)

mass of solution (kg) ​o ​concentration (ppb) = mass

​ of solute (μg)
 mass of solution (kg)
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 23 OF 29

SUMMARY ​Name Unit Solute Unit Solution Unit

Molarity ​mol per 1 L mol L​−1 ​or M

% by mass ​g per 100 g % m/m or % v/v

% by volume ​mL per 100 mL % v/v

Parts per million ​mg per kg ppm

Parts per billion ​μg per kg ppb

OUTCOMES
● investigate the use of solubility equilibria by Aboriginal and Torres Strait Islander Peoples when removing
toxicity from foods, for example: – toxins in cycad fruit

Many native foods eaten by Aboriginal and Torres Strait Islander people are poisonous and need to be
detoxified ​before consumption

There are several physical and chemical processes user for

detoxification:

COOKING OR ROASTING (CHEMICAL

REACTION)

• The food items are heated in an oven or fire

• The heat causes the toxins to decompose

LEACHING (PHYSICAL CHANGE)

• The food items are cut up into smaller pieces and soaked in running
water.
• Water-soluble toxins are washed away.

FERMENTATION OR PROLONGED STORAGE (CHEMICAL

REACTION)

• The food items are stored for long periods (several months to several
 years)
• During this time, various biological processes occur that break down the
toxins.
o ​They are digested by fungi, or broken down by the plant's natural enzymes. (Biological
catalysts)

CYCADS (MACROZAMIA)

Cycads are palm-like plants that produce seeds in cones. Cycad seeds are a rich source of carbohydrates
and have been eaten in regions of Northern Australia for thousands of years. However, the seeds contains
highly toxic chemicals.

The two main types are cycasin and b-methylamino-l-alanine

(BMAA).

To prepare them, Aboriginal and Torres Strait Islander people who ate these seeds would commonly
prepare them by:

- Cooking the seeds in an oven or fire

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 24 OF 29

- Cutting the seeds open and leach them in running water for around a week - Fermentation or storage for
several months, or several years (some groups stored them for more than three
years)

THE POISON, CYCASIN

• Cycasin (C8H16N2O7)
• Methylazoxmethanol glucoside
• Molar Mass = 252.22g/mol
• pKa = 12.21 (measure of acidity)

SOLUBILITY

• 56.6 g/L @ 25 in water/diluted ethanol

• Sparingly soluble in absolute ethanol
• Insoluble in benzene, chloroform + acetone
DECOMPOSITION

• Melting point @144

• Decomposes at 154
• Produces N2

MORETON BAY CHESTNUT (BLACK

BEAN)

The Moreton Bay Chestnut is found on the east coast of Australia. It produces pods containing large seeds
that are toxic. Eating unprocessed seeds causes vomiting and diarrhoea. When cooked, processed seeds
taste like sweet chestnuts.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 25 OF 29

SOLUBILITY
CALCULATIONS
OUTCOMES
● derive equilibrium expressions for saturated solutions in terms of ​K​sp a
​ nd calculate the

solubility of an ionic substance from its ​K​sp ​value

● predict the formation of a precipitate given the standard reference values for ​K​sp

CALCULATING ​K​sp FROM

​ SOLUBILITY

An equilibrium is only present in a ​saturated ​solution where the maximum amount of ionic compound has
dissolved. Therefore, the ​solubility ​of a substance, whether given in moles per litre or mass per volume, can
be used to ​calculate the solubility constant ​K​sp​.

PREDICTING THE FORMATION OF A

PRECIPITATE

Solubility constants can be used to predict if a ​precipitate will form ​when two solutions are
mixed.

+ 2OH​−​
Ba(OH)​2(s) ​⇋ Ba​2+​(aq) ​ (aq)

2+​ −​ 2
K​sp =
​ [Ba​ ][OH​ ]​

- The solubility constant for this reaction at 25°C is 2.55 × 10​−4 ​-

This means [Ba​2+​][OH​−​]​2 ​= 2.55 × 10​−4 ​in a saturated solution.

If the concentration of Ba​2+ ​and OH​- ​are h

​ igher ​than the amounts in a saturated solution, Q > K​sp and
​
precipitation ​will occur​.

If the concentration of Ba​2+ ​and OH​- ​are l​ ower ​than the amounts in a saturated solution, Q < K​sp and
​
precipitation ​will not occur​.

THE COMMON ION EFFECT

In an aqueous solution of an ionic compound, the ions are

dissociated​.

- This means that the ions ​separate ​into individual solvated ions. - Ions of the
same species are indistinguishable, regardless of where they originated.
This means that in a saturated solution, if ​another substance is added ​that has an ion in common with
the first substance, it will affect the position of equilibrium, leading to ​lower solubility​. This is known as
the ​common ion effect​.

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 26 OF 29

SOLUBILITY CURVES (SOLUBILITY AND
TEMPERATURE)

Since dissolution is a reversible process, the position of equilibrium (extent of dissolution) will
depend on ​temperature​.

The relationship between solubility and temperature can be seen on a ​solubility curve​, which shows the
maximum amount of solute that can dissolve at a range of temperatures.
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 27 OF 29
DISSOCIATION OF ACIDS
OUTCOMES
● explore the use of ​K​eq ​for different types of chemical reactions, including but not limited to: –
dissociation of acids and bases (ACSCH098, ACSCH099)
COMMON ACIDS
Name Formula
Hydrochloric acid HCl
Sulfuric acid H​2​SO​4
Nitric acid HNO​3
Phosphoric acid H​3​PO​4
Carbonic acid H​2​CO​3
Acetic acid (Vinegar/Ethanoic acid) CH​3​COOH
ACID STRENGTH
Acids differ in their ​strength​: the ​extent of ionisation ​or ​dissociation ​in water.
- A stronger acid will ionise further
Strong acids ​completely dissociate in water
- Straight arrows are used to indicate that these dissociations are irreversible and proceed to
completion.
Weak acids ​partially dissociate in water.
- Reversible arrows are used indicate that these dissociations proceed to equilibrium.
The ​acid dissociation constant ​is the equilibrium constant for the dissociation (ionisation) of
an acid into hydrogen ions (H​+​) and an anion (K​a​).
Acids that can produce more than one H​+ ​ion are known as ​polyprotic acids​.
​
- The dissociation of each H​+ ion occurs ​stepwise​, and an acid dissociation constant is
assigned to ​each step​.
+ H​ PO​ −​ [H​+​
H​3​PO​4(aq) ⇋​ H​+​(aq) ​ 2​
K​ ​ ​ ][H​2​PO​4​−​]
4​ (aq) ​ a1 =

= 7.52 × 10​−3 ​ + HPO​ 2−​ [H​+​

[H​3​PO​4​] ​ H​2​PO​4​−​(aq) ​⇋ H​+​(aq) ​ K​ ​ ​ ][HPO​4​2−​]
4​ (aq) ​ a2 =

−8 ​ +​ + PO​ 3−​ [H​+​

[H​2​PO​4​−​] =​ 6.23 × 10​ HPO​4​2−​(aq) ⇋​ H​ (aq) ​ K​ ​ ​ ][PO​4​3−​]
4​ (aq) ​ a1 =

−13
[HPO​4​2−​] =
​ 2.20 × 10​
Acid strength depends on the ​identity of the acid ​and the extent of its ​ionisation ​in water.
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 28 OF 29
STRONG ACIDS
- Perchloric: HClO​4 ​- Hydriodic: HI - Hydrobromic: HBr - Hydrochloric: HCl - Nitric: HNO​3 ​-
Sulfuric: H​2​SO​4
PH SCALE
The ​acidity ​of a solution is determined by both the ​strength ​and the ​concentration ​of the
acids present.
The concentration of the hydrogen ions in a solution are generally small. The pH scale, a
logarithmic ​scale, is a convenient way of expressing [H​+​] as a number generally between 0
(extremely acidic) and 14 (extremely basic).
A pH of 7 represents a ​neutral solution​. The further away from 7, the more acidic or alkaline
the solution.
pH can be calculated from the [H​+​] using the equation:
pH = −[H​+​]
- p stands for −log​10​, and the concentration of the hydrogen ions are in mol L​−1 ​- The notation
pH derives from the French ​pouvoir hydrogene​, meaning the “power of hydrogen”
DEGREE OF IONISATION
To calculate the ​percentage ​of any component in a sample, the formula is:
component
percentage (%) = ​
× 100
total ​
FOR A WEAK ACID HA:

HA​(aq) ​⇋ H​+​(aq) ​+ A​−​(aq)

The percentage ​ionised ​(degree of ionisation):
[H​
% ionised = ​ +​]​eqm
[H​−​
​ 100 = ​
[HA]​initial × ]​eqm
[HA]​initial ​× 100
The percentage ​unionised ​(percentage of ​intact molecules​):
[HA]​
% unionised = ​ eqm

[HA]​initial ×
​ 100 = 100 − % ionised
CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 29 OF 29

CHEMISTRY
MODULE 6
 Acid/Base Reactions
PROPERTIES OF ACIDS AND
BASES

Inquiry question: ​What is an acid and what is a

base?

