Key Knowledge

energy profile diagrams and the use of H

notation including: activation energy;
alternative reaction pathways for catalysed
reactions; and deduction of H for an
overall reaction given energy profiles or H
of two related reactions

Chemical energy
The chemical energy of a substance is
made up of its potential energy and kinetic
energy.
Potential energy attraction between
nuclei and electrons
Repulsion between
electrons
Repulsion between
nuclei

 Kinetic energy - movement of particles

Movement of electrons
Vibrations of and rotations around
bonds.
Actual movement in the substance
(gases vs liquids and solids)

Enthalpy
The chemical energy of a substance cannot
be directly measured, but it can be
determined theoretically.
It is known as enthalpy or heat content and
has the symbol H.
However, a change in enthalpy, H, for a
chemical reaction can be determined.

Measuring enthalpy
The change in temperature, T, gives an
indication of change in enthalpy.
If temperature increases during the
course of a reaction, then heat energy is
being released to the surroundings by the
reaction
So enthalpy of the products is less than
enthalpy of reactants.

Energy profile diagram

Exothermic reaction
We can visualise this change using an
energy profile diagram:

 If temperature decreases during the

course of a reaction, then heat energy is
being absorbed from the surroundings
by the reaction

So enthalpy of the products is greater

than enthalpy of reactants.

Energy profile diagram

endothermic reaction
To visualise the decrease in enthalpy when a
temperature decrease occurs we can also
use an energy profile diagram:

Definition of H
H = H(products) H(reactants)
So if the temp increases,
H(products) < H(reactants),
So H is negative
This is an exothermic reaction
If the temp decreases
H(products) > H(reactants),
So H is positive
This is an endothermic reaction

 We can recognise an exothermic

reaction by the increase in temperature
of the surroundings
eg Combustion reactions, neutralization
reactions
Endothermic reactions are much less
common. The temperature of the
surroundings decreases
eg chemical cold packs

Activation energy
The activation energy is the amount of
energy required to break the bonds of the
reactants.
It is the amount of energy needed to start
a reaction.
eg a spark to start
a fire, or to burn fuel
in an engine.

Reversing the reaction

If we were to turn products back into
reactants, then the activation energy could
still be determined from the energy profile
diagram:

Catalysts and activation energy

A catalyst increases the rate of a reaction.
It does this by creating an alternative
energy pathway for the reaction.
This pathway has a
lower activation
energy than the
original reaction.

Sample exam question energy profile

diagrams
The reaction A + B C involves a two step process.
A + B X: H positive and X C; H negative
Which one of the diagrams below best represents the
energy changes during the course of the reaction?

VCAA June
2007 Q19

Key Knowledge
energy profile diagrams and the use of H
notation including: (activation energy;
alternative reaction pathways for catalysed
reactions;) and deduction of H for an
overall reaction given energy profiles or H
of two related reactions

Thermochemical equations
More information about a reaction can be
included in a chemical equation by adding
the value of the change in enthalpy.
This creates a thermochemical equation
eg combustion of methane:
CH4(g) + 2O2(g)

CO2(g) + 2H2O(l) ; H = -890 kJ mol-1

In a thermochemical equation, the change

in enthalpy is directly related to the actual
amounts of reactants and products in the
equation.
This is because H is calculated from the
enthalpy absorbed when reactant bonds
are broken and the enthalpy released
when product bonds are made.
Bond breaking is endothermic
Bond making is exothermic

 The more reactants and products there are,

the more bonds there will be broken and
made and the greater the difference between
H(products) and H(reactants), H, there will
be.
Remember that

H = H(products) H(reactants)
Enthalpy for x mol
of reactants

Enthalpy for 2x mol of

reactants

Energy put in to break

reactant bonds

+200 kJ

+400 kJ

Energy released when

product bonds are formed

-600 kJ

-1200 kJ

-400 kJ

-800 kJ

 So while
CH4(g) + 2O2(g)

CO2(g) + 2H2O(l) ; H = -890 kJ mol-1

When the amounts are doubled:

2CH4(g) + 4O2(g)
2CO2(g) + 4H2O(l) ;
H = -1780 kJ mol-1
and halved:
CH4(g) + O2(g)

