Module 5

IQ1A: Entropy and Gibbs Free Energy

Inquiry question: How can enthalpy and entropy be used to explain reaction spontaneity?

• analyse the differences between entropy and enthalpy

• use modelling to illustrate entropy changes in reactions
• predict entropy changes from balanced chemical reactions to classify as increasing or decreasing entropy
• explain reaction spontaneity using terminology, including:
o Gibbs free energy
o Enthalpy
o Entropy
• solve problems using standard references and 𝛥𝐺 𝑜 = 𝛥𝐻 𝑜 − 𝑇𝛥𝑆 𝑜 (Gibbs free energy formula) to classify
reactions as spontaneous or nonspontaneous
• predict the effect of temperature changes on spontaneity

Spontaneous vs non-spontaneous reactions

- Spontaneous: reactions or state changes that occur on their own accord, without an external
force / intervention being constantly applied.
o Maybe need an initial energy input (to meet activation energy).
o Exergonic reaction: spontaneous reaction and work energy is released.
- Non-spontaneous: reactants will not form products without a constant external driving force.
o E.g., photosynthesis: without constant sunlight, reaction can’t proceed.
o Endergonic reaction: non-spontaneous reaction, requiring energy to be driven and
absorbs work energy.

Entropy
- Entropy: a measurement of the degree of randomness of energy in a system.
o The lower the entropy, the more ordered and less random it is and vice versa.
- ∆𝑆 = Σ𝑆products − Σ𝑆reactants
- ∆𝑆 increases when:
o The volume occupied by gases increases.
o The overall number of particles in a system increases.
o The temperature of the system increases.
o A substance changes from solid to liquid to gas.

The two driving forces for chemical reactions

1. A tendency to decrease the energy of the system.
o Exothermic reactions, where reactants lose energy, forming more stable, lower
energy products, are often spontaneous.
2. A tendency to increase the overall entropy of the system.

Gibbs free energy

Δ𝐺 𝑜 = Δ𝐻𝑜 − 𝑇Δ𝑆 𝑜
The effect of temperature on reaction spontaneity
Δ𝐻 < 0 Δ𝐻 > 0
ΔS < 0 Spontaneous at all T Spontaneous at high T
ΔS > 0 Spontaneous at low T Not spontaneous at all

IQ1: the Nature of Chemical Equilibrium

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

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

Reversibility of reactions
- Reversible reaction: a reaction that is able to proceed in
both directions.
- Reacting particles collide with sufficient energy (bonds
break and rearrange) to form products. As soon as products
start to concentrate, they will undergo collisions and if the
activation energy for the reverse reaction is not too high,
the reverse reaction will start to occur to re-form reactants.

Practical investigation of reversible reactions

CuSO4.5H2O (s) <-> CuSO4 (s) + 5H2O (g)

- Heating drives off water of hydration -> turns blue to white

- Adding water -> turns white to blue
- Prior to any stress being added to the system, the system is at equilibrium, no macroscopic
changes are visible.
- When a stress is applied, we move to position of equilibrium so either the reactant or
product is more dominant in the solution.

2Mg (s) + O2 (g) -> 2MgO (s)

- Goes to competition, non-equilibrium system

- Magnesium goes from a metallic to white solid – no sign products reform reactants
- Combustion releases large amounts of energy and hence, the reverse reaction requires a lot
of energy to take place -> irreversible or reach static equilibrium.

Open and closed systems

- Open: exchange both matter and energy with the external environment.
 - Closed: exchanges only energy (not matter) with the external environment.
- Isolated: not open to exchange matter or energy with the external environment.

Dynamic and static equilibrium

Static equilibrium Dynamic equilibrium
Irreversible in nature Reversible in nature
No further chemical reaction in system. Reactants and products still participating in
chemical reaction.
Forward and backward reaction rates are 0. Forward and backward reaction rates are equal.
Open and closed systems. Only closed systems.

When does forward reaction stop? When all reactants are used up OR when one of the reactants
limits the reaction. The reverse cannot occur because the ΔG is highly positive.

- Lying to the left: concentration of reactants > concentration of products.

- Lying to right: concentration of products > concentration of reactants.

Non-equilibrium systems
- Non-equilibrium system: irreversible and only proceeds in forward direction.
o Gibbs free energy is > 0 or < 0 but not = 0.
- Combustion: exothermic and non-reversible.
o Reverse reaction will not occur because products have stable bonds (high bond
energies) which require large amounts of energy to break.
- Photosynthesis: endothermic and non-reversible.
o Non-spontaneous as it is endothermic and the entropy decreases – Gibbs free
energy is > 0.
o In chloroplasts, reaction is coupled to a series of spontaneous exothermic reactions,
allowing it to occur (external force).
o Some heat from spontaneous reactions is lost and there is an overall entropy
increase in the universe.
o Even though reverse reaction would have a very negative Gibbs free energy, the
many spontaneous reactions coupled to the process, driving it forward could not
occur -> irreversible.

Static equilibrium Both Non-equilibrium

Reaches competition, no No longer proceeding in Reverse process is extremely
reverse reaction occurs to forward or reverse direction. complex with multiple steps –
counter the forward. not viable to undertake.
System is closed. One of the processes is non- System is open.
spontaneous.
Possible for reverse process to One or both of the processes Forward and reverse process
occur but reaction rate is do not meet energy occur in different locations
extremely low or does not requirements under standard (open system). E.g.,
occur at standard conditions. conditions. photosynthesis in chloroplasts,
respiration in mitochondria.
Reaction rate of both forward
and reverse is effectively 0.
Collision theory
2NO2(g) ⇌ N2O4(g)

- As the N2O4 molecules decompose to produce NO2, their concentration decreases and so
does their collision rate. This in turn reduces the rate of the forward reaction.
- As NO2 form, they can also collide and result in a reaction to re-form N2O4.
- In the beginning, the forward reaction rate is greater than the reverse reaction rate as there
are far more N2O4 than NO2. This results in a net decrease in [N2O4] and a net increase in
[NO2].
- However, as the reaction proceeds, the rate of the forward reaction gradually decreases, and
the rate of the reverse reaction gradually increases.
- This continues until the rates of the forward and reverse reaction become equal, where
equilibrium is established. At this point, forward and reverse reactions still occur due to the
collision between molecules but no changes in concentration are observed.
IQ2: Le Chatelier’s Principle
Inquiry question: What factors affect equilibrium and how?

• 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:
o heating cobalt(II) chloride hydrate
o interaction between nitrogen dioxide and dinitrogen tetroxide
o iron(III) thiocyanate and varying concentration of ions
• explain the overall observations about equilibrium in terms of the collision theory
• examine how activation energy and heat of reaction affect the position of equilibrium

Equilibrium position
- Equilibrium position describes a set of concentrations of reactants and products present in
the system at equilibrium.
- To the left = the reactants are favoured.
- To the right = the products are favoured.

Le Chatelier’s Principle
- If a system is at equilibrium and the equilibrium is disturbed by changing the reaction
conditions, the system will adjust so as to minimize the disturbance / stress.
- Reactant concentration (or partial pressure) increased -> shift to the right; product
concentration (or partial pressure) increased -> shift to the left.
- Temperature increased -> endothermic reaction will be favoured; temperature decreased ->
exothermic reaction will be favoured.
- Pressure increased -> side of reaction with fewer gas molecules favoured; pressure
decreased -> side of reaction with more gas molecules favoured.
- Adding a noble gas at constant volume -> pressure is increased but partial pressures of
gasses is not increased -> no change in equilibrium; adding a noble gas at constant pressure -
> increase in volume and shift to the side that produces more moles of gas.