Students:

● investigate the correct IUPAC nomenclature and properties of common inorganic acids and bases
(ACSCH067)
● conduct an investigation to demonstrate the preparation and use of indicators as illustrators of
the characteristics and properties of acids and bases and their reversible reactions (ACSCH101)
● predict the products of acid reactions and write balanced equations to
represent: – acids and bases – acids and carbonates – acids and metals
(ACSCH067)
● investigate applications of neutralisation reactions in everyday life and industrial
processes
● conduct a practical investigation to measure the enthalpy of neutralisation
(ACSCH093)
● explore the changes in definitions and models of an acid and a base over time to explain the limitations of
each model, including but not limited to: – Arrhenius’ theory – Brønsted–Lowry theory (ACSCH064,
ACSCH067)

USING BRØNSTED–LOWRY
THEORY

Inquiry question: ​What is the role of water in solutions of acids and

bases?

Students:

● conduct a practical investigation to measure the pH of a range of acids and

bases
● calculate pH, pOH, hydrogen ion concentration ([H​+​]) and hydroxide ion concentration ([OH​–​]) for a
range of solutions (ACSCH102)
● conduct an investigation to demonstrate the use of pH to indicate the differences between the strength of
acids and bases (ACSCH102)
● write ionic equations to represent the dissociation of acids and bases in water, conjugate acid/base
pairs in solution and amphiprotic nature of some salts, for example: – sodium hydrogen carbonate –
potassium dihydrogen phosphate
● construct models and/or animations to communicate the differences between strong, weak, concentrated
and dilute acids and bases (ACSCH099)
● calculate the pH of the resultant solution when solutions of acids and/or bases are diluted or
mixed

QUANTITATIVE ANALYSIS

Inquiry question: ​How are solutions of acids and bases

analysed?

Students:

● conduct practical investigations to analyse the concentration of an unknown acid or base by

titration
● investigate titration curves and conductivity graphs to analyse data to indicate characteristic reaction
profiles, for example: – strong acid/strong base – strong acid/weak base – weak acid/strong base
(ACSCH080, ACSCH102)

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 1 OF 40

● model neutralisation of strong and weak acids and bases using a variety of
media
● calculate and apply the dissociation constant (​K​a​) and ​pK​a ​(​pKa​ =
​ -log​10 (​ Ka
​ ​)​) to determine the
difference between strong and weak acids (ACSCH098)
● explore acid/base analysis techniques that are applied:
– in industries – by Aboriginal and Torres Strait Islander
Peoples – using digital probes and instruments
● conduct a chemical analysis of a common household substance for its acidity or basicity (ACSCH080) ,
for example: – soft drink – wine – juice – medicine
● conduct a practical investigation to prepare a buffer and demonstrate its properties
(ACSCH080)
● describe the importance of buffers in natural systems (ACSCH098,
ACSCH102)
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 2 OF 40

ACIDS/BASES &
INDICATORS
OUTCOMES
● investigate the correct IUPAC nomenclature and properties of common inorganic acids and bases
(ACSCH067)

ACIDS AND BASES

WHAT IS AN ACID?

Acids are a group of commonly used substances that share the following
properties:

• They taste ​sour

• They produce ​H+​ ​when dissolved in water (Arrhenius definition)
• Acids ​ionise ​in solution (HX + H​2​O → H​3​O​+ ​+ X​−​)
• ​pH below 7
• They are ​corrosive ​and will wear down materials like metal and
skin.
• Turns ​blue litmus indicator red
• Acids ​conduct electricity ​as it has mobile ions that are able to conduct
charge.
o ​Conductivity ​∝ ​[ions] ​o ​Strong
Acids = Strong electrolyte ​o ​Weak
Acids = Weak electrolyte

WHAT IS A BASE?

Bases are another group of commonly used substances. The properties of bases
include:

• They taste ​bitter ​and have a ​slippery ​or soap-like feel

• They produce ​hydroxide ions ​in water (Arrhenius definition)
• ​pH above 7
• They are ​corrosive (caustic)
• They turn ​red litmus indicator blue

OUTCOMES
● conduct an investigation to demonstrate the preparation and use of indicators as illustrators of
the characteristics and properties of acids and bases and their reversible reactions (ACSCH101)
INDICATORS

• Indicators give a ​qualitative ​indication of the [H​+​]

• Indicators changes colour in response to the surrounding pH
• An ​acidic ​solution has a high [H​+​], whereas a basic solution has low
[H​+​].

The equation for calculating pH is: pH = −log​10​[H​+​]

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 3 OF 40

HOW DO INDICATORS WORK?

Most indicators are organic ​weak acids ​or ​weak bases​. They are a special case of a
weak acid.

+ Ind​−​
HInd​(aq) ⇌​ H​+​(aq) ​ (aq)

Molecule (Colour I) ⇌ Hydrogen Ion + Anion (Colour II)

• ​Ind​: An abbreviation for “indicator” and represents the rest of the organic
molecule.
• The two forms are different colours (I and II). Changes in [H​+​] will shift
equilibrium.

LOW PH & HIGH PH

• Low pH == High [H​+​]

o ​Equilibrium will lie towards the LHS ​o ​Hind will
dominate and colour observed will be Colour I
• High pH == Low [H​+​]
o ​Equilibrium will lie towards the RHS ​o ​Ind​- ​will
dominate and colour observed will be colour II
 Indicator Colour at lower pH Colour at higher pH pH of colour change range

Methyl orange Red Yellow 3.1 – 4.4

Bromothymol blue Yellow Blue 6.0 – 7.6

Phenolphthalein Colourless Pink 8.3 – 10.0

Methyl red Red Yellow 4.8 – 6.0

Litmus Red Blue 4.5 – 8.3

Phenol red Yellow Red 6.8 – 8.4

Some limitations of indicators include:

• Approximate pH (not accurate)

• Cannot distinguish between strong/weak acid/base
• Destroys/contaminates solutions

Some advantages include:

• Cheap and relatively easy to use

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 4 OF 40

EVERYDAY USES OF INDICATORS

SWIMMING POOLS

Swimming pool pH needs to be ​maintained close to 7.4 ​to avoid ​irritation ​of the eyes and mucous
membranes (which are at approximately pH 7.4).

• Bromothymol blue or phenol red can be used to test the pH of the pool.
• If the pH needs to be lowered, acids such as HCl or solid (NaHSO​4​) can be
added.
• If the pH needs to be raised, sodium carbonate (Na​2​CO​3​) can be
added.
 CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 5 OF 40
OUTCOMES
● predict the products of acid reactions and write balanced equations to
represent: – acids and bases – acids and carbonates – acids and metals
(ACSCH067)

REACTIONS OF ACIDS

ACID + METAL HYDROXIDE/OXIDE (NEUTRALISATION)

HX​(aq) +
​ MOH​(s)/(aq) →
​ MX​(aq) +
​ H​2​O​(l)

Metal oxides ​are also bases and react with acids to form a salt and
water.

• 2HCl​(aq) ​+ MgO​(s) ​→ MgCl​2(aq) ​+ H​2​O​(l)

Ammonia ​is a special case of a base that will undergo neutralisation but will not produce water, as it
does not contain oxygen in its formula.

• Ammonia (NH​3​) is covalent molecular. It is a gas at room temperature and highly soluble at
RTP
 • Instead it will produce an ​ammonium salt ​as the product
• HBr​(aq) ​+ NH​3(aq) ​→ NH​4​Br​(aq)

ACID + METAL CARBONATE / HYDROGEN

CARBONATE

HX​(aq) +
​ MCO​3(s) →
​ MX​(aq) +
​ H​2​O​(l) +
​ CO​2(g)

ACID + REACTIVE METAL (REDOX

REACTION)

HX​(aq) +
​ M​(s) →
​ MX​(aq) ​+ H​2(g)

EVERYDAY USES OF
ACIDS/BASES

Bee stings and ant bites are acidic in nature. They can be neutralised using alkaline medicine such as baking
powder.

Wasp stings are alkaline in nature. Vinegar can be used to cure wasp stings because vinegar can neutralise
the sting.

When stung by a stingray, concentrated vinegar can be used to stop the nematocysts from firing off such
that you won’t get injected with more venom.