CO2(g) + H2O(l) ; H = -445 kJ mol-1

Also the reverse reaction is endothermic

CO2(g) + 2H2O(l) CH4(g) + 2O2(g) ; H = +890 kJ mol-1

Calculating H
The thermochemical equation for a
reaction can be used to calculate energy
released when any amount of reactants
react together.
Ratios are the key here:

H HEis the enthalpy of reaction in

which=n1 mole of reactant reacts
n1 E isn 2the energy
released/absorbed by n2 mole
reactant

of

Example calculating H
Find H for the reaction
2CH3OH(l) + 3O2(g) 2CO2(g) + 4H2O(g)
Given that the combustion of 0.2 mol of
methanol releases 145 kJ of energy.
H E
=
n1 n 2
H
2
H

145
0.200
145 2
1450kJ
0.200

Hess Law
This law states that the enthalpy
difference for a reaction will be the same,
no matter what pathway the reaction
takes.

 This leads us to being able to determine

H for two related reactions.
So, if A B ; but H1 is unknown, we can
use
A C ; H2 and C B ; H3
to work out H1,
since H2 + H3 = H1

Example using two related

equations to find H

Calculate the enthalpy of reaction for the formation of

NO2(g) according to the equation:
N2(g) + 2O2(g) 2NO2(g) H1 = ?
given the following thermochemical equations:
N2(g) + O2(g) 2NO(g)
H2 = +180 kJ mol-1
2NO2(g) 2NO(g) + O2(g) H3 = +112 kJ mol-1

Solution:
Reverse 2nd equation:
2NO(g) + O2(g) 2NO2(g) H4 = -112 kJ mol-1
Then add to 1st equation
N2(g) + O2(g) 2NO(g)
H2 = +180 kJ mol-1
When these are added together (and cancelled out) you
get the required equation, so you can also add the H
values.
2NO(g) + O2(g) + N2(g) + O2(g) 2NO2(g) + 2NO(g)
N2(g) + 2O2(g) 2NO2(g) ; H1 = H2 + H4
= +180 +(-112)
= +68 kJ mol-1

Sample exam question - H

The energy diagram below relates to the following two
reactions.

The enthalpy change for the reaction

NO2(g) N2O4(g) will be
A. +58 kJ mol-1
B. +29 kJ mol-1
C. -58 kJ mol-1
D. -29 kJ mol-1

VCAA Nov 2010 Q 15

Key Knowledge
collision theory and factors that affect the
rate of a reaction including temperature,
pressure, concentration and use of catalysts,
excluding: a formal treatment of the
Maxwell-Boltzmann distribution, reaction
mechanisms and rate laws

Collision Theory
For a reaction to occur, the molecules must
collide.
In a successful reaction, the molecules
collide
1. With the correct orientation
2. With enough energy to achieve the
activation energy (overcome the
activation energy barrier).

Colliding with correct orientation

Achieving the activation energy

Maxwell-Boltzmann distribution
While this does not have to be known
formally, it is useful to see another
representation of meeting the activation
energy

Rate of reaction
The rate of reaction is equal to the change in
concentration of reactants, or products per
unit time.
The greater the proportion of collisions that
are successful, the greater the rate will be..

Typical concentration-time graphs

Factors affecting the rate of a reaction

Factor

Affect of increase

Collisions

Increase in average kinetic

energy of particles

Increase in number and

energy of collisions

More particles available to react

Greater number of
collisions

Surface area

More particles at surface,

therefore available to react

Greater number of
collisions

Pressure

More particles available in a

given volume

Greater number of
collisions

Catalyst

Activation energy is lowered, so

greater proportion of particles
have enough energy to react

Increased proportion of
successful collisions

Temperature

Concentration

Summary
To increase the rate of a reaction
Increase the temperature
Increase concentration of an aqueous solution
Increase pressure of gases
Make particles of solids smaller
Use a catalyst (if possible)

Catalysts
A catalyst increases the rate of reaction by
providing an alternative reaction pathway
with a lower activation energy.

 With a lower Ea, a greater proportion of

particles have enough energy to react.

Sample exam question rates of

reaction

A 2.0 g piece of Mg ribbon was added to a known volume of

2.0 M HCl. The volume of H2(g) produced during the
reaction was measured and recorded. The graph below
shows the result of this experiment.

