2020 CHE Chemistry Notes Module 5 6 1 30

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 E Q )
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 Keq) for homogeneous reactions occurring in solution (ACSCH079,
ACSCH096)
● perform calculations to find the value of Keq 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 Keq (ACSCH093)
● conduct an investigation to determine Keq of a chemical equilibrium system, for example:
– Keq of the iron(III) thiocyanate equilibrium (ACSCH096)
● explore the use of Keq for 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 Ksp and calculate the solubility of an ionic
substance from its Ksp value
● predict the formation of a precipitate given the standard reference values for Ksp

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 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
- 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 < 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 , therefore Δ𝐻 is negative and heat energy released by the system (exothermic).
- 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 > 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 , therefore Δ𝐻 is positive and heat energy absorbed by the system (endothermic).
ENERGY PROFILE DIAGRAMS
HESS’S LAW OF HEAT SUMMATION
‘The total enthalpy change in a chemical reaction is constant, whether the reaction is performed in one step or
several steps.’
Hess’s law is a form of the law of conversation of energy (First law of Thermodynamics).

BOND ENERGIES
Bond energy (or bond enthalpy) is the amount of energy required to break one mole of a bond in a gaseous
molecule.
∆𝐻𝑟𝑥𝑛 = ∑ ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛 + ∑ ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑
∆𝐻𝑟𝑥𝑛 = ∑ ∆𝐻𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑ ∆𝐻𝑏𝑜𝑛𝑑 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.
Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + Δ𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 > 0
CALCULATING ENTROPY IN CHEMICAL REACTIONS
Δ𝑆𝑟𝑥𝑛 = ∑ Δ𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ Δ𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
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.

Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + Δ𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 > 0
−Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚
Δ𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 =
𝑇
−Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚
Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 − >0
𝑇
−𝑇Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 < 0
Josiah Willard Gibbs redefined the quantity −𝑇Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 as free energy or Gibbs Free Energy, 𝚫𝑮.
Δ𝐺𝑠𝑦𝑠𝑡𝑒𝑚 = Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚
The equation allows the comparison between the relative contributions of the two driving forces for a reaction,
entropy and enthalpy.
- If 𝚫𝑮 < 𝟎 (Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 < 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 ), a reaction is spontaneous

- If 𝚫𝑮 > 𝟎 (Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 > 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 ), 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 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
𝑞
∆𝐻𝐶𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = −
𝑛
𝑞
∆𝐻𝑆𝑜𝑙𝑛 = −
𝑛
∆𝐻𝑟𝑥𝑛 = ∑ ∆𝐻𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑ ∆𝐻𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Δ𝑆𝑟𝑥𝑛 = ∑ Δ𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ Δ𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Δ𝐺𝑠𝑦𝑠𝑡𝑒𝑚 = Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚

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 macroscopic 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

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

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.
6CO2(g) + 6H2O(l) → C6H12O6(s) + 6O2(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
N2(g) + 3H2(g) ⇋ 2NH3(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.

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:
● 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 Ea.
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.

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.

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:
“If a system at dynamic equilibrium is disturbed by changing the conditions, the system undergoes a reaction which
minimises the effect of the disturbance to attain a new equilibrium”
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
N2(g) + 3H2(g) ⇋ 2NH3(g) ∆𝐻 = −92𝑘𝐽 𝑚𝑜𝑙 −1
ADDING A REACTION COMPONENT
Addition of H2(g) increases [H2(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 N2(g) decreases [N2(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

Boyle’s Law states that pressure and volume 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 endothermic.
N2(g) + 3H2(g) ⇋ 2NH3(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 appear indicating the
2 4
formation of nitrogen dioxide (NO ). The intensity of the brown colour indicates the amount of nitrogen dioxide
2
present in the vessel. The dimerization of nitrogen dioxide is an exothermic process

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”