Shifts in terms of collision theory and rates

Disturbance Prediction Explanation
⬆ concentration / Forward rate When more reactant molecules are added, more
partial pressure increases collisions can occur so the rate of forward reaction
of reactant increases. The rate of the reverse reaction is initially
⬆ concentration / Reverse rate unchanged but as the forward reaction rate increases,
partial pressure increases reactants are used up and less collisions occur, so the
of product forward rate slowly decreases. The reverse rate slowly
increases as extra product collisions occur after the
forward reaction rate initially increases. The rates
eventually equalize, reaching equilibrium.
And vice versa.
⬆ pressure Side with fewer gas When pressure is increased, the concentration / partial
molecules favoured pressure of all gasses increases but the reaction rate
⬇ pressure Side with more gas involving the greater number of molecules becomes
molecules favoured greater than the reaction involving less molecules.
Then, as more product is formed, the rate of the
reverse reaction will steadily increase as the forward
 reaction slows, and the rates eventually equalize,
reaching equilibrium.
When the pressure is decreased, the effect is less for
the reaction involving fewer molecules compared to
that involving more molecules. The rate of reaction
producing more moles of gas begins to overtake that of
the reaction producing less moles.
⬆ temperature Endothermic Exothermic forward reaction will have lower activation
reaction favoured energy than the reverse reaction. Endothermic froward
⬇ temperature Exothermic reactions will have higher activation energy than the
reaction favoured reverse reaction.
Exothermic reaction is less temperature dependant –
increase / decrease in temperature impacts the
endothermic reaction more.
This means, at lower temperature, more particles in the
exothermic reaction will have the required activation
energy compared to the endothermic reaction.
At a higher temperature, the ‘advantage’ of the
exothermic reaction is reduced and more of the
particles of the endothermic reaction will posses their
activation energy, resulting in more successful
collisions.

Practical investigation
Fe3+ + SCN- <-> FeSCN2+ ΔH = -ve

Concentration vs time graphs and rate vs time graphs

2NO2 (g) <-> N2O4 (g) + heat

Disturbance Concentration vs time Rate vs time

⬆ concentration / partial
pressure of reactant

⬆ pressure
⬆ temperature

Adding a catalyst Would reach equilibrium faster

but if at equilibrium – no effect
IQ3: Equilibrium Constants
Inquiry question: How can the position of equilibrium be described and what does the equilibrium constant represent?

• deduce the equilibrium expression (in terms of Keq) for homogeneous reactions occurring in solution
• 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
• qualitatively analyse the effect of temperature on the value of Keq
• conduct an investigation to determine Keq of a chemical equilibrium system, for example:
o Keq of the iron(III) thiocyanate equilibrium
• explore the use of Keq for different types of chemical reactions, including but not limited to:
o dissociation of ionic solutions
o dissociation of acids and bases

Equilibrium and reaction quotients

Products over reactants = K (PoRK)

For reaction aA + bB <-> cC + dD

[𝐶]𝑐 × [𝐷]𝑑
𝐾=
[𝐴]𝑎 × [𝐵]𝑏

Concentrations are measure in molL-1

Reaction quotients
- If Q = K, then the product has reached equilibrium
- If Q < K, then the products need to be increased -> the reaction will need to proceed in the
forward direction
- If Q > K, then the products need to be decreased -> the reaction will need to proceed in the
reverse direction

There can be an infinite number of values for Q but there is only one value for K at a particular
temperature

Homogeneous and heterogeneous equilibria

- Homogeneous: all reactants and products in the same phase.
- Heterogeneous: reactants and products in different phases.

Pure liquids and pure solids have constant concentrations -> while a pure liquid or solid is
participating in a reaction, its concentration does not change and does not affect K. Therefore, they
are not include in K calculations when they are heterogenous

Working with equilibrium constants

- If one equation is the reverse from the other, the equilibrium constants are the inverse
(reciprocal) of each other.
- If the coefficients of an equation are doubled, the value of K is squared.
- If the coefficients of an equation are halved, the value of K is the square root of the original.

The meaning of K
K provides information on the equilibrium position:
 1. The extent of a reaction – how far the forward reaction proceeds before equilibrium is
established.
2. The equilibrium yield – the amount of product present at equilibrium.
- K > 104 – almost all reactants are converted to products
- K < 10-4 – very little product made
- 10-4 < K < 104 – mixture of reactants and products

Effect of temperature on equilibrium constants

- Increase temperature
o Endothermic -> K increases
o Exothermic -> K decreases
- Decrease temperature
o Endothermic -> K decreases
o Exothermic -> K increases

Calculating equilibrium constants and concentrations

ICE – Initial, Change (amount reacting and final amount), Equilibrium

Significant figures
- If you multiply or divide, use the smallest number of significant figures in the initial values
- If you add or subtract, use the smallest number of decimal places in the initial values

Dissociation of ionic solutions and acids and bases

Ionic solutions
AgCl (s) <-> Ag+ (aq) + Cl- (aq)

Ksp = [Ag][Cl]

The higher the Ksp, the more soluble the substance

Acids
- Acids ionise in water to create hydronium ions (H3O+)
- Strong acid: HCl (aq) + H2O (l) -> Cl- (aq) + H3O+ (aq)
- Weak acid: CH3COOH (aq) + H2O (l) <-> CH3COO- (aq) + H3O+ (aq)
[CH3 COO− ][H3 O+ ]
E.g., Ka =
[CH3 COOH]

- The greater the concentration of ionised species present, the higher the Ka value
- Therefore, stronger acids (those who ionise more completely), have a higher Ka value

Bases
- Bases ionise in water to create hydroxide ions (OH-)
- Strong base: NaOH (aq) + H2O (l) -> Na+ (aq) + OH- (aq) + H2O (l)
- Weak base: NH3 (aq) + H2O (l) <-> NH4+ (aq) + OH- (aq)
[NH4 + ][OH− ]
E.g., Kb =
[NH3 ]
- The greater the concentration of ionised species present, the higher the Kb value
- Stronger bases (those which ionise more completely), have a higher Kb value

IQ4: Solution Equilibria

Inquiry question: How does solubility relate to chemical equilibrium?

• 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:
o 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:
o potassium chloride and silver nitrate
o potassium iodide and lead nitrate
o sodium sulfate and barium nitrate
• 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

Different types of equilibrium constants

Type of chemical General equation Name and symbol of Expression for K
system equilibrium constant
Any general aA + bB <-> cC + dD Keq [𝐶]𝑐 [𝐷]𝑑
chemical reaction General equilibrium 𝐾𝑒𝑞 =
[𝐴]𝑎 [𝐵]𝑏
constant
A system involving A (s) <-> cC (aq) + dD (aq) Ksp 𝐾𝑠𝑝 = [𝐶]𝑐 [𝐷]𝑑
an ionic solid in A is an ionic solid The solubility product
contact with the composed of ions of C
saturated solution and D
of the solid
A system involving HA (aq) + H2O (l) <-> H3O+ Ka [𝐻3 𝑂+ ][𝐴− ]
a weak acid (an (aq) + A- (aq) The acid dissociation 𝐾𝑎 =
[𝐻𝐴]
acid that does not constant
fully ionise) in an
aqueous solution
of its ions

Solubility product
The solubility product, Ksp, is the equilibrium constant for a solid substance dissolving in an aqueous
solution. It represents the extent to which a solute dissolves in water. The more soluble a substance
is, the higher the Ksp value it has.

Important notes
1. Common ion effect: the solubility of the reaction is reduced by the common ion. For a given
equilibrium, a reaction with a common ion present has a lower Ksp, and the reaction without
the ion has a greater Ksp
2. Salt effect (diverse ion effect): having an opposing effect on the Ksp value compared to the
common ion effect, uncommon ions increase the Ksp value. Uncommon ions are ions other
than those involved in equilibrium.
 3. Ion pairs: with an ionic pair (a cation and an anion), the Ksp value calculated is less than the
experimental value due to ions involved in pairing. To reach the calculated Ksp value, more
solute must be added.