(b) In a second experiment, 2.0 g of Mg powder was added

to the same volume of 2.0 M HCl as used in the first
experiment. On the axes above, sketch the expected graph of
volume of hydrogen against time for this second
experiment. Give an explanation for the shape of your graph.
VCAA Nov 2008 Q1

Key Knowledge
equilibrium: representation of reversible
and non-reversible reactions:
homogeneous equilibria and the
equilibrium law (equilibrium expressions
restricted to use of concentrations), Le
Chateliers Principle and factors which affect
the position of equilibrium

Reversible reactions
Changes of state:
Eg H2O(l) H2O(g)
indicates a reversible reaction
When heat is added, the liquid water
evaporates,
When heat is removed (ie cooled), the reverse
reaction can occur gaseous water condenses.

Incomplete reactions
Some reactions can be reversed
As a result these reactions appear to be
incomplete it is impossible to achieve a 100%
yield.
A reaction may be reversed if the reactants and
products stay in contact with one another.

 The reaction between copper sulfate and water is

reversible:
CuSO4(s) + 5H2O(l) CuSO4.5H2O
white
blue

Rechargeable batteries involve reversible

reactions.
The forward reaction releases energy while the
backward reaction requires energy.

Reaching equilibrium
When two reactants are mixed, they react to make
products
As soon as products are made, there is a chance
that they may collide and make reactants.
As the concentration of products increases, the
chance of the backward reaction occurring
increases.

As the concentration of products increases, the

rate of the backward reaction gradually increases.
Similarly, the rate of the forward reaction is
decreasing because the concentration of reactants
is decreasing.
Finally the rate of the forward reaction becomes
equal to the rate of the backward reaction this is
called equilibrium.

Dynamic equilibrium
At equilibrium, the reaction has not stopped.
So, it is termed dynamic (still proceeding)
The macroscopic properties of the reaction
become constant eg
Colour
pH
Temperature
Gas pressure

Only a closed system can reach equilibrium

A closed system is a reaction in a sealed container
nothing can enter or escape.
If the products can leave the reaction vessel, the
reaction cannot be reversed.
Eg The reaction between CaCO3 and HCl does not
reach equilibrium because the CO2 escapes

Homogeneous equilibria
This is when all the reactants and products
are in the same state.
All the reactants and products could be
gaseous, or in aqueous solution or liquid
(organic reactions such as esterification)
The opposite of homogeneous equilibria is
heterogeneous equilibria.

Sample exam questions - equilibria

Phosphorus(V) chloride decomposes to form PCl3 and Cl2
according to the equation
Some gaseous PCl5 is placed in an empty container. When
equilibrium is reached, the mass of the gas mixture, compared to
the initial mass of PCl5, is
A. halved
B. unchanged
C. one and a half times greater
D. doubled.
VCAA Nov 2008 Q10

2. When 2-propanol reacts to form an equilibrium

mixture with propanone and hydrogen, which
one of the graphs below best represents how the
rates of the forward and back reactions change
over time?

VCAA June 2007 Q7

Key Knowledge
equilibrium: representation of reversible
and non-reversible reactions: homogeneous
equilibria and the equilibrium law
(equilibrium expressions restricted to
use of concentrations), Le Chateliers
Principle and factors which affect the
position of equilibrium

The equilibrium law

A system at equilibrium can be identified by a
constant.
This is called the equilibrium constant, Kc.
The equilibrium constant is temperature
dependent
ie it only changes if the temperature changes.

The equilibrium constant expression

For a general reaction
aA + bB + pP + qQ +
The equilibrium constant, K, is expressed as:

[ P] [Q ] ...
a
b
[ A] [ B] ....
p

examples
For the equation
PCl5(g) PCl3(g) + Cl2(g)
The equilibrium constant expression is
[PCl3 ][Cl 2 ]
K=
[PCl5 ]
For the equation
CO(g) + 2H2(g) CH3OH(g)
The equilibrium constant expression is
K

[CH 3OH ]
[CO ][ H 2 ]2

 The equilibrium constant that we will study

this year is a concentration fraction
Concentration fractions can be calculated for
the reaction at any time, not just when it is at
equilibrium, but these are then not called the
equilibrium constant! (they are just
concentration fraction)

Using the value of K to determine whether

equilibrium has been reached
When the reaction is approaching equilibrium,
the value of the concentration fraction will
change with time.
As the reaction proceeds, more products are
being made and the value of the fraction will
increase (numerator is increasing)
When the reaction has reached equilibrium, the
concentration fraction (equilibrium constant)
will remain constant.