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 6 OF 40

THEORIES OF ACIDS AND

 BASES
OUTCOMES
● explore the changes in definitions and models of an acid and a base over time to explain the limitations of
each model, including but not limited to: – Arrhenius’ theory – Brønsted–Lowry theory (ACSCH064,
ACSCH067)

LAVOISIER – 1776 “FATHER OF CHEMISTRY”

(OXIDES)

Antoine Lavoisier was a French chemist who established the quantitative science of chemistry. He
investigated ​oxides ​of different elements, and found that ​non-metal oxides reacted with water,
producing acidic solutions​. He concluded that an ​acid ​must contain oxygen. Eg:

SO​2(g) ​+ H​2O​
​ (l) →
​ H​2SO​
​ 3(aq)

CO​2(g) ​+ H​2O​
​ (l) ​→ H​2​CO​3(aq)

DAVY – 1810 (HYDROGEN)

English chemist Humphry Davy (famous for his redox and electrolytes works) demonstrated that
hydrochloric acid ​did not contain oxygen, thus disproving Lavoisier’s theory. Davy suggested that
hydrogen ​must be the ​unifying component of acids ​rather than oxygen.

LIEBIG – 1838 (ACID + METAL)

The German chemist Justus von Liebig expanded on Davy’s idea. In 1838, he proposed that acids ​contain
hydrogen ​which could be ​displaced by a reaction with a metal​. Eg:

Mg​(s) ​+ 2HCl​(aq) ​→ MgCl​2(aq) ​+ H​2(g)

Zn​(s) +
​ H​2​SO​4(aq) ​→ ZnSO​4(aq) ​+ H​2(g)

ARRHENIUS – 1884 (H+ AND OH-)

Svante Arrhenius proposed the first concept of acids and bases we still
use.
 - Arrhenius’ work centred on the ​conductivity ​of electrolytes. He postulated that ​electrolytes
dissociated ​in
water into ions. - He defined acids and bases according
to their ​effect in water​.

An ​Arrhenius acid ​is a substance that produces a ​H+​​ (aq) ​in

water.

+ Cl​−​
HCl​(aq) →
​ H​+​(aq) ​ (aq)

Arrhenius also notated that the ​most reactive acids ​also had the highest ​electrical conductivities​. This
led to the concept that the ​strongest acids ​were the ​most dissociated ​in aqueous solution.

An ​Arrhenius base ​is a substance that produces ​OH​-​(aq) ​in

water.

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 7 OF 40

LIMITATIONS OF THE ARRHENIUS DEFINITION

Arrhenius’ definition does not explain the basic behaviour of substances like ​ammonia​, which do not
contain hydroxide ions in their formulae and hence should not be able to produce OH​-​.

It does not explain why neutralisation reactions between some acids and bases produced solutions that
were ​not neutral​.

- The reaction between ammonia and hydrochloric acid produces an acidic solution. (NH​4​Cl – an acidic
salt) - The reaction between acetic acid and sodium hydroxide produces a basic solution (NaCH​3​OO – a
basic salt)

The Arrhenius definition only covers acids and bases in ​aqueous

solutions​.

BRONSTED-LOWRY ACIDS AND BASES (CONCEPTUAL

DEFINITION)

In 1923, Danish chemist Johannes Nicolaus Bronsted and English chemist Thomas Martin Lowry
independently proposed a new definition of acids and bases.

Acids and bases are defined by their ​role ​in a

reaction:
 - The ​proton donor ​is the Bronsted-Lowry ​acid ​-
The ​proton acceptor ​is the Bronsted-Lowry ​base

The Bronsted-Lowry definition allows ​many more species ​to be defined as acids or bases. It can explain
the basic behaviour of ​ammonia​. The NH​3(aq) ​is accepting a proton from HCl in the aqueous solution.
NH​3(aq) ​is a Bronsted Lowry base and HCl is a Bronsted Lowry acid.

HCl​(aq) +
​ NH​3(aq) →
​ NH​4​+​(aq) ​+ Cl​−​(aq)

Bronsted Lowry theory also explains the basic behaviour of ​ionic compounds ​in
solution.

Soluble carbonates and hydrogen carbonates ​contain Bronsted Lowry bases​. They produce basic
solutions.

1) First the compound ​dissolves ​in water to produce aqueous ions. This step proceeds completely,
since all
Group 1 ionic compounds are soluble:

+ CO​
Na​2​CO​3(s) ​→ 2Na​+​(aq) ​ 3​
2−​
(aq)

2) The dissolved carbonate or hydrogen carbonate ion is a Bronsted Lowry base which ​reacts with
water ​to
produce hydroxide ions:

−​
CO​3​2−​(aq) +
​ H​2​O​(l) ⇌
​ HCO​3​−​(aq) +
​ OH​ (aq)

The Bronsted Lowry definition is broad enough that some species like water can be classified ​both ​an ​acid

and a ​base​. ​- For example, when ammonia dissolves in water, water ​donates H​+ ​to ammonia and is acting

as a ​Bronsted
Lowry acid​.

NH​3(aq) ​+ H​2​O​(l) ​⇌ NH​4​+​(aq) ​+ OH​−​(aq)

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 8 OF 40

- When HCL dissolves in water, water ​accepts H​+ ​from HCl and is acting as a ​Bronsted Lowry
base​.
 + Cl​−​
HCl​(aq) +
​ H​2​O​(l) →
​ H​3​O​+​(aq) ​ (aq)

A substance that is capable of ​both donating and accepting protons ​(depending on the other reagent)
is known as an ​amphiprotic substance​.

HYDRONIUM IONS

- A H​+ ​ion is a bare proton with a +1 charge. This means that any H​+ ​ion in water immediately combines
with a
water molecule to form a more stable ​hydronium ion,
H​3​O​ . ​- H​+ ​does not technically exist independently in solution.
+​

+ H​ O​ → H​ O​+​
H​+​(aq) ​ 2​ (l) ​ 3​ (aq)

STRENGTHS OF ACIDS AND

BASES

STRONG/WEAK ACIDS

A ​strong acid ​is a ​strong electrolyte ​that ​ionises completely ​in water to produce hydronium ions in
aqueous solutions. Eg:

+ Cl​−​
HCl​(aq) →
​ H​+​(aq) ​ (aq)

List of strong acids:

• HCl
• HNO​3
• H​2​SO​4
• HBr (Hydrobromic acid)
• HI (Hydroiodic acid)

• HClO​4 ​(Perchloric acid)

• HClO​3 ​(Chloric acid)

All other acids are ​weak ​acids, which ​ionise ​partially in water to form hydronium ions in solution. They are
weak ​electrolytes​. Eg:
 + F​−​
HF​(aq) ⇌​ H​+​(aq) ​ (aq)

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 9 OF 40

ACID DISSOCIATION CONSTANT (K​A​)
The higher the K​a ​the stronger the acid strength as it favours the RHS.
Most acids are ​monoprotic​: they can only produce one proton. However, some acids have
more than one K​a ​value. These acids can produce more than one H​+ ​ion and are known as
polyprotic acid​.
For example, phosphoric acid is a ​triprotic acid​.
+ H​ PO​ −​ [H​+​
H​3​PO​4(aq) ⇋​ H​+​(aq) ​ 2​
K​ ​ ​ ][H​2​PO​4​−​]
4​ (aq) ​ a1 =

= 7.52 × 10​−3 ​ + HPO​ 2−​ [H​+​

[H​3​PO​4​] ​ H​2​PO​4​−​(aq) ​⇋ H​+​(aq) ​ 4​ (aq) ​ a2 ​= ​
K​ ][HPO​4​2−​]
−8 ​ +​ + PO​ 3−​ [H​+​
[H​2​PO​4​−​] =​ 6.23 × 10​ HPO​4​2−​(aq) ⇋​ H​ (aq) ​ K​ ​ ​ ][PO​4​3−​]
4​ (aq) ​ a3 =

−13
[HPO​4​2−​] =
​ 2.20 × 10​
The number of protons an acid produces is unrelated to its strength.
STRONG/WEAK BASES
Strong bases ​include ​Group 1 and 2 metal hydroxides​. When they dissolve, they produce
free hydroxide ions. ​Carbonates ​are weak bases.
- NaOH (Caustic soda, drain cleaner, oven cleaner) - KOH - Ca(OH)​2 (​ Lime water) - Ba(OH)​2
Although Group 2 hydroxides are ​strong bases​, they are ​poorly soluble in water​.
A ​weak base ​is one that ​reacts partially ​with water to indirectly form hydroxide ions in solution.
NH​3(aq) ​+ H​2​O​(l) ​⇌ NH​4​+​(aq) ​+ OH​−​(aq)
STRENGTH VS CONCENTRATION
- ​Acid strength ​depends on the ​identity of the acid a
​ nd the extent of its ​ionisation ​in water. -
Concentration ​depends on the ​amount ​of acid in a given volume of solution
Solution Strong or Weak? Concentrated or Dilute?
10 M HCl Strong Concentrated
 10 M HF Weak Concentrated
0.01 M HCl Strong Dilute
0.01 M HF Weak Dilute
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 10 OF 40
CONJUGATE ACIDS AND
BASES

The ionisation of an acid can be represented by the following

equation:

+ A​−​
HA​(aq) ⇌​ H​+​(aq) ​ (aq)

When the equation above is read in reverse, it shows A​- ​accepting a proton and acts as a Bronsted
Lowry base.