Solubility rules
1. All salts containing Group I cations and ammonium are soluble
2. All nitrates are soluble
3. All acetates are soluble
4. All chlorides are soluble except Ag+, Pb2+, Hg2+
5. All sulphates are soluble except Ag+, Pb2+, Hg2+, Ba2+ (Ca2+ is slightly soluble)
6. Most carbonates are insoluble except Na+, K+, NH4+
7. Most carbonates are insoluble except Na+, K+, NH4+
8. Most hydroxides are insoluble except Na+, K+, NH4+, Ba2+ (Ca2+ is slightly soluble)

As a general rule a substance is considered:

- Soluble: > 0.1 mol/L

- Partially soluble: 0.01 mol/L – 0.1 mol/L
- Insoluble: < 0.01 mol/L

Dissolving as a process
- Aquo-cation: a hydrated cation; a cation surrounded by electrostatically attracted H2O
- Aquo-anion: a hydrated anion; an anion surrounded by electrostatically attracted H2O
- Ligand: an ion/molecule that binds to a central metal atom to form a complex
- Ion-dipole bond: an electrostatic bond that occurs when sufficient differences in
electronegativity appear between dipoles and charged ions
- Solvent: the major component of a solution
- Solute: the minor component of a solution
o In solutions of two liquids or two solids, the solute is defined as the substance
present in the lowest amount
- Solutions are homogenous mixtures when a solute is dissolved in a solvent

Water, ‘the universal solvent’, can generally dissolve:

- Many ionic substances

- Many polar covalent molecular substances
- Some non-polar solutes

Water cannot generally dissolve:

- Many non-polar solutes

- Covalent networks
- Polymers

As a simple general rule:

- If the solvent and solute form similar adhesive forces between particles, the solute will
dissolve in the solvent.
- If they cannot form similar adhesive forces with the solvent, the solute will not dissolve.
Ionic substances dissolving in water
The dissolving of an ionic salt is an example of dynamic equilibrium.

When ionic substances are added to water, the positive ends of the water molecules surround the
negative ions. The negative ends of the water molecules surround the positive ions. As the water
molecules move around, the forces of attraction between the water molecules and the ions may be
strong enough to pull the lattice apart, and the substance will dissolve. In solution, the ions do not
move around separately. They are in fact, hydrated. This means they are surrounded by a number of
water molecules with the positive ends of a number of water molecules close to the anions and the
negative ends of other water molecules close to the cations.

At first, the only process occurring is the salt dissolving (dissociations of the salt into ions). Then,
some of the ions in the water begin to collide with the salt crystal and are pulled back into the solid
salt, i.e. precipitation occurs. Eventually (at equilibrium), the rate of dissociation equals the rate of
precipitation. The solution is saturated and is at equilibrium.

Dissolving is a physical process, which can be reversed by allowing the solution to dry out so that the
water evaporates.

Solubility and Gibbs free energy

If a substance is soluble, it means the dissolving process is spontaneous, ΔG is negative. Whereas an
insoluble substance’s ΔG is positive.

Using solubility product expressions

Calculating Ksp values from molar solubility
The molar solubility of a compound is the concentration of ions that have dissociated from the solid
to produce a saturated solution of that compound.

How to convert between solubility of a salt and its Ksp: e.g., solubility of CaSO4 = 0.225g/100g

1. Equation: CaSO4 (s) <-> Ca2+ (aq) + SO42- (aq)

Always use equilibrium arrows
2. Expression of Ksp: [Ca2+][SO42-]
[] must be molar concentrations at equilibrium
3. Convert solubility of compound into mol/L
n(CaSO4) = 0.255/(40.08+32.07+16x4)x10=0.0187 mol/L
 4. ICE:

CaSO4 Ca2+ SO42-

I 0.0187 0 0
C -0.0187 +0.0187 +0.0187
E 0 0.0187 0.0187

Ksp = 0.0187x0.0187 = 3.50x10-4

Calculating molar solubility from Ksp values

Comparing Ksp values
Ksp values can only be used to compare the solubilities of salts that produce the same total number
of ions on dissolution.

If the salts produce different numbers of ions, Ksp values cannot be used to compare their solubilities.

Determining when a precipitate forms – Qsp vs Ksp

If we have information about the ion concentrations, we can substitute them into the expression to
determine whether a precipitate would form or not. There are 3 scenarios:

- Q = K: there is the exact concentration of ions that make a saturated solution without a
precipitate forming.
- Q > K: there are more products than at equilibrium, hence more ions present than the
minimum required to form a precipitate and a precipitate forms.
- Q < K: there are less products than at equilibrium, hence less than the required ion
concentration to form a precipitate and no precipitate forms.

The common ion effect

Whenever a solution of an ionic substance comes into contact with another ionic compound with a
common ion, the solubility of the ionic substance decreases significantly.

The solubility products Ksp’s are equilibrium constants in heterogeneous equilibria. If several salts are
present in a system, they all ionise in the solution. If the salts contain a common cation or anion,
these salts contribute to the concentration of the common ion. For example, a solution containing
sodium chloride and potassium chloride will have the following relationship:

[Na+] + [K+] = [Cl-]

Consideration of charge balance or mass balance or both leads to the same conclusion.

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.
Example 1
What are [Na+], [Cl−], [Ca2+], and [H+] in a solution containing 0.10 M each of NaCl, CaCl2, and HCl?

Due to the conservation of ions, we have [Na+] = [Ca2+] = [H+] = 0.10M

But [Cl−] = 0.10 (due to NaCl) + 0.20 (due to CaCl2) + 0.10 (due to HCl) = 0.40M

Example 2
Le Chatelier’s Principle
By Le Chatelier’s Principle the addition of the common ion will shift the solubility equilibrium to the
left i.e it will increase the Precipitation Reaction Rate (reverse reaction rate). This means that there is
more solid salt in the reaction mixture and thus the solubility is lowered.
Removing toxicity from food
- Cycad seeds are used to make bread by Indigenous Australians (the Gamilaraay/Kamilaroi
people).
- Cycad seeds are toxic. Cycasin (the toxin) can cause cancer and damage to the nervous
system.
- The toxins are removed via leaching, an application of solution equilibria.
- Cycasin is soluble in water (56.5 g/L) -> cycasin in the cycad seed will dissolve in water until
the saturation point (dynamic equilibrium).

- Indigenous Australians use running water during leaching to prevent the reaction from
reaching a dynamic equilibrium -> equilibrium is constantly being disrupted due to an open
system.
- Thus, more cycasin can be removed from the seed, in order to reach a safe enough level.
Module 6
IQ1: Properties of Acids and Bases
Inquiry question: What is an acid and what is a base?