A point to note
The direction that is defined as forward is from
left to right as the equation has been written.
If the equation is written around the other way,
then the equilibrium constant is rewritten (it is
the inverse)

What does the value of the equilibrium

constant mean?
The larger the equilibrium constant, the larger
the ratio of products to reactants
When the reaction has almost gone to
completion, it will have a very large value of K
When the reaction hardly proceeds (ie mostly
reactants are present), the value of K will be
very small.

Calculations
Calculate the equilibrium constant for the
reaction:
PCl3(g) + Cl2 PCl5(g) at 20 C
Given that the equilibrium concentrations of
the species involved are :
[PCl3] = 1.50 10-3 M, [Cl2] = 8.25 10-2 M,
[PCl5] = 1.67 M

Solution
K=

[PCl5 ]
[PCl3 ][Cl2 ]

1.67
=
3
1.50 10 8.25 10
= 1.34 104 M-1

Example 2
Calculate the equilibrium concentration of
Ag+(aq) ions, given the following:
Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)
K = 1.60 104 M2 at 25 C,
[NH3] = 5.00 10-3 M and [Ag(NH3)2+] = 0.401
M

Solution [Ag(NH ) + ]
3 2
K=
+
2
[Ag ][NH3 ]
0.401
+
[Ag ] =
= 1.00 M3 2
4
1.60 10 (5.00 10 )

Example 3
4.00 mol of HI was admitted to an evacuated
2.0 L reaction vessel and allowed to reach
equilibrium at constant temperature
according to the equation:
H2(g) + I2(g) 2HI(g)
At equilibrium 0.250 mol of I2 had formed
(a) Determine the equilibrium concentrations
of all species
(b) Determine the equilibrium constant for
this reaction

2.00 L

4.00

[HI]2
[H 2 ][I 2 ]

Example 4
1.800 mol of ammonia is introduced into an
evacuated 5.00 L vessel and allowed to come
to equilibrium. The concentration of Nitrogen
at equilibrium was determined to be
0.0435M.
Calculate the equilibrium constant for the
reaction shown below, given that the
temperature remained constant at 160 C
throughout the experiment.
N2(g) + 3H2(g) 2NH3(g)

solution
5.00 L

Sample exam question - The

Equilibrium law
The concentrations of reactants and products were
studied for the following reaction
H2(g) + F2(g) 2HF(g); K = 313 at 25 C
In an experiment, the initial concentrations of the
gases were [H2] = 0.0200 M, [F2] = 0.0100M and [HF]
= 0.400M. When the reaction reaches equilibrium at
25 C, the concentration of HF will be
A. 0.400 M
B. 0.420 M
C. Between 0.400M and 0.420 M
D. Less than 0.400 M

Key Knowledge
equilibrium: representation of reversible
and non-reversible reactions: homogeneous
equilibria and the equilibrium law
(equilibrium expressions restricted to use of
concentrations), Le Chateliers Principle
and factors which affect the position of
equilibrium

Changing the equilibrium position of a

reaction
When a closed system is at equilibrium, products
and reactants are both present in the mixture.
When a change is made to a system at
equilibrium, the system will adjust to partially
oppose the change
This is called Le Chateliers principle

Changes that could be made to a

system at equilibrium
1.
2.
3.
4.
5.
6.
7.
8.