HA and A​- ​are known as a ​conjugate acid/base

pair​.

- The two species in a conjugate pair differ by a proton (H​+​) - When a Bronsted Lowry acid ​loses a

proton​, it forms the ​conjugate base ​of that acid. (HNO​3​/NO​3​−​) -​ When a Bronsted Lowry base
gains a proton​, it forms the ​conjugate acid ​of that base. (F​−​/HF) - An acid’s ​conjugate base ​has
1 less proton, ​while a base’s ​conjugate acid ​has ​1 more proton​.

−​ + ​H​ O​+​
​ ​H​2​O​(l) ​→ ​CH​3​COO​ (aq) ​
CH​3​COOH​(aq) + 3​ (aq)

- ​Conjugate acid-base pair ​-

Conjugate base-acid pair

Acid → Donates H​+ ​→ Conjugate

Base

Base → Accepts H​+ ​→ Conjugate

Acid

RELATIVE STRENGTH OF CONJUGATE

PAIRS

The two species in conjugate pair have ​inverse

strength​.
 - A ​strong acid ​will have an extremely weak (in practice, ​neutral​) ​conjugate base​. (e.g.
HCl/Cl​−​) - A ​weak acid ​will have a ​relatively strong conjugate base​. (e.g.
CH​3​COOH/CH​3​COO​−​) - The same situation applies for ​bases ​and their ​conjugate acids​.

A ​strong acid ​has a ​strong tendency ​to give up a ​H+​​ , and ​completely ionise
in water.

+ Cl​−​
HCl​(aq) +
​ H​2​O​(l) →
​ H​3​O​+​(aq) ​ (aq)

- The equilibrium lies ​far to the right ​- If the reaction is viewed in ​reverse​, it shows that the ​chloride
ion ​has a ​very weak tendency ​to accept a
proton, as the reverse reaction ​barely proceeds​. - Therefore, HCl has an ​extremely weak
conjugate base​. It practically has ​negligible proton-accepting ability​,
and produces a ​neutral
solution​.

A ​weak acid ​has a ​relatively strong conjugate

base​.

+​ + F​−​
HF​(aq) +
​ H​2​O​(l) ⇌
​ H​3​O​ (aq) ​ (aq)

- The equilibrium lies ​far to the left​. - H

​ igh tendency ​for the fluoride ion to accept a proton.
Therefore, it will be a strong conjugate base.

Rule: The ​weaker the acid​, the ​stronger the conjugate base​. (Vice versa for
weak bases)

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 11 OF 40

EXAMPLE QUESTION 1

Explain why the presence of nitrate ions in an aqueous solution will not make it basic. (i.e. will not produce
extra OH​- ​ions).

+ NO​
HNO​3(aq) ​+ H​2O​
​ (l) →
​ H​3​O​+​(aq) ​ −​
3​ (aq)

This reaction goes to ​virtual completion​. The reverse reaction does not occur to any significant
extent.
∴ NO​3​−​(aq) has
​ no tendency to accept a H​+ ​and is a neutral ion. It will not accept any H​+ ​from water to

produce OH​- ​ions. NO​3​− ​is also the conjugate base of a strong acid.

EXAMPLE QUESTION 2

Explain why an aqueous solution containing fluoride ions will be

basic.

+​ + F​−​
HF​(aq) +
​ H​2​O​(l) ⇌
​ H​3​O​ (aq) ​ (aq)

F​- ​has a relatively ​high tendency ​to accept H​+ ​as it is a ​conjugate base ​of a w
​ eak acid ​HF. It will accept H​+
from water to produce OH​- ​ions resulting in a basic solution of pH > 7.
 CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 12 OF 40

APPLYING BRONSTED LOWRY

THEORY
OUTCOMES

● write ionic equations to represent the dissociation of acids and bases in water, conjugate acid/base
pairs in solution and amphiprotic nature of some salts, for example: – sodium hydrogen carbonate –
potassium dihydrogen phosphate
NON-NEUTRAL SALT SOLUTIONS

Many ions are not neutral when dissolved in water. They will have ​acidic ​or ​basic
properties.

- This means that in neutralisation reactions, the salt product is not necessarily neutral (pH =
7). - pH depends on the ​nature of the salt.

To show that an ionic compound will form an acidic, basic or neutral

solution:

1) Write an ​equation ​showing the ​dissociation o ​ f the compound into its two ions. 2)
Determine if either ion is ​acidic ​or ​basic ​by examining their conjugates. 3) Write an
equation showing the ​acidic ​or b​ asic ​ion r​ eacting with water ​to form H​3​O+​ ​or OH​-​.

- Strong acid + Weak base → Acidic -

Strong acid + Strong base → Neutral -
Weak acid + Strong base → Basic

EXAMPLE QUESTION 1

Will a solution of potassium fluoride be acidic or

basic?

+ F​−​
KF​(aq) →
​ K​+​(aq) ​ (aq)

F​- ​is a conjugate base of a weak acid HF. Therefore, it will have a relatively high tendency to react with water
+ H​ O​ ⇌ OH​−​ + HF​ )
to form OH​- ​resulting in a basic solution of pH > 7. (F​−​(aq) ​ 2​ (l) ​ (aq) ​ (aq)​

AMPHIPROTIC SUBSTANCE

Water can be classified as both a Bronsted-Lowry acid and base. A molecule or ion that can ​accept and
donate protons ​is called ​amphiprotic​. Amphiprotic species will lose or gain a proton ​depending on the
other reactant​.

- If the other species is a stronger base, it will act as a Bronsted-Lowry

acid - If the other species is a stronger acid, it will act as a Bronsted-Lowry
base.
 ​
Examples include: HCO​3-​​ , HSO​4-​​ , H​2​PO​4-​​ , HPO​42-
​ and

NH​3

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 13 OF 40

Amphiprotic substances are a subset of ​amphoteric ​substances, which are substances that can ​react with
both acids and bases​.

- In laboratories, NaHCO​3 ​is commonly used for neutralising acid spills as it is a weak, amphoteric base
that
produces CO​2 ​during neutralisation.
o ​It is a weak base therefore neutralisation is ​not as exothermic​. ​o
Amphoteric/amphiprotic therefore will absorb OH​- ​if too much is added. ​o
Produces CO​2 ​therefore it can be seen when neutralisation is complete ​o
Solid, therefore will not contribute to the size of the spill

ACID/BASE BEHAVIOUR OF OXIDES

An ​acidic oxide ​is one which either reacts with ​water ​to form an ​acidic solution ​or reacts with ​bases ​to
form ​acidic salts​. Common acidic oxides are CO​2 ​and P​4​O​10 ​(diphosphorus pentoxide) and SO​2​.

+ HCO​ −​
CO​2(g) ​+ H​2​O​(l) ​⇌ H​2​CO​3(aq) ​⇌ H​+​(aq) ​ 3​ (aq)

CO​2(g) +
​ 2NaOH​(aq) →
​ Na​2​CO​3(aq) +
​ H​2​O​(l)

Non-metal ​from the RHS of the periodic table tend to form ​acidic oxides​. These elements
have ​high electronegativity ​and share electrons when bonding with oxygen, so non-metal
oxides are ​covalent​.

A ​basic oxide ​is one that reacts with ​water ​to form an ​alkaline solution ​or reacts with ​acids ​to form ​basic
salts​. Metals from the LHS of the periodic table tend to form basic oxides. These elements have ​low
electronegativity​, so metal oxides are ​ionic​.
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 14 OF 40

PH SCALE
OUTCOMES
● calculate pH, pOH, hydrogen ion concentration ([H​+​]) and hydroxide ion concentration ([OH​–​])
for a range of solutions (ACSCH102)
● calculate and apply the dissociation constant (​K​a​) and ​pK​a ​(​pKa​ =
​ -log​10 (​ Ka
​ ​)​) to determine the
difference between strong and weak acids (ACSCH098)
PH AND H​+ ​CONNECTION
+​ -​
​ ​ ] = [OH​ ])
- pH 7 is neutral at 25°C ([H​3O
The pH (potential of hydrogen) scale is ​logarithmic ​(base 10), not linear. ​Significant figures
for logs are those ​after the decimal point​.
- pH = −log​10​[H​+​] - [H​+​] = 10​−pH
PH OF STRONG AND WEAK ACIDS
pH can deduce the ​relative strength ​and c​ oncentration ​of different acidic solutions.
- ↑ Acid strength → ↑ Degree of ionisation → ↑ [H​+​] → ↓ pH - ↑ [Acid] → ↑ [H​+​] → ↓ pH - Acid
strength and concentration both affect the pH of a solution.
 For a ​monoprotic strong acid​, the concentration of H​+ ​is the same as the ​concentration of
the acid ​(HX → H​+ ​+ X​−​)
For ​weak acids​, the concentration of H​+ ​will depend on its strength and ​concentration ​of the
acid solution.
HA ⇌ H​+ ​+ A​− ​Where K​a = [H​+​ −​
​ ​ ][A​ ]
[HA]
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 15 OF 40
POH OF STRONG AND WEAK BASES

pOH ​is a measure of ​OH​- ​concentration ​that is similar to

pH.