• investigate the correct IUPAC nomenclature and properties of common inorganic acids and bases
• 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
• predict the products of acid reactions and write balanced equations to represent:
o acids and bases
o acids and carbonates
o acids and metals
• investigate applications of neutralisation reactions in everyday life and industrial processes
• conduct a practical investigation to measure the enthalpy of neutralisation
• 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:
o Arrhenius’ theory
o Brønsted–Lowry theory

Properties of acids and bases

Acids Bases
Sour taste Bitter taste
pH < 7 pH > 7
+
Ionises to increase [H ] Ionises to increase [OH-]
Dissolves in water to create conductive solutions - electrolytic
Turns blue litmus red Turns red litmus blue
Corrosive, burns Corrosive, soapy / slippery
Neutralised by bases Neutralised by acids

Naming acids
- Inorganic acids containing 2 elements (H and a halogen)
o Prefix is hydro followed by name of anion with ic as suffix
o NB: HCN is named in a similar way. CN- is the cyanide anion so the acid is hydrocyanic
acid
- Inorganic acids containing 3 elements (H, O, and another metal), aka oxyacids
o Prefix derived from other non-metal and either ends with ic (most oxygen / non-
metal in higher oxidation state) or ous (1 less oxygen / non-metal in lower oxygen
state)
o E.g., sulfuric acid (H2SO4) and sulfurous acid (H2SO3)
- Organic acids: methanoic/formic acid (HCOOH), ethanoic/acetic acid (CH3COOH)

Naming bases
- Metal oxides (especially if metal is to the left of the periodic table)
o Basicity of oxides decreases as you move right of the periodic table
- Metal hydroxides
- Metal carbonates
- One important base that doesn’t contain a metal is ammonia (NH3)
Acid-base indicators
Indicators work because they have two forms, each having a different colour. The indicator system
will come to equilibrium if it is left undisturbed.

- One form can be represented as HIn (where the indicator, In, can be a very complex species
bonded to a H atom).
- The other form is the In- species, where the H has been removed (ie the indicator molecule
has been ionised).

- Adding more acid (containing H+ ions) makes the reaction shift to the left and the colour
changes to colour 1.
- Adding more base (containing OH- and reacting with and removing free H+) makes the
reaction shift to the right and the colour changes to colour 2.

pH and indicators
Indicator pH range Colour change
Methyl orange 3.2 - 4.4 Red - yellow
Bromothymol blue 6.0 - 7.4 Yellow - blue
Phenolphthalein 8.3 - 10.0 Colourless - magenta

Making an indicator
Aim: to extract coloured solution from red cabbage and test it to determine if it is an effective acid-
base indicator.

Risk assessment:

Identify Likelihood Severity Control

Burning skin on tripod Moderate Low Use hot hands /
silicon mits
Solutions of low pH or high Moderate Low Wear goggles and a
pH are corrosive and can lab coat
irritate, burn skin and eyes

Method:

1. Roughly chop the cabbage on a chopping board with a knife.

2. Place some chopped up cabbage in a 250 mL beaker and cover with water.
3. Heat the water until it boils using a Bunsen Burner. Continue heating until the water is visibly
coloured with the dye from the cabbage.
4. Remove the cabbage and water from the heat and pour the mixture through a sieve into a
large beaker or bowl.

To test the solution:

Place the solution in spotting tiles which contain a few drops of buffer solutions of known pH (1-14).
For a solution to be an effective indicator, it must display at least one distinct colour change over the
pH range.

Common acid reactions

Acid + base -> salt + water + heat (all neutralisation reactions are exothermic)

Acid + carbonate -> salt + water + carbon dioxide

Acid + active metal -> salt + hydrogen gas

Naming anions from diprotic and triprotic oxyacids

H2SO4 is diprotic. When the acid molecule is placed into water, the acid ionises in two steps:

1. H2SO4 (l) -> H+ (aq) + HSO4- (aq)

(Almost goes to competition)
2. HSO4- (aq) <-> H+ (aq) + SO42- (aq)
(Goes to equilibrium with a position to the left)

Rules to naming anions such as HSO4- which are derived from diprotic or triprotic ac

1. The name of the final anion formed once all H are ionised is preceded with the name
hydrogen. Thus HSO4- is called the hydrogen sulfide ion.
2. If more than one H is attached, the name of the anion is preceded by dihydrogen.

Species Name
H3PO4 Phosphoric acid
H2PO4- Dihydrogen phosphate
HPO42- Hydrogen phosphate
PO43- Phosphate

Changing theories about acids

Theory Description Benefits Limitations
Lavoisier After experimenting on Many acids do contain Many acids such as
oxides of non-metals, oxygen. hydrochloric acids do not
Lavoisier came to the contain oxygen.
conclusion that acids were
substances that contained
oxygen atoms.
Davy Electrolysis of HCl revealed The vast majority of Didn’t explain why
that it only contained known acids containing H. hydrogen containing
hydrogen and chlorine, no Also, when metals are compounds aren’t acidic
oxygen. Concluded that an added to acids, hydrogen (e.g., water, methane) nor
acid + base produced a gas is released, and the why solutions that didn’t
salt. resulting solution is less contain hydrogen are
acidic. acidic.
Doesn’t explain hydrogen’s
role in conferring acidic
properties.
 Arrhenius Acids ionise in water First theory to explain Confined all acid-base
(aqueous environments) to known properties of acids reactions to aqueous
produce H+ which is the such as why they were environments. However,
cause of acidic properties. electrolytes and why they corrosive hydrogen
Bases dissociate in water were neutralised by chloride gas can react with
to produce OH- which is bases. ammonia gas to produce a
the cause of its basic Most common acids salt (neutralisation occurs),
properties. Neutralisation contain H+ and most without any water present.
occurs when H+ reacts with common bases contain
the OH- to form H2O. OH-.
Bronsted- Acids are proton (H+) Not confined to aqueous Still doesn’t explain why
Lowry donors and bases are environments – can occur some metal ions in
proton acceptors. Acid- in any state. solution have acidic
base reactions are proton- properties.
transfer reactions.
Lewis A Lewis acid is an electron
pair acceptor. A Lewis base
is an electron pair donor.

Classifying acids
- Monoprotic – ionises to release 1 H+ per acid molecule
- Diprotic – ionises to release 2 H+ per acid molecule
- Triprotic – ionises to release 3 H+ per acid molecule

Amphiprotic substances
Amphiprotic substance: a species that can act as both a proton donor and acceptor, depending on
what they react with.

To be amphiprotic, a substance must have a chemical composition which both includes at least one
ionisable H+ and has the bonding capacity to allow it to bond and accept another H+.

Water and hydrogen salts are good examples of amphiprotic species.

Neutralisation reactions in industry and everyday life

Solutions with high [H+] or [OH-] are corrosive and adding an acid to a base will decrease both
concentrations and make neutral water… so this makes neutralisation reactions very useful.

Acid effluents - Liquid waste from industrial processes must be neutralised before
being dumped to reduce its effect on the water system.
- Many effluents contain sulphuric acid and can be neutralized with a
base e.g., limestone (calcium carbonate).
- H2SO4 (aq) + CaCO3 (s) -> CaSO4 (aq) + H2O (l) + CO2 (g)
 Drinking water - To avoid adverse health effects, drinking water is treated to be neutral.
- The industrial treatment of drinking water involves several
neutralization stages: it’s made alkaline for the cleaning process and
must be neutralised before consumption.
Chemical spills - Dangerous spills can be neutralised with substances such as NaHCO3.
- This requires a cheap powdered substance that is easy to disperse,
stable, easily stored, very soluble, and amphiprotic if the pH of the spill
is unknown.
Antacids - Excess acid may be produced in the stomach, resulting in acid reflux. At
the top of the stomach, there is a ring valve of muscles called the
oesophageal sphincter. If this is not functioning correctly, excess acids
may rise up into the oesophagus, causing a burning sensation.
- Medicines containing bases (e.g., Al(OH)3 and Mg(OH)2, MgCO3) can
neutralize excess stomach acid to treat indigestion.
- Stomach acid’s low pH is largely due to hydrochloric acid.

Heat (enthalpy) neutralisation

Neutralisation reactions are always exothermic.

For reactions involving strong acids and alkalis, the values are always very similar, often ranging
between -57 and -58 kJ/mol (-57.3 kJ/mol).