Add or remove reactants

Add or remove products
Decrease volume of a gaseous system
Increase volume of a gaseous system
Increase volume of an aqueous system
Increase the temperature
Decrease the temperature
Add a catalyst

Adding a reactant
The addition of one reactant will temporarily
increase the concentration of that reactant.
Since all reactants are still present in the system,
the system will act to oppose the change by
making the concentration of the reactant
decrease by reacting it with the other reactant
More products will be made
The position of equilibrium has moved to the
right
OR there is a net forward reaction

Removing a reactant
Concentration of that reactant is temporarily
decreased
The system will act to oppose the change by
making the concentration of the reactant increase
by making products turn into reactants
(backward reaction)
More reactants will be made
The position of equilibrium has moved to the left
OR there is a net backward reaction

Adding a product
This has exactly the same effect as removing a
reactant
The position of equilibrium moves to the left

Removing a product
This has exactly the same effect as adding a
reactant
The position of equilibrium moves to the right

Gaseous reactions
Decreasing volume of system
The concentration of all reactants and products is
temporarily increased (same amounts in smaller
volume)
The system will act to oppose the change by
making the concentration of particles decrease
What follows is dependant on the particular
reaction:

1. There are more reactant particles than

product particles
eg N2 + 3H2 2NH3
4 particles
2 particles
To decrease the concentration of particles
overall, the system must convert reactants to
products
The position of equilibrium moves to the
right

2. There are equal numbers of reactant

particles and product particles
eg I2 + H2 2HI
2 particles 2 particles
There is nothing the system can do to
decrease the concentration of particles
overall,
The position of equilibrium does not move

3. There are less reactant particles than

product particles
eg N2O4 2NO2
1 particle
2 particles
To decrease the concentration of particles
overall, the system must convert products to
reactants
The position of equilibrium moves to the left

Increasing the volume of a system

The concentration of all reactants and products is
temporarily decreased (same amounts in smaller
volume)
The system will act to oppose the change by
making the concentration of particles increase
The position of equilibrium will move
depending on the equation (as before)

Increasing the volume of an aqueous

system ( by adding water)
This is the same as increasing the volume of a
gaseous system.
The concentration of all reactants and products
will initially be decreased, so the system will act to
oppose the change in which ever manner
matches the stoichiometry of the particular
reaction.

Sample exam question Le Chateliers

Principle
The following reaction systems are at equilibrium in
separate sealed containers. The volumes of the
containers are halved at constant temperature. Which
reaction has the largest percentage change in the
concentration fraction immediately after the volume
change?
A. N2O4(g) 2NO2(g)
B. H2(g) + I2(g) 2HI(g)
C. 2CO2(g) 2CO(g) + O2(g)
D. CO(g) + 2H2(g) CH3OH(g)
VCAA Nov 2010 Q7

Solution:

Key Knowledge
equilibrium: representation of reversible
and non-reversible reactions: homogeneous
equilibria and the equilibrium law
(equilibrium expressions restricted to use of
concentrations), Le Chateliers Principle
and factors which affect the position of
equilibrium

Changing the temperature

This is the only change that can affect the value of
Kc
It is a permanent change, unlike those described
earlier.
The value of H influences the direction in which
the equilibrium moves

Exothermic reaction
eg N2 + 3H2 2NH3 H = -92 kJ mol-1
When the products are made, heat is also released
(could think of it as a product)
If the temperature is increased, it is like adding a
product (adding heat), so the position of
equilibrium moves to the left (to oppose the
change)
The extra heat energy is used in the backward
reaction that occurs (but the change is not
undone)

 If the temperature is decreased, it is like

removing a product (removing heat), so the
position of equilibrium moves to the right (to
oppose the change)
Extra heat energy is produced in the forward
reaction that occurs.
So An exothermic reaction is favoured (more
products made) by decreasing the temperature

Endothermic reaction
eg NH4NO3(s)+ aq NH4+(aq)+ NO3-(aq) ;
H = +25 kJ mol-1
Heat can be considered to be a reactant (it is
used to make products)
If the temperature is increased, it is like adding
a reactant (adding heat), so the position of
equilibrium moves to the right (to oppose the
change)

 If the temperature is decreased, it is like removing

a reactant(removing heat), so the position of
equilibrium moves to the left (to oppose the
change)
So An endothermic reaction is favoured (more
products made) by increasing the temperature

Using graphs to indicate these

changes to an equilibrium system
Graphs of concentration vs time are often
used to track the response of a system at
equilibrium to a change.
These are typified by a horizontal line at the
points where the system is at equilibrium.

Graph examples
Addition of a product

At time = 10 mins, some H2 was added. The

system acted to oppose the change and used up
the H2 while also making CH4 in a 3:1 ratio

Change in volume
2NO2 N2O4

The volume was decreased, so the concentration of

both reactant and product increased
instantaneously.
[N2O4] continued to increase, while [NO2] decreased
(in a 1:2 ratio) as the new position of equilibrium was
reached.