- pOH = −log​10​[OH​−​] -
[OH​−​] = 10​−pOH

Strong bases ​are Group 1 and 2 hydroxides. The concentration of hydroxide ions depends on the
number of hydroxide ions ​in the formula.

For ​weak bases​, the concentration of OH​- ​will depend on its strength and the concentration of the base
solution.

AUTOIONISATION OF WATER

The concentration of ​H+​ ​and ​OH​- ​in any aqueous solution are ​directly related​. This is because water is a
very weak acid ​which forms the following ​exothermic ​equilibrium reaction.

- The equilibrium constant for this equilibrium is called the ​ionisation constant for
water​.

+​ −​ −14 ​
K​w =
​ [H​3​O​ ][OH​ ] = 1.0 × 10​ at 25°C

pK​w =
​ pH + pOH

pH + pOH = 14

pH = 14 + log​10​[OH​−​]
PK​A ​AND PK​B

Since K​a ​values are usually very small, ​pK​a ​values ​are often cited
instead:

pK​a =
​ −log​10 K​
​ a

−pK​
K​a =
​ 10​ a

↑ Strong acid → ↑ K​a ​→ ↓pK​a

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 16 OF 40

PH CALCULATIONS
OUTCOMES
● calculate pH, pOH, hydrogen ion concentration ([H​+​]) and hydroxide ion concentration ([OH​–​])
for a range of solutions (ACSCH102)
EXAMPLE QUESTION 1
Benzoic acid, a food preservative, is a weak monoprotic acid. The pH of 0.50M benzoic acid
solution is 2.25. What is the K​a ​of benzoic acid?
+ A​−​
HA​(aq) ​⇌ H​+​(aq) ​ (aq)

[H​+​] = 10​−pH ​= 10​−2.25 ​= 5.62341325 × 10​−3 ​mol/L

HA H​+ ​A​− ​Mole Ratio 1 1 1 [Initial] 0.50 0 0 [Change] −10​−2.25 ​+10​−2.25 ​+10​−2.25 ​[Final] 0.50 −
10​−2.25 ​10​−2.25 ​10​−2.25
[H​+​ −​
​ ​
K​a = ][A​ ]
= (10​−2.25​
[HA] ​ )(10​−2.25​)
= 6.4 × 10​−5 ​
0.50 − 10​−2.25 ​ (2 s.f)
EXAMPLE QUESTION 2
Acetic acid has a K​a ​of 1.8 x 10​-5​. Calculate the pH of a 0.20M solution of acetic acid.
+ H​+​
CH​3​COOH​(aq) ​⇌ CH​3​COO​−​(aq) ​ (aq)

−​ H​+​
CH​3​COOH​(aq) ​CH​3COO​
​ (aq) ​ (aq) ​Mole Ratio 1 1 1 [Initial] 0.20 0 0 [Change] −x +x +x [Final]
0.20 − x x x
[CH​ COO​−​ +​
​ ​
K​a = 3​ ][H​ ]
= (x)(x)
[CH​3​COOH] ​
= 1.8 × 10​−5
(0.20 − x) ​
Assume 0.20 − x ≈ 0.20
= 1.8 × 10​−5
(x)(x) (0.20) ​
x = 1.879736660 × 10​−3
= 0.96% Therefore, assumption is valid
x 0.20−x ​

pH = −log​10​[H​+​] = −log​10​[x] = 2.72 (2 s.f)

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 17 OF 40
DEGREE OF IONISATION
All acids ionise in water, the degree of which is different for individual acids.
To calculate the ​percentage ​of any component in a sample, the formula is:
component
percentage (%) = ​
× 100
total ​
FOR A WEAK ACID HA

HA​(aq) ​⇋ H​+​(aq) ​+ A​−​(aq)

The percentage ​ionised ​(degree of ionisation):
[H​
% ionised = ​ +​]​eqm
[A​−​
​ 100 = ​
[HA]​initial × ]​eqm
[HA]​initial ×
​ 100
The percentage ​unionised ​(percentage of ​intact molecules​):
[HA]​
% unionised = ​ eqm

[HA]​initial ×
​ 100 = 100 − % ionised
PH MEASUREMENTS
PH PROBE
A ​pH probe ​or ​pH meter ​can be used to measure pH.
- Advantages: Precision, non-destructive - Disadvantages: Initial costs, requires calibration
before use
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 18 OF 40

PH OF MIXED SOLUTIONS
OUTCOMES
● calculate the pH of the resultant solution when solutions of acids and/or bases are diluted or
mixed
DILUTION CALCULATIONS
The ​total moles of solute ​in a concentrated solution and the diluted solution are ​the same​.
- c​1​V​1 =
​ c​2​V​2
EXAMPLE QUESTION 1
Calculate pH when 1.0 mL of 1.0M HCl is diluted to 1.25L.
c​1​V​1 = ​ c​2​V​2
(0.001)(1.0)
c​2 ​= ​
= 0.0008 mol/L
1.25 ​
[HCl] = [H​+​] = 0.0008 M
pH = −log[H​+​] = −log(0.0008) = 3.10 (2 s.f)
PH OF SOLUTIONS AFTER MIXING
EXAMPLE QUESTION 2
Calculate the pH of the resultant solutions when 50.0 mL of 0.020 M NaOH solution and 100
mL of 0.012 M Ba(OH)​2
n(NaOH) = (0.050)(0.020) = 0.001 moles
n(OH​−​) = n(NaOH) = 0.001 moles
n(Ba(OH)​2​) = (0.100)(0.012) = 0.0012 moles
n(OH​−​) = 2 × n(Ba(OH)​2​) = 2 × 0.0012 = 0.0024 moles

n(OH​Total ​− ​) = 0.0024 + 0.001 = 0.0034 moles

V = 50.0 + 100 = 150 mL = 0.150 L
0.0034
[OH​−​] = ​
= 0.0226667 mol/L
0.150 ​
pH = 14 + log[OH​−​] = 12.36 (2 s.f)
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 19 OF 40
PH AFTER NEUTRALISATION
When a strong acid and strong base react and undergo a neutralisation reaction, the pH of the
final solution will depend on the ​concentration o
​ f the ​reactant in excess​.
EXAMPLE QUESTION 1
Calculate the pH of the resultant solution when 35.0mL of 0.250M HCl and 45.0mL of 0.350M
NaOH are mixed.

HCl​(aq) ​+ NaOH​(aq) ​→ NaCl​(aq) +

​ H​2​O​(l)
 n(HCl) = 0.250 × 0.035 = 0.00875 mol
n(NaOH) = 0.350 × 0.045 = 0.01575 mol
Therefore, HCl is the limiting reagent and NaOH will be in excess. pH > 7 & NaCl is a neutral
salt.
n(NaOH left over) = 0.01575 − 0.00875 = 0.007 mol
0.007
[NaOH] = ​
= 0.0875 M = [OH​−​
0.08 ​ ]
pH = 14 + log​10​[0.0875] = 12.942
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 20 OF 40

BUFFER
S
OUTCOMES
● describe the importance of buffers in natural systems (ACSCH098,
ACSCH102)

HOW DO BUFFERS WORK?

A buffer solution is a solution that can ​resist pH change ​when small amounts of an acid or base are added.
In order for it to work, it must be able to ​compensate ​for the addition of either of an acid or base, otherwise
the pH will change significantly.

Buffers are commonly made by mixing a ​weak acid ​and its ​conjugate base ​(or vice versa) typically in
equimolar ​amounts of each.

- For example, a buffer solution containing CH​3​COOH and CH​3​COO​− ​(in the form of
NaCH​3​COO) - The mixture exists in ​equilibrium​, so all of the species in the equation are
present.

CH​3​COOH​(aq) +
​ H​2​O​(l) ⇌
​ CH​3​COO​(aq) ​− ​+ H​3O​
​ (aq) +
​

When a small amount of ​acid ​is added, the concentration of H​3​O+​

increases.