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

Concentrations are flat Nothing, at equilibrium

EQUILIBRIUM CONSTANT
OUTCOMES
● deduce the equilibrium expression (in terms of Keq) for homogeneous reactions occurring in solution
(ACSCH079, ACSCH096)
– dissociation of ionic solutions
EQUILIBRIUM CONSTANT EXPRESSION
A quantitative way of describing the position of equilibrium is the equilibrium constant (𝐾𝑒𝑞 ).
𝑎𝐴 + 𝑏𝐵 ⇋ 𝑐𝐶 + 𝑑𝐷
- Capital letters represent chemical substances

- Lower case letters represent the stoichiometric coefficients of the balanced equation
[𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠] [𝐶]𝑐 [𝐷]𝑑

𝐾𝑒𝑞 = 𝐾𝑐 = 𝐾 = =
[𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] [𝐴]𝑎 [𝐵]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:
𝐶𝑎𝐶𝑂3(𝑠) ⇋ 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(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 Keq 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)
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.

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]𝑐 [𝐷]𝑑
𝑄=
[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
approximation: [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡]𝑖𝑛𝑖𝑡𝑖𝑎𝑙 − 𝑥 ≈ [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡]𝑖𝑛𝑖𝑡𝑖𝑎𝑙
- However, the assumption must be checked to be valid. The calculated value of 𝑥 must be less than 5% of
the reactant’s initial concentration.
−𝑏±√𝑏 2−4𝑎𝑐
If the assumption is invalid, the quadratic formula has to be used: 𝑥 =
2𝑎
OUTCOMES
● qualitatively analyse the effect of temperature on the value of Keq (ACSCH093)
EFFECT OF TEMPERATURE ON 𝑲𝒆𝒒
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.

IRON(III) THIOCYANATE
OUTCOMES
● conduct an investigation to determine Keq of a chemical equilibrium system, for example:
– Keq of the iron(III) thiocyanate equilibrium (ACSCH096)
IRON (III) THIOCYANATE EQUILIBRIUM REACTION
When mixed together, aqueous solutions of iron(III) nitrate (Fe(NO3)3) and potassium thiocyanate (KSCN) combine,
in a reversible exothermic process, to form the aqueous iron(III) thiocyanate complex ([Fe(SCN)]2+(aq)).
𝐹𝑒 3+ (𝑎𝑞) + 𝑆𝐶𝑁 − (𝑎𝑞) ⇌ [𝐹𝑒(𝑆𝐶𝑁)]2+ (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 [Fe3+] and [SCN-]: Add more FeCl3 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 [Fe3+] and [SCN-]: Add NaOH and AgNO3
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.

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).
𝐼0
𝐴 = log10
𝐼
- A: Absorbance, a number typically between 0.3 – 2.5. It is dimensionless but often expressed in absorbance
units (AU)
- I0: 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 and 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

SOLUBILITY
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.

- 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(PO4)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:
∆𝑆𝑠𝑜𝑙𝑢𝑡𝑒 + ∆𝑆𝑠𝑜𝑙𝑣𝑒𝑛𝑡 = 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.”

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) + AgNO3(aq) → AgCl(s) + NaNO3(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
All Group 1 (Li+ Na+ K+ Rb+ Cs+) and ammonium NONE

(NH+) salts are soluble
All nitrate (NO3-), acetate (CH3COO-) and NONE

bicarbonate (HCO3-) salts are soluble
All chloride (Cl-), bromide (Br-) and iodide (I-) Ag+, Pb2+ and Hg2+ halides are
salts are soluble insoluble
All sulfate (SO42-) salts are soluble Ag+, Pb2+, Hg2+, Ba2+, Ca2+, Sr2+
sulfates are insoluble
All hydroxides (OH-) salts are insoluble Group 1 and NH4+ hydroxides
are soluble,
Ba2+ and Ca2+ are slightly soluble
All carbonate (CO32-) and phosphate (PO43-) Group 1 and NH4+ carbonates
salts are insoluble are soluble

OUTCOMES
● derive equilibrium expressions for saturated solutions in terms of Ksp and calculate the solubility of
an ionic substance from its Ksp 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 (𝐾𝑠𝑝 ).
- The equilibrium constant is for the equation written in the direction of the dissolution.