Change in temperature

At time = 4 mins, the gradual change in all

concentrations suggests a change in temperature.
Since the reaction is endothermic and the forward
reaction is favoured, we can conclude that the
temperature increased.

Catalysts and equilibrium

The addition of a catalyst does not
change the position of equilibrium in
any way.
It does, however, allow equilibrium to
be reached more quickly, as it lowers
the activation energy and increases the
rate of both the forward and backward
reactions.

Sample exam questions temperature

changes and graphs
The following gaseous equilibrium is established at high
temperatures in the presence of a finely divided Ni catalyst.
A particular reaction is carried out using equal amounts of CH4(g)
and H2O(g). Which one of the following sets of changes in
conditions would lead to the greatest increase in the proportion of
the reactants converted to products?

A.

Volume of
Temperature
reaction vessel
increased
increased

B.

increased

decreased

C.
D.

decreased
decreased

increased
decreased

VCAA Nov 2008 Q1

2. Hydrogen iodide dissociates into its elements

according to the following equation
2HI(g) H2(g) + I2(g) H = +9 kJ mol-1
A mixture of H2(g), I2(g) and HI(g) rapidly comes
to equilibrium in a 2.0 L container. After the
reaction has been at equilibrium for 10 minutes,
the volume of the container is suddenly reduced
to 1.3 L at constant temperature. Which one of the
following graphs best represents the effect of this
decrease in volume on the concentration of the
gases in the mixture?

Key Knowledge
pH as a measure of strength of acids and
bases; Kw, (Ka for weak acids)
equilibrium: representation of reversible
and non-reversible reactions:
homogeneous equilibria and the
equilibrium law (equilibrium expressions
restricted to use of concentrations), Le
Chateliers Principle and factors which
affect the position of equilibrium

The self-ionisation of water

Water is both a weak acid and a weak base, so in
any aqueous solution, water molecules react
together:
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
This is called the self-ionisation of water
The equilibrium constant for this reaction is

 The equilibrium constant for this reaction

would be written as

Since the concentration of water is vastly

greater than that of H3O+ or OH-, it can be
removed from the equation to become
part of a new constant, the ionisation
constant of water, Kw

Kw = [H3O+][OH-]

Temperature dependence of Kw
The temperature of the water must be stated
before a value can be assigned.
At 25C, Kw = 1.0 10-14 M2

The self-ionisation of water is an endothermic

reaction
H2O(l) + H2O(l) H3O+(aq) + OH-(aq); H = +57 kJ mol-1

So as the temperature increases, Kw increases and

as the temperature decreases, Kw decreases.

How Kw changes with temperature

Temperature ( C)
0
5
15
25
35
45
55

Kw (M2)
1.14 10-15
1.85 10-15
4.51 10-15
1.00 10-14
2.09 10-14
4.01 10-14
7.29 10-14

pH
Recall that pH is a measure of the acidity
of an aqueous solution.
The lower the pH, the more acidic a
solution is
It is defined mathematically:

pH = -log10 [H3O+]

Finding pH from Kw
Kw = [H3O+][OH-]
Since [H3O+] = [OH-] in pure water,
then Kw = [H3O+]2
=1.0 10-14 M2
14
+
so [H3O ] = 1.0 10
= 1.0 10-7 M at 25C
Since pH = log10 [H3O+]
= log10 1.0 10-7 M
= 7

Acid, base, neutral

An acidic solution is defined as one in
which [H3O+] > [OH-]
In a neutral solution [H3O+] = [OH-]
And in a basic solution [H3O+] < [OH-]
At 25C, an acidic solution has a pH < 7,
neutral solution has pH= 7 and basic
solution has a pH > 7
BUT .

 pH is calculated only from [H3O+]

At 55C, Kw = 7.29 10-14 M2
So if [H3O+] = [OH-] in pure water (a
neutral solution),
14
+
then [H3O ] = 7.29 10
= 2.7 10-7
and pH = -log10(2.7 10-7 ) = 6.57
(not 7 )

 At 15C, Kw = 4.51 10-15 M2

so [H3O+] = 4.51 10 15
= 6.71 10-8
and pH = -log10(2.7 10-7 ) = 7.17
In summary, the pH of a neutral solution
is less than 7 above 25C and greater
than 7 below 25C.