- When HCl is added to the buffer solution, ↑ [H​3​O+​​ ] which is a disturbance - It will shift
to minimise the disturbance by shifting to the LHS and forming the products. - Role of
conjugate base is to ​react with excess H​3​O+​​ . ​It ‘absorbs’ the additional H​3​O+​
When a small amount of ​base ​is added, the situation is slightly more
complicated.

- There are two acids that could react with the base CH​3​COOH and H​3​O​+ ​- Because the concentration of
H​3​O​+ ​is far lower than the concentration of CH​3​COOH, the majority of OH​−
will react with CH​3​COOH​, ​producing ​water ​and CH​3​COO​− ​- Thus the concentration of
H​3​O​+​does not change significantly​, and the pH stays ​relatively constant​.

It can also be explained when H​3​O​+ ​and OH​− ​react, causing equilibrium to shift to right to minimise the
disturbance

H​3​O​(aq) ​+ ​+ OH​(aq) −​ ​⇌ 2H​2​O​(l)

BUFFER CAPACITY

The ​effectiveness ​of a buffer is known as ​buffer

capacity​.

- It is defined as the moles of H​3​O​+ ​or OH​− ​necessary to ​change the pH ​of the buffer solution by ​one
unit ​- Buffer capacity depends on both the ​pH ​of the buffer and the ​total concentration ​of the weak
acid and
conjugate base (or vice versa)

A buffer is most effective when the ​amounts of weak acid ​and ​conjugate base ​present are ​similar
(equimolar).

- When pH = pK​a​, the concentrations of weak acid and conjugate base are equal. - Therefore, a buffer
solution is most effective when the ​pH is within 1 unit of its pK​a​. ​- When the pH is too high, there is
not enough acid to react with the added OH​−​. When the pH is too low,
there is not enough conjugate base to react with any
H​3​O​+​.

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 21 OF 40

 Name Formulae pK​a ​Effective pH
Range

Acetic acid / Acetate CH​3​COOH​(aq) +

​ H​2​O​(l) ⇌
​ CH​3​COO​(aq) −
​ ​+ H​3O​ ​ ​4.76 3.6 − 5.6
​ (aq) +

Ammonium / Ammonia NH​3(aq) +

​ H​2​O​(l) ⇌ ​ (aq) +
​ NH​4+​ ​ OH​(aq) −
​ ​9.25 8.8 − 9.9

Carbonic acid / O​3​−​(aq) +

​ OH​(aq) ​− ​10.33 9.5 − 11.1

Hydrogen carbonate

2​O​(l) ​⇌
ihydrogen phosphate /
HCO​3−​​ (aq) +
​ H​3​O​(aq) ​+ ​6.35 6.0 − 8.0
Hydrogen phosphate

Hydrogen carbonate / O​4​−2​(aq) ​+ OH​(aq) −​ ​7.20 5.8 − 8.0

Carbonate
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 22 OF 40

TITRATION CALCULATIONS
OUTCOMES
● conduct practical investigations to analyse the concentration of an unknown acid or base by
titration
DIRECT TITRATION CALCULATIONS
The steps for a titration calculation are:
1) Write a balanced chemical equation for the reaction 2) Calculate the number of moles of
Reactant A (of known concentration) in the volume used 3) Using the number of moles of A and
the mole ratio in the equation, calculate the number of moles of
Reactant B (unknown concentration) used. 4) Calculate the concentration of reactant B.
For ​neutralisation ​reactions, the ​strength of the acid is irrelevant ​as the base is stronger
than water. All of the protons in a ​polyprotic ​acid will be irreversibly removed by the base.
EXAMPLE QUESTION 1
Alex wanted to analyse a solution of NaOH. She first prepared 250 mL of a standard solution
using 4.72 g of solid sodium carbonate. She then reacted 25.0 mL of HCl of unknown
concentration with the standard solution. The following volumes of standard solution were
required:
Trial ​1 2 3 4 ​Volume (mL) ​31.50 29.85 29.75 29.80
25.0 mL of the HCl solution was then titrated against the NaOH solution. The average volume
of NaOH required to reach the equivalence point was 30.85 mL.

Na​2​CO​3(aq) ​+ 2HCl​(aq) ​→ 2NaCl​(aq) +

​ CO​2(g) ​+ H​2O​
​ (l)
4.72
n(Na​2​CO​3​) = ​
= 0.0453250307 mol
105.99 ​
n(Na​ CO​ )
[Na​2​CO​3​] = ​ 2​ 3​

= 0.0453250307
0.250 ​
= 0.1781300123 M
0.250 ​
Average Na​2​CO​3 used
​ = 29.8 mL

HCl​(aq) ​+ NaOH​(aq) ​→ NaCl​(aq) +

​ H​2​O​(l)
n(Na​2​CO​3​) = 0.1781300123 × 0.0298 = 0.00530827436 mol
n(HCl) = 2 × n(Na​2​CO​3​) = 0.01061654873 mol
n(NaOH) = n(HCl) = 0.01061654873 mol
n(NaOH)
[NaOH] = ​
= 0.01061654873
0.03085 ​
= 0.344 M
0.03085 ​
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 23 OF 40
DILUTION – TITRATION CALCULATIONS
When analysing a substance, the concentration may be too high for a direct titration experiment
tom be efficiently carried out. Instead, the substance would be ​diluted ​by a known amount, and
then the diluted solution would be ​titrated​.
WORKED EXAMPLE 1
21.55 mL of a hair dye product containing ammonia was diluted to 250.0 mL. 20.0 mL aliquots
of the diluted dye were titrated against 0.048 M sulfuric acid. The average titre was 18.35 mL.
The density of the hair product was measured to be 1.1 g/mL.
Calculate the percentage by weight of ammonia in the hair dye.

2NH​3(aq) ​+ H​2SO​
​ 4(aq) ​→ (NH​4)​​ 2​SO​4(aq)

n(H​2​SO​4​) = 0.048 × 0.01835 = 0.0008808 mol

n(NH​3​) = 2 × n(H​2​SO​4​) = 0.0017616 mol
n(NH​ )
[NH​3​] = ​ 3​

= 0.0017616
0.020 ​
= 0.08808 M
0.020 ​
n(NH​3​) = 0.08808 × 0.250 = 0.02202 mol
m(NH​3​) = 0.02202 × 17.034 = 0.37508868 g
Mass of hair dye = 21.55 × 1.1 = 23.705g
w​ = m(NH​ )
%​ w ​ 3​

= 0.37508868
23.705 ​
= 1.6%
23.705 ​
BACK TITRATION CALCULATIONS
A back titration, or indirect titration, is a ​two-stage ​analysis:
- Reactant A (of unknown concentration) is reacted with ​an excess ​of Reactant B (of known
concentration and
volume). - A titration is the performed on the excess Reactant B by determining the moles of
Reactant C required to
neutralise the excess.
Summary:
1) Sample is reacted with known excess of reagent. (e.g. known amount of a particular acid) 2)
Leftover excess is added 3) Excess is titrated to find moles of reagent reacted with solution.
Back titrations are generally used when:
- One of the reactants is ​volatile (​ e.g. ammonia) - An acid or base is an ​insoluble salt ​(e.g.
calcium carbonate) - Direct titration would involve ​weak acid/weak base ​titration (making it
difficult to determine the
equivalence point).
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 24 OF 40
EXAMPLE QUESTION 1
A student wanted to determine the calcium carbonate present in a 0.250 g sample of chalk. The
student placed the chalk sample in a 250 mL conical flask and pipetted 50.00 mL of 0.100 M
sulfuric acid into the flask. The excess acid was titrated with 0.340 M sodium hydroxide. The
results for the volume of sodium hydroxide required are tabulated below:
Trial ​1 2 3 4 ​Volume NaOH (mL) ​23.40 21.95 22.10 21.90
Calculate the mass percentage of calcium carbonate in the chalk sample.

H​2​SO​4(aq) ​+ CaCO​3(aq) →
​ CaSO​4(aq) ​+ CO​2(g) ​+ H​2O​
​ (l)

H​2​SO​4(aq) ​+ 2NaOH​(aq) ​→ Na​2SO​

​ 4(aq) ​+ 2H​2O​
​ (l)
Average v(NaOH) = 21.9833 mL
n(NaOH) = 0.0219833 × 0.340 = 0.00747433 mol
n(H​2​SO​4 reacted
​ with NaOH) = 0.5 × n(NaOH) = 0.0037371666 mol
n(H​2​SO​4 initial)
​ = 0.050 × 0.100 = 0.005 mol
n(H​2​SO​4 reacted
​ with CaCO​3​) = 0.005 − 0.003737166 = 0.0012628333 mol
n(CaCO​3​) = n(H​2​SO​4 reacted
​ with NaOH) = 0.0037371666 mol
m(CaCO​3​) = 100.94 × 0.0037371666 = 0.1263969883 g
w​ = 0.1263969883
%​ w ​
= 50.558795% = 50.6% (3 s.f)
0.250 ​
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 25 OF 40
EXAMPLE QUESTION 2
A student was asked to determine the concentration of ammonia in a commercial sample of
“cloudy ammonia cleaning solution”. The student first pipetted 25.00 mL into a 250 mL
volumetric flask and filled it to the mark with distilled water. She then transferred a 25.00 mL
aliquot to a clean conical flask, and added exactly 40.00 mL of 0.100 M HCl. She then titrated
the excess HCl with 0.050 M sodium carbonate. 21.30 mL of sodium carbonate solution was
required.