Practical investigation
1. Measure 50.0 mL of 1.0 HCL and 50.0 mL of 1.0 M NaOH.
2. Measure and record the temperature of each solution by placing the thermometer in the
measuring cylinder. Make sure to rinse and dry the thermometer before transferring to the
other solution. Average the two temperatures to determine the initial temperature.
3. Pour the HCl into the calorimeter (doubled polystyrene cups) and pour the NaOH into the
HCl solution. Insert the thermometer.
4. Stir with the thermometer. Record the highest temperature.

HCl (aq) + NaOH (aq) -> NaCl (aq) + H2O (l)

Temperature increase = 6oC

n(HCl) = 0.05 mol = n(NaOH)

n(H2O produced) = 0.05 mol

q = mCΔT = 100 x 4.18 x 6 = 2508 J

ΔH = - 2.508 / 0.05 = - 50.16 kJ/mol

Why heats of neutralisation for all strong acids and bases have similar values
The full equation for the reaction between hydrochloric acid and sodium hydroxide solution is: HCl
(aq) + NaOH (aq) -> NaCl (aq) + H2O (l)

… but what is actually happening is: H+ (aq) + OH- (aq) -> H2O (l)

If the reaction is the same in each case of a strong acid and strong alkali, it isn’t surprising the
enthalpy change is similar.

Why do weak acids or weak alkalis give different values?

In a weak acid at ordinary concentrations, something like 99% of the acid is not actually ionised. This
means the enthalpy change of neutralisation will include other enthalpy terms involved in ionising
the acid as well as the reaction between the hydrogen ions and hydroxide ions. And in a weak alkali
like ammonia solution, the ammonia is also present mainly as ammonia molecules in solution. Again,
there will be other enthalpy changes involved apart from the simple formation of water from
hydrogen ions and hydroxide ions.

Why are neutralisation reactions always exothermic?

In the reaction: H+ (aq) + OH- (aq) -> H2O (l)

The reactants are already free ions so little energy is needed to break bonds in reactants (in reality,
the H+ exists as H3O+ so one bond needs breaking).

However, the two O-H bonds are formed in the product. This process must produce much more
energy than that required to break one of the bonds in the H3O+ ion. This is why the overall change is
negative.
IQ2: Brønsted-Lowry Theory
Inquiry question: What is the role of water in solutions of acids and bases?

• 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
• conduct an investigation to demonstrate the use of pH to indicate the differences between the strength of acids
and bases
• 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:
o sodium hydrogen carbonate
o potassium dihydrogen phosphate
• construct models and/or animations to communicate the differences between strong, weak, concentrated and
dilute acids and bases
• calculate the pH of the resultant solution when solutions of acids and/or bases are diluted or mixed

Amphiprotic substances
Amphiprotic substance: a substance that is able to donate or accept protons depending on the
substance it reacts with.

Even in a sample of pure water, when 2 molecules collide at the correct orientation, one may donate
a proton to the other. This is because a water molecule has both a proton to donate as well as
bonding capacity to allow it to accept and bond to a proton.

2𝐻2 𝑂(𝑙) ↔ 𝐻3 𝑂+ (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞)

Many ions produced by the ionisation of polyprotic acids are amphiprotic.

Conjugate acid/base pairs

Most acid-base reactions are reversible. The substance that donates the proton in the forward
reaction (the acid) produces a substance with one less proton, which acts as a base in the reverse
reaction. Similarly, the base in the forward reaction accepts a proton, forming a substance which can
then donate the proton in the reverse reaction, thus acting as an acid.

A conjugate base has one less proton than the acid from which it was formed. A conjugate acid has
one more proton than the base from which it was formed.

The pH scale
- The term pH stands for ‘hydrogen power’
o This came about because the pH scale is based on the concentration of hydrogen
ions in solution. In aqueous solutions, the hydrogen attaches to the water molecule
to form the hydronium ion, H3O+. This means the pH scale is based on the [H3O+].
 - The pH scale reflects the importance of the Brønsted-Lowry definition of an acid as a proton
donor. The pH scale is a measurement of the number of hydronium ions present in a solution
(that is the number of H+ ions the acid has donated to water to form hydronium ions).
- The pH scale quantitatively measures the acidity of a solution.

What does the pH scale look like?

- The scale does from 0 to 14, although there are values outside this range.
- The lower the pH, the more acidic a solution, the higher the pH, the more basic a solution.
- At 298K, acids have a pH of less than 7, bases have a pH greater than 7, and a substance that
has a pH equal to 7 is neutral.
- pH = – log10[H3O+] (H3O+ can be substituted for H+ since they mean the same thing).
- An increase in 1 pH unit is equal to a 10-fold decrease in [H3O+].
- pOH = – log10[OH-]

Applying the self-ionisation of water

From the self-ionisation of water… 2𝐻2 𝑂(𝑙) ↔ 𝐻3 𝑂+ (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞)

Kw (the ionic product constant for water) = [H3O+] [OH-], where Kw = 1.0 x 10-14 at 298 K

In pure water (and other neutral substances), [OH-] = [H3O+]

Thus, at 298 K, [H3O+] = 10-7

Measuring pH
Probes
- Use a pH probe (often a glass electrode) and a data logger
- Benefits: provides a digital reading of the pH – more accurate, not subjective; non-
destructive
- Limitations: more difficult to use, expensive
Indicators
- Synthetic or natural where the colour changes over a range of pH values are used.
- Benefits: cheap, easy to use.
- Limitations: subjective.
- Universal indicator: provides a specific colour for each pH value. It is a mixture of a number
of different indicators.

Concentration vs strength of acids

The reaction of an acid with water is called an ionisation reaction as ions are formed. When a base
dissolves in water, it forms separate ions in a dissociation reaction.

The concentration of an acid refers to the amount of solute dissolved in a specific amount of
solution, most commonly represented by morality.

Acids are classified as strong or weak depending on how well they transfer their protons to water to
form hydronium ions. Strong acids completely ionise, transferring almost 100% of their protons while
weak acids only partially ionise.

Similalrly, bases can also be strong and weak depending on the number of molecules or ionic
compounds that dissociate in aqueous solutions.

Strong acids Strong bases

Hydrochloric acid, HCl Sodium hydroxide, NaOH
Nitric acid, HNO3 Potassium hydroxide, KOH
Sulfuric acid, H2SO4 Barium hydroxide, Ba(OH)2
Sodium oxide, Na2O
Weak acids Weak bases
Ethanoic acid, CH3COOH Ammonia, NH3
Carbonic acid, H2CO3 Methylamine, CH3NH2
Hydrofluoric acid, HF
Citric acid, C6H8O7

Percentage ionisation
[𝐴− ]
Percentage ionisation = × 100%
[𝐻𝐴]

Calculations for dilutions

pH and dilution
- Changing the concentration by adding or removing the solvent will change the pH.
 - Diluting a strong acid or base by a factor of 10 (0.1 M to 0.01 M) causes a change in pH by 1
unit.
- Diluting a weak acid or base by a factor of 10 causes a change in pH by less than 1 unit.

pH of weak acids
[𝐻3 𝑂+ ][𝐴− ]
𝐾𝑎 =
[𝐻𝐴]

We can make the following assumptions:

1. At equilibrium, [HA] is the same as the initial concentration; the weak acid only ionizes to a
small degree in water.
2. [H3O+] produced by the self-ionization of water is negligible and has no effect on calculations.