Using Kw in other calculations

Just as pH = -log10 [H3O+] ,
also pOH = -log10 [OH-]
p in front of a quantity means that -log10
should be taken.
So pKw = -log10 Kw
The value of Kw can be used to calculate
pH of a basic solution

Kw = [H3O+][OH-] = 1.0 10-14 M2 at 25C

1.010-14
So [H3O+] = [OH - ]
1.010-14
or [OH-] = [H O+ ]
3

Also pKw = pH + pOH = 14

(This may be useful in some circumstances)

Sample exam question

The value of the ionisation constant, Kw, of a sample of
pure water at different temperatures is shown in the
graph below.

Which one of the following statements about the effect

of increasing temperature on the pH and acidity of
water is correct?
A. The pH is always 7 and the water remains neutral
B. The pH decreases and the water remains neutral
C. The pH decreases and the water becomes acidic
D. The pH increases and the water remains neutral.

Key Knowledge
pH as a measure of strength of acids and
bases; (Kw), Ka for weak acids
equilibrium: representation of reversible
and non-reversible reactions:
homogeneous equilibria and the
equilibrium law (equilibrium expressions
restricted to use of concentrations), Le
Chateliers Principle and factors which
affect the position of equilibrium

Acidity Constants
When an acid-base reaction is considered
as an equilibrium, an equilibrium constant
can be written for it.
For strong acids, the concentration of
reactants is very tiny due to complete
dissociation of the acid, however for weak
acids, there is a significant concentration
of both reactants and products.

Consider the equilibrium involving the dissociation

of the weak acid, ethanoic acid:
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Given that the concentration of H2O is virtually

constant, the equilibrium constant becomes an
acidity constant when [H2O] is taken out
The acidity constant will therefore be:
+

[H 3O ][CH 3COO ]
Ka =
[CH 3COOH]

What is the use of Ka?

The smaller the value of Ka is for an acid, the
weaker the acid is.
Table 12 in the data book gives you a range of Ka
values for some weak acids.
In that table, the ammonium ion, NH4+, with a Ka of
5.6 10 -10 is the weakest acid
and hydrofluoric acid, HF with
a Ka of 7.6 10 -4 is the
strongest acid, although
it is still very much a weak acid.
Stronger acids have larger Kas!

Table 12 on p11 of Data book

Calculating the pH of a weak acid

The expression for Ka and its value can be used
to find [H3O+] and hence the pH of any acid, but
it is most useful for a weak acid.
When a weak acid, HA, dissociates in water, we
assume that the concentration of H3O+ formed
is equal to the concentration of the conjugate
base, A-, of the weak acid
HA + H2O H3O+ + Aweak acid
conjugate base
We also assume that the concentration of HA
is effectively constant because it is such a weak
acid.

 This means that we can simplify the

expression
+
[H 3O ][A ]
Ka =
[HA]
+ 2

[H 3O ]
Ka =
[HA]
Since pH = -log[H3O+] we can find pH if we
know [H3O+]
to

[H3O+]

Ka [HA]

and pH = -log Ka [HA]

Percentage ionisation
Consider the dissociation of a weak acid in
water
HA + H2O H3O+ + A The acid is being ionised, so we can
calculate the percentage ionisation by using
[A-] and [HA]
% ionisation =

[A - ] 100
[HA] 1

Dilution of strong and weak acids

It is important to recognise that pH changes to a
different extent when strong and weak acids are
diluted.
The dissociation of a strong acid is represented
by the equation:
HA + H2O H3O+ + A When a solution of a strong acid is diluted 10
fold, [H3O+] is decreased by a factor of 10, so pH
increases by 1 unit.

 For a weak acid, the dissociation is an equilibrium:

HA + H2O H3O+ + A When a solution of a weak acid is diluted 10
fold, the water used for diluting is also a
reactant, so according to Le Chateliers Principle,
the system will adjust to partially oppose the
change
So the position of equilibrium moves to the right
and more H3O+ is made.
As a result the [H3O+] does not decrease as much
as for a strong acid and so the pH increases by
less than 1 unit.