2HCl​(aq) ​+ Na​2CO​
​ ​ CO​2(aq) ​+ H​2O​
3(aq) ​→ 2NaCl​(aq) + ​ (l)

n(Na​2​CO​3​) = 0.01230 × 0.050 = 0.0010615 mol

n(HCl reacted) = 2 × n(Na​2​CO​3​) = 0.00213 mol
 n(HCl initial) = 0.040 × 0.100 = 0.004 mol

HCl​(aq) ​+ NH​3(aq) ​→ NH​4Cl​

​ (aq)

n(HCl reacted with NH​3​) = 0.004 − 0.00213 = 0.00187 mol

n(NH​3​) = n(HCl) = 0.00187 mol
0.00187
[NH​3​] = ​
= 0.0748 M
0.025 ​
0.025 × C​1 ​= 0.250 × 0.0748
C​1 =
​ 0.748 M = 0.75 M (2 s.f)
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 26 OF 40

TITRATIO
N
OUTCOMES
● conduct practical investigations to analyse the concentration of an unknown acid or base by
titration

TITRATION TERMINOLOGY

Term Definition

Titration Volumetric analytical technique used for determining the concentration of a solution, when
the concentration of the other reacting solution is known and volumes of the 2 solutions
are accurately measured.

Aliquot An accurately known volume of liquid. In titration this usually refers to the liquid transferred
via ​pipette ​into the ​conical
flask​.

Analyte A substance being analysed. This is usually a solution of ​unknown concentration​.

Back Titration A two-stage analysis in which an excess of reactant is added to the analyte, then the
excess is
determined to calculate the concentration of the
analyte.

Burette A graduated piece of glassware which dispenses measured amounts of the solution (the
 titrant).

Endpoint The point in titration when the indicator permanently changes colour.

Equimolar Same concentration.

Equivalence Point The point in a neutralisation reaction when the amounts of reactants are just
sufficient to
consume both reactants, without an excess of either. (i.e. in stoichiometric
ratio)

Pipette A piece of glassware used to transfer a very accurately measured volume of solution.

Primary standard A substance of sufficiently high purity and stability that a solution of accurately
known
concentration can be prepared by weighing out the desired mass, dissolving in water
and making the volume up to a known value.

Titrand The solution to which another reagent (titrant) is added during titration (usually in the conical
flask)

Titrant The solution that is added during a titration (usually from a burette)

Titre The volume of titrant used in a titration

Volumetric flask A piece of glassware which can hold a set volume of solution very
accurately

TYPES OF ANALYSIS

- Qualitative analysis: Involves ​observations only ​- Quantitative

analysis: Involves ​measurements ​(mass, volume etc.)
o ​Volumetric analysis: involves measurements of ​volume ​o
Gravimetric analysis: involves measurements of ​mass/weight

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 27 OF 40

GENERAL TITRATION PROCEDURE

In a titration experiment, the ​number of moles ​of a target material (the ​analyte​) is determined. This can
then be used to calculate the ​concentration​.
A measured volume of the solution of unknown concentration, the ​analyte​, is usually placed in a
conical flask (​titrand​) with a ​burette ​containing the t​ itrant ​above it.

A ​burette ​is a piece of volumetric glassware. It is a long tube with a tap at one end so measured volumes
of titrant can be accurately added to the titrand.

Before the experiment begins, an ​indicator ​will normally also be added to the conical flask to
determine the approximate equivalence point.

To perform the experiment the titrant is slowly added and stepwise to the conical flask, with swirling,
until the indicator undergoes a ​permanent colour change ​(the ​end point​).

Acid-base titrations are the most common titrations:

- An acid and a base are reacted in a neutralisation reaction during the titration. - A suitable
acid-base indicator ​is added to show when the reaction is just complete. However, indicators change
colour over a range of pH, making it difficult to ​accurately determine the equivalence point​. - For
greater ​accuracy​, a ​pH meter ​can be used.

The ​pH changes rapidly ​towards the end point of the titration and it is easy to add too much titrant. The
titrant must be added very carefully, in ​small volumes ​close to the end to successfully determine the exact
amount required for complete reaction.
 CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 28 OF 40
DETAILED TITRATION PROCEDURE

For titrating HCl against NaOH. HCl is placed into the conical flask and NaOH in the
burette.

PREPARING THE TITRAND (IN THE CONICAL

FLASK)

- Rinse the inside of the pipette with a small with a small amount of HCl solution 3 times. - Use a pipette
filler to fill the pipette with HCl until the bottom of the meniscus rests on the calibration line. - Hold the
pipette so that its tip is resting against the inside of a clean conical flask. Let the solution run out. - Once
the liquid level has stabilised, leave the pipette tip touching the flask for a few seconds before
removing. (The pipette is calibrated to deliver the correct volume when a small amount of liquid remains
in the tip – do not shake it into the flask). - Use a wash bottle containing distilled water to wash any
solution that might be on the inside wall to the
bottom of the conical flask.

PREPARING THE TITRANT (IN THE

BURETTE)

- Rinse the inside of the burette with a small amount of NaOH solution 3 times, including through the
tap. - Clamp the burette vertically - Pour NaOH solution into the burette

TITRATION

- Add a few drops of indicator into the conical flask and swirl gently. -
Record the initial burette reading - Place the conical flask under the
burette - Add NaOH to the conical flask until a permanent colour
change occurs - Record the final burette reading - Repeat the
experiment 3 times with fresh aliquots of HCl.

WASHING
Burette and pipette: Used to deliver the solutions used in the titration. Final rinsing with ​the solution
to be delivered​.

Conical flask: Used to hold the aliquot or titrand. Final rinsing with ​distilled
water​.

The washing procedure affects the accuracy of the calculated

concentration.

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 29 OF 40

TITRATION TECHNIQUE
RINSING
It is important to ​rinse ​each piece of ​glassware ​with the ​appropriate solution ​after cleaning
with distilled water and immediately prior to use.
The solution that is to be transferred using a ​pipette ​is of accurately known concentration, or its
concentration is to be accurately determined. If droplets of distilled water are present in the
pipette, it will dilute the reagent being delivered.
- Rinse ​burette ​and ​pipette ​with solutions - Rinse ​conical flask ​and ​volumetric flask ​with
distilled water
VOLUMETRIC ERRORS
All glassware in titration is calibrated to be accurate when measurements are taken at the
bottom of the meniscus​.
Any ​air bubbles ​in the liquid must be removed for volumes to be accurate.
PIPETTE CALBIRATION
The pipettes used in titration are calibrated to ​deliver the specified volume ​of solution with no
additional force.
- They are marked TD (to deliver) or EX (to expel) - This means that there should be a ​small
volume of liquid left in the tip ​of the pipette after the aliquot has
been accurately transferred. This should not be shaken out into the conical flask.
DEVIATION
 Accessing accuracy – How close you are to the accepted value
% deviation = |experimental
​ value−accepted value|

accepted value
CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 30 OF 40
STANDARD SOLUTION

A standard solution is a solution containing a precisely known concentration of a substance. They can be
categorised as ​primary ​or ​secondary​.

A ​primary standard ​is produced when a substance of high purity dissolved in a known volume of
solvent.

1) Accurately ​weigh ​out a mass of solid close to the required mass in a beaker. Record the actual
mass
weighed. 2) Add enough distilled water to dissolve the solid. 3) Carefully transfer all the
weighed mass to a clean volumetric flask of the approximate size, using a wash
bottle and funnel. All the equipment that came into contact with weighed mass should be ​rinsed ​into the
flask. 4) Add distilled water until the ​bottom of the meniscus is resting on the line ​on the neck of the
flask. Add the
last few drops with a dropper. 5) Stopper the flask. Firmly holding the stopper in place,
invert ​several times to ensure the solution is
homogeneous​. 6) Label the flask with the exact concentration,
solution, date and name.

A substance suitable for preparing a ​primary standard solution ​should have the following
features:

- High purity - Unaffected by exposure to air -

Non-hygroscopic (does not absorb water from air) - Have a
large molecular mass to reduce percentage errors - Be a
solid for easier weighing - Cheap and readily available -
Have a high water solubility

A ​secondary standard ​is produced when its concentration is determined via

stoichiometry.