NB: pKa = -log10Ka -> small pKa values correspond to greater acid strength

pH of weak bases
Reaction of weak base with water: B (aq) + H2O (l) <-> BH+ (aq) + OH- (aq)

The dissociation constant (equilibrium expression) is…

[𝐵𝐻+ ][𝑂𝐻 − ]
𝐾𝑏 =
[𝐵]
We can make the following assumptions:

1. At equilibrium, [B] is the same as the initial concentration; weak bases only ionise to a small
extent in water.
2. [OH-] produced by the self-ionization of water is negligible and has no effect on the
calculations.

pKb = -log10Kb

For conjugate acid-base pairs, Ka x Kb = Kw and pKa + pKb = 14

pH of polyprotic acids
The pH of a 0.1 M H2SO4 solution is not 1.0 but 0.88. This means it is more acidic than a 0.1 M
solution of a monoprotic acid. The smaller pH indicates there are more hydronium ions in solution
when H2SO4 is dissolved compared to that of the monoprotic acid HCl, of the same concentration.

The ionization of sulfuric acid happens in 2 steps:

1. H2SO4 (aq) + H2O (l) -> H3O+ (aq) + HSO4- (aq) Ka < 1
2. HSO4- (aq) + H2O (l) <-> H3O+ (aq) + SO42- (aq) Ka = 1.2 x 10-2

Sulfuric acid is a strong acid so large numbers of molecules ionise in the first equation. HSO4- is a
much weaker acid than H2SO4 so not many molecules will react with water and ionise.

Total [H3O+] = [H3O+] in step 1 + [H3O+] in step 2

When a diprotic acid ionizes, the first ionization always produces more [H3O+] than the second
ionization. For H2SO4, the first proton ionizes 100%, leaving behind HSO4- which is negatively charged
and therefore less inclined to lose the second proton since it is positively charged.
Ka of polyprotic acids
For polyprotic acids, we add the equilibria equations together and hence, multiply the K values
together to find total K.

Neutralisation and the pH of salt solutions

Calculating the pH of a mixture
1 Write an equation 2HNO3 + Ba(OH)2 -> Ba(NO3)2 + 2H2O
2 Find moles of both acid and bases n(HNO3) = CV = 0.1 x 0.1 = 0.01 mol
separately n(Ba(OH)2) = 0.02 x 0.2 = 0.004 mol
3 Determine limiting reagent Ba(OH)2 limits and is consumed
4 How many moles of excess are consumed? Moles HNO3 consumed = 0.004 x 2 = 0.008
mol
5 Moles of excess in final solution Initial moles – moles consumed
0.01 – 0.008 = 0.002 moles
6 Concentration of excess in final solution C = n / V = 0.002 / 0.12 = 0.0167 M
7 Calculate pH as usual pH = -log0.0167 = 1.8

pH of salt solutions
When salt ions dissociate in solution, the ions may act as weak acids or bases with water, therefore
producing hydronium or hydroxide ions.

Hydrolysis reaction – where one or both of the ions in a salt donate a proton to the water or accept a
proton from the water, resulting in the production of H+ or OH-.

To predict pH of a salt solution:

- Strong acid + strong base -> neutral salt

- Weak acid + weak base -> neutral salt
- Strong acid + weak base -> acidic salt
- Weak acid + strong base -> basic salt

Steps to determine the pH of a salt solution:

1. Write the dissociation equation of the salt.

2. Identify if any ion undergoes hydrolysis.
3. Write hydrolysis equation.

Tips for hydrolysis equations:

- Any hydrolysis equation has an ion and water as the reactants.

- Should use a reversible arrow.
- Show either a hydronium ion or a hydroxide ion as a product.

Cations
Many cations are acidic, being the conjugates of bases, or being able to act as Lewis acids.
a. Conjugate acids of weak bases
NH4+ + H2O <-> NH3 + H3O+
b. Metal ions with a high charge to radius ratio (Al3+, Cr3+, Fe3+)
(1) Hydration: Al3+ + 6H2O <-> Al(H2O)63+ (aq)
 (2) Hydrolysis: Al(H2O)63+ + H2O <-> Al(OH)(H2O)52+ + H3O+
Exceptions (neutral since no cations are basic): relatively large for their charge and don’t hydrolyse.
Li+, Na+, K+, Rb+, Cs+, Ba2+, Sr2+, Ca2+ (i.e. group 1 and 2 cations)
Anions
Most anions are basic, being the conjugate bases of acids.
The weaker the parent acid, the stronger the conjugate base -> the following are strong bases
from weak acids:
Acetate: C2H3O2- + H2O <-> HC2H3O2 + OH-
Cyanide: CN- + H2O <-> HCN + OH-
Bicarbonate*: HCO3- + H2O <-> H2CO3 + OH-
* This is an amphiprotic ion but its reaction as a base in water occurs to a greater extent than its
reaction as an acid.
Exceptions (mostly neutral): mostly conjugate bases of strong acids, most commonly…
Cl-, Br-, I-, NO3-, ClO4-, SO42-
A few anions are acidic: typically contain hydrogen. E.g., HSO42-. These are amphiprotic, but their
reaction as an acid occurs to a greater extent then their reaction as a base.
HSO4- + H2O <-> SO42- + H3O+
IQ3: Acid and Base Analysis
Inquiry question: How are solutions of acids and bases analysed?

• 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:
o strong acid/strong base
o strong acid/weak base
o weak acid/strong base
• model neutralisation of strong and weak acids and bases using a variety of media
• calculate and apply the dissociation constant (Ka) and pKa (pKa = -log10 (Ka)) to determine the difference
between strong and weak acids
• explore acid/base analysis techniques that are applied:
o in industries
o by Aboriginal and Torres Strait Islander Peoples
o using digital probes and instruments
• conduct a chemical analysis of a common household substance for its acidity or basicity, for example:
o soft drink
o wine
o juice
o medicine
• conduct a practical investigation to prepare a buffer and demonstrate its properties
• describe the importance of buffers in natural systems

Concentration and dilution

- Concentration refers to the relative amount of solute present in the solution.
- A concentrated solution has a high proportion of solute vs a dilute solution has a low
proportion of solute.
- Concentration = solute / solution (not solvent)
- C=n/V
- Some units for concentration: M (mol/L), ppm (mg/L), g/L, %w/w (g/100g), %v/v
(mL/100mL), %w/v (g/100mL).

Dilutions
Dilution steps:

1. Draw up a known volume of the original solution using a volumetric pipette.

2. Transfer this solution to a clean, dry volumetric flask.
3. Add distilled water to the flask until the total volume reaches the calibration line.

CoVo = CdVd

Introduction to titrations
Titrations are a type of quantitative analysis.

Quantitative analysis Any analysis of a chemical which involves measuring how much of a
component is present in the chemical.
Qualitative analysis Any analysis of a chemical which involves determining aspects of its
composition (e.g., which elements it contains, type of bonds, etc) but not
how much of each component is present.
Titrations are also classed as volumetric analysis because the technique relies on accurate
measurements of volume delivered from the burette.

Purpose is to measure the concentration of acid or base, achieved by reacting the unknown (=
analyte) with an acid or base of known concentration (a standard = titrant).

In a titration:

- A measured volume of one of the solutions is placed in a conical flask using a volumetric
pipette.
- A few drops of an appropriate indicator are placed in the flask so that the colour change will
occur when the neutralisation reaction between the acid and base is complete.
- The other solution is then added to the flask from a burette. Sufficient solution is added from
the burette to completely react with the solution in the flask (end point is reached).
- From the measured volume and known concentration of the solution used, it is possible to
calculate the amount of substance being determined.

Solving titration problems:

1. Write a balanced equation for the neutralisation reaction.

2. Determine the moles of the known (standard solution).
3. Use the mole coefficients in the equation to determine the moles of the unknown.
4. Calculate the concentration of the unknown in the desired units.

Basic equipment in titration

Name Picture Function
Burette Slowly delivering a solution to a
reaction vessel until the reaction goes
to completion. The scale markings
allow for the volume added (the titre)
to be known precisely and accurately.