UNITS OF CONCENTRATION
MOLARITY
Molarity is the main unit of concentration used 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 substance relative to the total mass. This is the
same as percentage weight (% w/w).
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
o Percentage is given by the formula: % 𝑏𝑦 𝑚𝑎𝑠𝑠 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 × 100
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.

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
- The Percentage by volume is given by the formula: % 𝑜𝑓 𝑣𝑜𝑙𝑢𝑚𝑒 = × 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.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑚𝑔)
o 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝑝𝑝𝑚) = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑘𝑔)
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝜇𝑔)
o 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝑝𝑝𝑏) = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑘𝑔)

SUMMARY
Name Unit Solute Unit Solution Unit
Molarity 𝑚𝑜𝑙 per 1𝐿 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

- 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.

SOLUBILITY CALCULATIONS
OUTCOMES
● derive equilibrium expressions for saturated solutions in terms of Ksp and calculate the solubility of
an ionic substance from its Ksp value
● predict the formation of a precipitate given the standard reference values for Ksp
CALCULATING 𝑲𝒔𝒑 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 𝐾𝑠𝑝 .
PREDICTING THE FORMATION OF A PRECIPITATE
Solubility constants can be used to predict if a precipitate will form when two solutions are mixed.
𝐵𝑎(𝑂𝐻)2(𝑠) ⇋ 𝐵𝑎2+ (𝑎𝑞) + 2𝑂𝐻 − (𝑎𝑞)
𝐾𝑠𝑝 = [𝐵𝑎2+ ][𝑂𝐻 − ]2
- The solubility constant for this reaction at 25℃ is 2.55 × 10−4

- This means [𝐵𝑎2+ ][𝑂𝐻 − ]2 = 2.55 × 10−4 in a saturated solution.
If the concentration of Ba2+ and OH- are higher than the amounts in a saturated solution, 𝑄 > 𝐾𝑠𝑝 and precipitation
will occur.
If the concentration of Ba2+ and OH- are lower than the amounts in a saturated solution, 𝑄 < 𝐾𝑠𝑝 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.

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.

DISSOCIATION OF ACIDS
OUTCOMES
– dissociation of acids and bases (ACSCH098, ACSCH099)
COMMON ACIDS
Name Formula
Hydrochloric acid HCl
Sulfuric acid H2SO4
Nitric acid HNO3
Phosphoric acid H3PO4
Carbonic acid H2CO3
Acetic acid (Vinegar/Ethanoic acid) CH3COOH
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 (𝐾𝑎 ).
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.
𝐻3 𝑃𝑂4(𝑎𝑞) ⇋ 𝐻 + (𝑎𝑞) + 𝐻2 𝑃𝑂4 − (𝑎𝑞) [𝐻+ ][𝐻2 𝑃𝑂4 − ]

𝐾𝑎1 = = 7.52 × 10−3
[𝐻3 𝑃𝑂4 ]
𝐻2 𝑃𝑂4 − (𝑎𝑞) ⇋ 𝐻 + (𝑎𝑞) + 𝐻𝑃𝑂4 2− (𝑎𝑞) [𝐻+ ][𝐻𝑃𝑂4 2− ]
𝐾𝑎2 = = 6.23 × 10−8
[𝐻2 𝑃𝑂4 − ]
𝐻𝑃𝑂4 2− (𝑎𝑞) ⇋ 𝐻+ (𝑎𝑞) + 𝑃𝑂4 3− (𝑎𝑞) [𝐻 + ][𝑃𝑂4 3− ]
𝐾𝑎1 = = 2.20 × 10−13
[𝐻𝑃𝑂4 2− ]
Acid strength depends on the identity of the acid and the extent of its ionisation in water.