- The process of producing a secondary standard is called

standardisation

EQUIVALENCE POINT
The ​equivalence point ​of a titration is the point at which the amount moles of acid and bases added
match the stoichiometric ratio​.

- It is the point at which reaction is complete, with ​no excess reactant ​- The ​pH ​of the solution
at the equivalence point determines the ​appropriate indicator ​to be used.

PH OF THE EQUIVALENCE POINT

As the pH of water is neutral, the pH of the equivalence point will depend entirely on the ​salt ​produced:
whether it is acidic, basic or neutral.

If an ​acidic or basic salt ​is produced by the neutralisation reaction in a titration experiment, the
equivalence point will not be neutral.

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 31 OF 40

- Neutral salts are formed when ​strong acids ​react with ​strong
bases​. - Acidic salts are formed when ​strong acids r​ eact with ​weak
bases​. - Basic salts are formed when ​weak acids ​react with ​strong
bases​.

Note: When ​strong acids ​react with ​metal carbonates ​(weak bases), the neutral salt is formed, but the
resulting solution is still ​acidic​. This is because the carbon dioxide dissolves in water to produce an acidic
solution.

INDICATOR SELECTION

Indicators can be used to find the approximate equivalence point of a

titration.

- The ​equivalence point ​is when exactly ​enough moles ​of ​titrant ​have been added to react with
all the
titrand​. - The ​end point ​is when the indicator first undergoes a ​permanent colour change.
- An indicator should be selected so that the ​end point ​is as ​close as possible ​to the equivalence
point.
(Systematic error. Will impact validity and
accuracy)
 Indicator Colour at lower pH Colour at higher pH pH of colour change range

Methyl orange ​Red Yellow 3.1 – 4.4

Bromothymol blue ​Yellow Blue 6.0 – 7.6

Phenolphthalein ​Colourless Pink 8.3 – 10.0

Methyl red Red Yellow 4.8 – 6.0

Litmus Red Blue 4.5 – 8.3

Phenol red Yellow Red 6.8 – 8.4

BROMOTHYMOL BLUE

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 32 OF 40

PHENOLPHTHALEIN
METHYL ORANGE

EXAMPLE QUESTION 1

Explain why 0.20 M acetic acid and 0.20 M hydrochloric acid require the same volume of sodium hydroxide
solution to reach equivalence point, but the pH values at their equivalence points are different.

CH​3​COOH​(aq) +
​ NaOH​(aq) ​→ CH​3​COONa​(aq) ​+ H​2​O​(l)
 HCl​(aq) + ​ H​2​O​(l)
​ NaOH​(aq) ​→ NaCl​(aq) +

CH​3​COO​(aq) −​ ​+ H​2O​
​ (l) ​⇌ CH​3COOH​
​ (aq) ​+ OH​(aq) −
​

Both acetic acid and hydrochloric acid are monoprotic acids that reacts to completion when reacted with a
strong base. As the concentration are the same, the same amount is needed to neutralise the strong base,
NaOH. CH​3​COO​− ​is the conjugate base of a weak acid and will react with water to produce a basic solution.
Therefore, resulting in a pH > 7. Cl​− ​is the conjugate base of a strong acid and will not react hence the
solution remains pH = 7.

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 33 OF 40

APPLICATION OF
TITRATION
STRONG ACID-STRONG BASE TITRATION

The equivalence point is located at the ​most vertical point ​(point of inflection). All three common indicators
for titration are suitable for determining the equivalence point for a strong acid-strong base. This is because
there is a large rapid change in pH near the equivalence point so all of the indicator would change colour
when the same volume of based is added, therefore it is not critical which indicator is used.
WEAK ACID-STRONG BASE TITRATION

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 34 OF 40

STRONG ACID-WEAK BASE TITRATION
WEAK ACID-WEAK BASE TITRATION

Never use indicators for weak acid and weak

base.
 CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 35 OF 40
OUTCOME
● investigate titration curves and conductivity graphs to analyse data to indicate characteristic reaction
profiles, for example: – strong acid/strong base – strong acid/weak base – weak acid/strong base
(ACSCH080, ACSCH102)

CONDUCTIVITY GRAPHS

During a titration, the conductivity of the solution changes. The equivalence point may be located by
plotting the conductance as a function of the volume of titrant added.

The electrical conductivity of a solution depends

on:

- The ​concentration ​ions present -

The ​mobility ​of the ions present
o ​More mobile ions, the more conductive it is ​o ​H+​
 and OH​- ​are highly mobile - H​+ ions
​
are more
-​
conductive than OH​ ions

Conductometric titrations are useful for titrations of coloured solutions, analysis of dilute solutions, and
when reversible reactions are used (e.g. weak acid-weak base titration).

General rule:

- Strong → Linear -
Weak → Curved

STRONG ACID + STRONG BASE

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 36 OF 40

WEAK ACID + STRONG BASE
 1) Conductivity is initially low as acetic acid is a ​weak acid ​and only ​partially ionises in
water​. 2) [Not shown on the graph] As the base is initially added, conductivity decreases
o ​H+​ ​is replaced by Na​+ ​which is less conductive ​o ​The presence of the newly formed acetate
ions also decreases the ionisation of acetic acid due to

the common ion effect. ​o ​CH​3​COOH​(aq) ​+ NaOH​(aq) ​→ CH​3COONa​

​ (aq) ​⇌

CH​3​COO​(aq) ​− ​+ Na​(aq) ​+
-​
▪ The initial production of the CH​3C
​ OO​ ions results in the suppression of the CH​3​COOH ionisation

due to the common ion effect. 3) Conductivity then increases are more Na​+ ​and CH​3​COO​- ​are
produced.
o ​There is a ​minimal change ​in pH due to the buffer region. The mixture of
-​
CH​3​COO​ /CH​3​COOH 4) Reaches the equivalence point 5) Conductivity ​increases more rapidly ​as
Na​+ ​and highly conducting OH​- ​are added. (Excess strong base)

Initially, the conductance is low due to the low ionisation of the weak acid. On the addition of the strong base,
there is a decrease in conductance due to the replacement of the H​+ ​by Na​+ but
​
also supresses the
dissociation of the acetic acid due to the common ion acetate.

The conductance increases on adding NaOH as it neutralises the undissociated CH​3​COOH to NaCH​3​COO
which is a strong electrolyte. Conductivity increases due to the highly conductive OH​- ​ions.
 CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 37 OF 40
STRONG ACID + WEAK BASE

HCl​(aq) +
​ NH​3(aq) ​→ NH​4Cl​
​ (aq)

NH​4​+​(aq) ​+ H​2​O​(l) ⇌​ NH​3(aq) +

​ H​3O​
​ (aq) +
​

Before the equivalence point, conductivity ​decreases ​like in the strong acid-strong base
graph.

After the equivalence point, the graph is ​almost horizontal ​as the excess weak base is not significantly
ionised due to the presence of its conjugate acid.
Initially, the conductance is high due to the strong acid. The conductance decreases due to the replacement
of H​+​. After the equivalence point has been reached in the graph becomes almost horizontal, since the
excess weak base (aqueous ammonia) is not easily ionised in the presence of the salt.

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 38 OF 40

WEAK ACID + WEAK BASE

[Not shown on the graph]

 1) CH​3​COOH is a weak acid and therefore only partially ionise. 2) [H​+​] gets used up.
CH​3​COO​- ​gets produced which supresses the ionisation of CH​3​COOH. 3) Production
of more ions 4) Equivalence point 5) Excess NH​3 ​is suppressed due to the common
ion effect

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 39 OF 40

OUTCOMES
● conduct a chemical analysis of a common household substance for its acidity or basicity (ACSCH080) ,
for example: – soft drink – wine – juice – medicine

ANALYSIS OF COMMON HOUSEHOLD

SUBSTANCES

Substance Major Acidic or Basic Species

Soft Drink Carbonic acid, phosphoric acid

Wine Tartaric acid

 Orange juice Citric acid

Aspirin Acetylsalicylic acid

Hair dye Ammonia

Vinegar Acetic acid

Antacids Metal hydroxides and carbonates

Chalk Calcium carbonate

The exact procedures will vary depending on the nature of the substance to be
analysed:

- ​Indicators ​may not be suitable for ​intensely coloured

substances - ​Insoluble ​solids may need to be dissolved before
titration - Many substances will require ​dilution ​before titration.

OUTCOMES
● explore acid/base analysis techniques that are applied:
– in industries – by Aboriginal and Torres Strait Islander
Peoples

USE IN THE WIDER WORLD

Industry Aboriginal and Torres Strait Islander

Analysis of contents of wine. (Ethanoic acid) Big face plants (carpobrotus)

Determining the strength of antacids

Analysis of juice/fruits (Vitamin C)

CHEMISTRY MODULE 6: ACID/BASE REACTIONS PAGE 40 OF 40