Volumetric pipette To measure out a precisely known

volume of a solution. Can be used
alongside a volumetric flask for
dilutions, or to prepare an aliquot for a
titration.

Volumetric flask To measure out a precisely known

volume of a solution. To prepare
solutions of known concentration or
known dilution factor.
Conical flask The vessel where the titration reaction
takes place. The conical shape allows
for swirling with low chance of spilling.
The experimenter carefully observes
the solution in the conical flask to see if
the indicator has changed colour.

Glossary of key terms

Term Meaning
Molarity concentration in moles per litre
An accurate determination of the amount or concentration
Quantitative analysis
of a chemical substance, e.g. titration.
Qualitative analysis A determination based on non-numerical information.
A quantitative analysis involving accurately known
Volumetric analysis
volume(s).
End-point The pH at which an indicator changes colour.
The point in a reaction when the stoichiometric ratios of
Equivalence point
the reactants match the numbers of moles added.
Titre The volume added from the burette in a titration.
The volume of reactant (added to the conical flask) to
Aliquot
which the titre is added.
A solution of known concentration, used for determining
Standard solution
the concentration of an unknown solution.
A concentrated standard from which more dilute standards
Primary standard solution
(suitable for titration) can be prepared.

Standard solutions
- Titrants are used to titrate analytes. Standard solutions are used as titrants.
- Titrants are either “primary standards” or “secondary standards”.
- Primary standards are highly pure and can only be made with certain compounds.
o Make the solution up from a known mass of solid and then calculate the
concentration.
- Secondary standards are not necessarily pure or able to be known when first made because
they are standardised (titrated) against a primary standard.
o Perform a titration on a solution by reacting the unknown solution with a standard
solution -> once concentration is determined, becomes a standard solution.

Making up a primary standard

1. From the required volume and concentration specified, calculate the moles and then mass of
the solute needed.
2. Weigh this amount out using an electronic balance.
3. Carefully transfer this mass into a beaker and add some distilled water to dissolve it.
4. Transfer all of the solution to a clean dry volumetric flask.
5. Add more distilled water to reach the calibration line (bottom of meniscus should be
 6. on the line.
7. Stopper the flask and invert to thoroughly mix the contents.
8. Label the solution with the name of the chemical, its concentration and the date.

Suitable solids for the preparation of primary acid and base standards
A suitable solid must:

1. Be available in pure form – free of moisture.

2. Have a relatively high formula mass (= molar mass).
3. Be soluble in water.
4. Not react with air or moisture in the air as it is being weighed.

A suitable solid for preparing a basic primary standard solution: anhydrous sodium carbonate
(Na2CO3).

A suitable solid for preparing a acidic primary standard solution: oxalic acid-2-water (H2C2O4.2H2O).

Some reasons that some common substances are unsuitable for making primary standards are:

- Sodium / potassium hydroxide – absorbs moisture in air, react with CO2 in air, thus, not
sufficiently pure.
- Solutions of acids and bases – not in pure dry form. Many solutions of acids lose acidity as
volatile gases leave the solution.

Common acids like HCl, H2SO4 and HNO3 are volatile and the acidic solutes which formed them leave
the solution over time, resulting in a decrease in acidity. Thus, we can never really know the
concentration of these acids accurately. For this reason, simply diluting a concentrated solution of
these acids never makes the diluted solution a standard solution because we never really knew the
concentration of the original solution accurately enough. The only way to produce a standard
solution of these common acids is to perform a titration between the acid and a primary basic
standard.

Neutralisation reactions and acid-base titrations

Acid + base -> salt + water

Net ionic: H+ + OH- -> H2O

Acid + carbonate -> salt + water + carbon dioxide

Net ionic: 2H+ + CO32- -> H2O + CO2

pH salts and indicator choice
Nature of Nature pH of salt Example Reason for pH
acid of base
Strong Strong 7 NaCl Neither ion of salt undergoes
hydrolysis. Na+ is neither acidic or basic
and Cl− is too weak a conjugate base
since it comes from a strong parent
acid.
Strong Weak Less than 7 (4- NH4Cl NH4+ is a conjugate acid of a weak base
6) and is therefore a moderately weak
acid and will undergo hydrolysis in
water, producing H3O+. The Cl− ion will
not undergo hydrolysis
Weak Strong Higher than 7 NaCH3COO The Na+ is neither acidic nor basic in
(8-11) nature. CH3COO− is the conjugate base
of a weak acid and is thus a moderately
weak base and will undergo hydrolysis
forming the OH− ion.
Weak Weak Difficult to NH4CH3COO Both ions are conjugate acids/bases of
predict weak bases/acids. Both will undergo
(possibly close hydrolysis and the pH of the solution
to 7) will depend upon relative strength of
ions.

Indicators
In titration, the role of the indicator is to change colour very close to when the acid and base have
just been neutralized (i.e., at the equivalence point when all of the acid and base are consumed
because they are present in the correct mole ratios).
NB: for strong acid and base, indicator could be phenolphthalein because of its higher accuracy
(more distinct colour change).

- There is a point during an acid-base reaction at which [H+] = [OH-]. This is called the
equivalence point.
- The point at which the indicator changes colour is the end point.
- The closer the two points are to each other, the smaller the titration error.
- Choosing an appropriate indicator is therefore critical in accurately determining an unknown
concentration. The pH of the salt must be considered when choosing an indicator.

Accuracy and reliability

Validity: does it achieve the aim? The aim is to determine quantitatively the concentration of an
unknown acid or base. Therefore, any factor that reduces the chance of achieving an accurate result
will reduce the validity.

The final determination of the concentration of the unknown will only be accurate if you:

1. Choose the most appropriate equipment and use it correctly (to reduce systematic errors).
2. Take measurements correctly to reduce random errors such as parallax error.
3. Control variables (e.g., depth of colour change at end point) i.e., be consistent.
4. Choose an appropriate indicator (which changes colour close to equivalence point).

Systematic and random errors

Systematic errors are those that cause the measured results to differ from the “true” value by some
consistent amount in the same direction. They affect the accuracy of the results but not the precision
or reliability.

Random errors are those that cause a broader spread in repeat measurements. They may cause an
individual measurement to increase or decrease by an inconsistent amount.

Potential errors
Judge colour change consistently (end-point colour): in each titre, ensure the same volume of
solution is placed in the conical flask and that the colour at the endpoint is similar in depth. Placing
the flask on a white tile and retaining samples for colour comparison are good ideas.

Rinse glassware appropriately: rinse equipment used to accurately measure volume (burette,
pipette) with water and then filling solution – ensures water hasn’t diluted. Rinse conical flask with
distilled water since precise number of moles of acid and base have already been measured.

Scenario Effect on Unknown

Known diluted Decrease no. moles of known, therefore more volume
(burette or pipette rinsed with water only) of known is required for neutralisation.
or Increase number of moles of unknown, therefore
Too much unknown added fewer moles of known required for neutralisation
(eg conical flask rinsed with filling solution)
Unknown diluted Decrease no. moles of unknown, therefore more
(eg burette or pipette rinsed only with water) volume of unknown is required for neutralisation.
or Increase number of moles of known, therefore fewer
Too much of known added moles of unknown required for neutralisation
(eg conical flask rinsed with filling solution)
Equivalence point using pH curves
- Changes in the pH od the solution in the conical flask can be used to determine the
equivalence point, rather than using the colour change of an indicator. This is particularly
useful if the solutions being analysed are coloured.
- A pH probe could be used to measure pH as the solution from the burette is being added to
the conical flask.
o Alternatively, a drop-counter and pH probe could be used in conjunction with a data
logger to log the pH change in the flask vs volume added from the burette – this is
called a titration curve.
Type of titration curve Nature of acid and base involved

High initial pH implies strong base initially in conical flask. As acid

is slowly added, the pH falls gradually until a point when one
more drop of acid is enough to completely react with the base.
This causes the sudden drop in pH (vertical line).