STRONG ACIDS
- Perchloric: HClO4
- Hydriodic: HI
- Hydrobromic: HBr
- Hydrochloric: HCl
- Nitric: HNO3
- Sulfuric: H2SO4
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 −𝑙𝑜𝑔10 , 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 + ]𝑒𝑞𝑚 [𝐻 − ]𝑒𝑞𝑚
% 𝑖𝑜𝑛𝑖𝑠𝑒𝑑 = × 100 = × 100
[𝐻𝐴]𝑖𝑛𝑖𝑡𝑖𝑎𝑙 [𝐻𝐴]𝑖𝑛𝑖𝑡𝑖𝑎𝑙
The percentage unionised (percentage of intact molecules):
[𝐻𝐴]𝑒𝑞𝑚
% 𝑢𝑛𝑖𝑜𝑛𝑖𝑠𝑒𝑑 = × 100 = 100 − % 𝑖𝑜𝑛𝑖𝑠𝑒𝑑
[𝐻𝐴]𝑖𝑛𝑖𝑡𝑖𝑎𝑙

2020 CHE Chemistry Notes Module 5 6 1 30

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CHEMISTRY MODULE 5

Equilibrium and Acid Reactions

FACTORS THAT AFFECT EQUILIBRIUM

Inquiry question: What factors affect equilibrium and how?

CALCULATING THE EQUILIBRIUM CONSTANT ( K E Q )

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

Inquiry question: How does solubility relate to chemical equilibrium?

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

ENERGY PROFILE DIAGRAMS

HESS’S LAW OF HEAT SUMMATION

CHEMISTRY MODULE 5: EQUILIBRIUM AND ACID REACTIONS PAGE 3 OF 29

∆𝐻𝑟𝑥𝑛 = ∑ ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛 + ∑ ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

∆𝐻𝑟𝑥𝑛 = ∑ ∆𝐻𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑ ∆𝐻𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

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.

FACTORS THAT CHANGE ENTROPY

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

SECOND LAW OF THERMODYNAMICS

Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + Δ𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 > 0

CALCULATING ENTROPY IN CHEMICAL REACTIONS

Δ𝑆𝑟𝑥𝑛 = ∑ Δ𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ Δ𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

GIBBS FREE ENERGY

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

−𝑇Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 < 0

Δ𝐺𝑠𝑦𝑠𝑡𝑒𝑚 = Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚

- If 𝚫𝑮 < 𝟎 (Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 < 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 ), a reaction is spontaneous

∆𝐻𝑟𝑥𝑛 = ∑ ∆𝐻𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑ ∆𝐻𝑏𝑜𝑛𝑑 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

Δ𝑆𝑟𝑥𝑛 = ∑ Δ𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ Δ𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Δ𝐺𝑠𝑦𝑠𝑡𝑒𝑚 = Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚

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

Physical changes are generally reversible

STATIC AND DYNAMIC EQUILIBRIUM

There are no macroscopic changes when a closed system is at equilibrium.

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

ADDITION/REMOVAL OF A REACTION COMPONENT

CHANGE IN VOLUME OR PRESSURE

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

6CO2(g) + 6H2O(l) → C6H12O6(s) + 6O2(g)

SPONTANEITY AND EQUILIBRIUM

N2(g) + 3H2(g) ⇋ 2NH3(g) ∆𝐺 = −33.3 𝑘𝐽𝑚𝑜𝑙 −1

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

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

RATE OF REACTION (FROM MODULE 3)

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ∝ 𝐹𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝑜𝑓 𝐸𝑓𝑓𝑒𝑐𝑡𝑖𝑣𝑒 𝐶𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛𝑠

FACTORS AFFECTING THE RATE OF REACTION

The rate of reaction increases when the concentration of reactants is increased.

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

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

- The total number of collisions increase.

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

A chemical system at equilibrium can be disturbed in the following ways:

THE HABER PROCESS

N2(g) + 3H2(g) ⇋ 2NH3(g) ∆𝐻 = −92𝑘𝐽 𝑚𝑜𝑙 −1

ADDING A REACTION COMPONENT

REMOVING A REACTION COMPONENT

CHANGE IN VOLUME (OR PRESSURE)

MOLES, VOLUME AND PRESSURE

𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 ∝ 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑔𝑎𝑠

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