Equivalence point at pH = 7 means that the salt produced is

neutral. Since the base was strong, the acid must also be strong,
as strong acids and bases produce neutral salts.

After the sudden drop, the pH gradually decreases as excess acid

is added.

This curve also shows the reaction between a strong acid and a
strong base (see above) but the acid was in the conical flask and
the base was added from the burette.

Initial pH > 7. The conical flask contains a base.

However, pH is not as high as in the first example. This suggests

that a weak base was used.

The substances are 1 M (text above table). If a strong base had

been used, the initial pH would have been 13.

At equivalence pH < 7, ie the salt produced is acidic. This is

further evidence for a weak base initially in the conical flask.
Acidic salts are made when strong acids neutralise weak bases.
The weak base produces a fairly strong conjugate acid, which is
why the pH at equivalence is around 5.

This curve is also for a weak base and strong acid, but the acid
was present in the flask initially and base slowly added to it. The
equivalence point is still around 5.
 Now we have a strong base initially present (see high pH) but the
pH at equivalence is in the basic range, indicating a basic salt has
been produced. Thus, the acid added must have been a weak
acid, which produce fairly strong conjugate bases-hence the high
pH at equivalence.

Polyprotic acid titration curves

Titrating the weak polyprotic acid H3A with a strong base: 3 equivalence points.
Thermometric and conductive titrations
Thermometric titrations

Benefits:

- Coloured solutions can be analysed

- Test in non-destructive
- Subjective matter of colour choice is removed

Conductivity titrations
Reaction Graph Stages Concentration Conductivity
of mobile ions
Strong acid, Initially High [H3O+] High
strong base
Gradual Decrease in Decreases
addition of [H3O+] due to
base neutralisation
Equivalence [H3O+] = [OH-] At minimum:
point only larger,
slow-moving
ions present
Continued High [OH-] Increases
addition of
base
Strong acid, Initially High [H3O+] High
weak base
Gradual Decrease in Decreases
addition of [H3O+] due to
base neutralisation
Equivalence [H3O+] = [OH-] At minimum:
point only larger,
slow-moving
ions present
Continued Low [OH-] Remains
addition of approximately
base constant
because of
partial
ionization weak
base and
 minimal
concentration
of OH- ions
Weak acid, Initially Low [H3O+] Low: the partial
strong base ionization of
the weak acid
produces low
concentration
of mobile H3O+
ions
Gradual Neutralises acid Gradually
addition of to produce less increasing due
base mobile to increasing
conjugate base concentration
ions of conjugate
base ions
Equivalence [H3O+] = [OH-] Significant
point because of a
high
concentration
of conjugate
base ions
Continued High [OH-] Increases
addition of
base

Back titrations
Use in situations including:

- The substance analysed is insoluble

- The substance analysed is volatile and would evaporate during titration

In back titration, a deliberate excess of a reagent is added t react with all of the acid or base in the
test sample. After the reaction is complete, a regular titration is performed between the remaining
chemical in excess and a standard solution.
Other types of titration
Redox titration
A variety of chemical reagents can be used as indicators in such titrations.

Titrations involving a series of reactions that lead to an endpoint

A good example of this type of titration is the ‘Winkler’ method for determining the concentration of
dissolved oxygen in water samples.

The amount of dissolved oxygen is an indicator of the cleanliness of water. A high level of dissolved
oxygen in a water sample shows that the water is clean and unpolluted. In an experiment to
determine the dissolved oxygen levels in some river water, the Winkler method was used.
Ka and pKa

Buffers
Buffers are solutions that resist changes in the pH when small additional amounts of acid or base are
added.

Buffers are made by mixing equimolar solutions of a weak acid with its conjugate base, or a weak
base with its conjugate acid.

Procedure to make a buffer:

Mix 50 mL of 0.1 M CH3COOH and 50 mL of 0.1 M NaCH3COO (where Na+ is a spectator ion). Since
both solutions are of the same concentration and volume, the number of moles of CH3COOH and
CH3COO- are the same.

The composition of the buffer (i.e. which weak acid/conjugate base is present) determines the pH of
the buffer system.

- Acidic: weak acid and conjugate base

- Basic: weak base and conjugate acid

pH = pKa + log10[A-]/[HA]

Since A- and HA are equimolar with equal volumes, log10[A-]/[HA] = log101 = 0

Thus, pH = pKa
Equilibrium system in buffers
Equation: CH3COOH ⇌ CH3COO− + H+
Solution of ethanoic high very low very low
acid alone ~ 99% ~ 1% ~ 1%
(not a buffer)
Buffer solution equal equal still very low
(due to addition of
equimolar amount of
NaCH3COO)

Buffers in natural systems

- The pH of blood of animals must be maintained very close of 7.4. Even small changes in the
pH would result in death. Blood contains a buffer based on the weak acid, carbonic acid and
the hydrogen carbonate ion. The acid is in equilibrium with the conjugate base as simplified:
H2CO3 <-> HCO3- + H+
- If the [H+] in the blood rises by the addition of an acid to the blood, the equilibrium is
disturbed. A shift to the left occurs as we have added more of the H+ and as a result, much of
the additional H+ ions react with base HCO3−, thereby minimising the disturbance caused by
the increase in [H+]. Therefore, the pH level will not fall considerably.
- If the [OH−] in the blood rises by the addition of a base, the [H+] on the right decreases, as
the OH− and H+ react to produce water. Hence more of the carbonic acid ionises as the
equilibrium shifts to the right to minimise the disturbance, thereby maintaining the pH level.

Analysis of household substances

- Common household substances (wine, juices, coffee, medicines, etc) all have pH values that
affect their effectiveness.
- Medicines need to maintain pH to be absorbed in certain parts of the digestive system /
medicinal interactions.
- Wine tastes are affected by acidity.
- Juices can have their vitamin C measured by titrations.
- Soft drinks contain various acids and have a pH of approx. 3. They contain carbonic acid
(dissolved CO2), phosphoric acid (preservatives), and sometimes citric acid.

Alternative titrations are necessary:

- Juices contain multiple acids and are rarely colourless – conductometric titrations are used.
- Medicines often contain very weak acids (such as aspirin) – back titrations or conductometric
titrations are used.
- Medicines such as antacids have weak bases (carbonates) – back titrations are used.
Application of acid-base analysis
Digital instruments used
Probes and digital measurements allow monitoring to be accurate, reliable and precise – they do
require regular calibration. It does not alter the analytes chemically. It also allows industrial
processes to be automated or monitored on very large scales.

Industrial analysis
- Many industrially produced fertilisers are the products of neutralisation reactions.
- These reaction vessels can be monitored using industrial pH probes as a method of knowing
when reactions are complete or which reagent needs increasing.
- Ammonium nitrate is reacted with nitric acid in a neutraliser. Here the pH is measured to
ensure that indeed the correct mixture has been achieved.
- Ammonium nitrate has a pH of 5.3 as HNO3 is a strong acid.
- Other aspects of this production need to be monitored as NH4NO3 is an extremely effective
explosive that will combust without the presence of oxygen.

Aboriginal and Torres Strait Islander Analysis

Bull ants and bracken fern

- Bracken fern has alkaline juices in the leaves when crushed.

- Bull ants inject painful formic acid as it stings.
- The alkali juices of the bracken fern have been known to neutralise the formic acid.

Let BOH be the alkaline substance in the bracken fern:

HCOOH (aq) + BOH (aq) -> BHCOO+ (aq) + H2O (l)