Sample exam question- acid-base equilibria

The table below lists the pH of 0.10M solutions of
four different acids at 25 C
Acid

pH

I
II
III
IV

1.0
3.0
0.7
2.1

(a) Which one of the four acids listed has the

smallest Ka value?
VCAA Q3 Nov 2008

(b) Which acid must have more than one acidic

hydrogen per molecule? Give a reason for your
answer.

(c) Using the concentration and the pH of acid IV,

calculate the percentage ionization of acid IV in
the 0.10M solution

(d) Calculate the value of the ratio

[OH-] acid II/[OH-]acid I present in the
solutions of acids II and I.

(e) Samples of the solutions of acids I and IV are

diluted by a factor of 10. The resulting change in
pH units would be
(Tick one of
the boxes)

Greater for acid I than acid IV

Greater for acid IV than for acid I
The same for both acids

(f) Methanoic acid is a weak monoprotic acid.

(i) Calculate the concentration of a methanoic
acid solution that will have the same pH as acid IV.

(ii) The dissociation of methanoic acid in water

is exothermic. If a solution of the acid is heated,
will the pH of the solution increase, decrease or
remain constant? Explain

Key Knowledge
application of equilibrium and rate
principles to the industrial production of
one of ammonia, sulfuric acid, nitric acid:
factors affecting the production of the selected
chemical
waste management including generation,
treatment and reduction
health and safety considerations
uses of the selected chemical.

Assessed by one SAC (not exam)

Uses of sulfuric acid

Sulfuric acid is mostly used for making other
chemicals
Major industrial uses
Fertilizers
Paper manufacture,
Household detergents,
pigments, dyes and drugs.
car batteries (the electrolyte)
petroleum refining
metallurgical processes

Laboratory uses
Strong diprotic acid
H2SO4(l) + 2H2O(l) 2H3O+ (aq) + SO42-(aq)
Dehydrating agent
Used for removing water from gas mixtures
Can even remove water from compounds

Strong oxidant

Production of sulfuric acid

The Contact process

First stage (the burner)

Unless SO2 is used, the first stage is to burn
sulfur in air (O2)

Second stage (converter)

Sulfur dioxide is oxidised to sulfur
trioxide by oxygen

This is an exothermic equilibrium, so the

yield is increased by lower temperatures
and a catalyst (in layers) helps increase
the rate of reaction.

Third stage (absorption)

Sulfur trioxide is absorbed into sulfuric acid
Reaction between sulfur trioxide and water does
make sulfuric acid, but the reaction is highly
exothermic and results in a mist of acid being
formed

Absorption into sulfuric acid is less exothermic

H2SO4 is finally produced in two stages

in the absorption tower:
1. Sulfur trioxide is absorbed into Sulfuric
acid to make oleum

2. Oleum is mixed with water to make 98%

sulfuric acid

Compromises related to the control of

the equilibrium at stage 2
1. Increased rate of reaction is achieved by high
temp
But it is an exothermic reaction more
products made at only moderate temperatures
(400-450 C)
So a catalyst is used
2. Excess of reactants will favour products, so
excess air (oxygen - cheap reactant) is used

3. Gaseous reaction - greater rate at high

pressures
More products made at high pressures
But high pressure vessels are very expensive
Moderate pressures are used (1-2 atm) and
achieve a 99.5% conversion of SO2 to SO3
4.

V2O5 catalyst is used - not the most effective

catalyst, but catalysts can be poisoned and
other catalysts are too expensive.
Large surface area is used to make it more
effective.

Waste Management
Use of SO2 (a waste from other industries) is
environmentally and economically attractive.
Emission of SO2 into atmosphere is strictly
controlled, so conversion to SO3 must be
maximised
Double absorption process where gases are
recycled back to the converter is used for this
purpose

 Catalyst (vanadium(V) oxide) improved by

adding caesium (doping)
Low air pollution due to H2SO4 because it has a
high bpt (low vapour pressure)
Little solid waste is produced in the process
spent catalyst goes to landfill
Waste energy (exothermic processes) is used in
other locations on site

Health and safety

Risk
Transportation of
H2SO4

H2SO4 is highly
corrosive, can cause
severe burns to skin
and eyes, even
blindness

Controlled by
Minimising transport,
industries are situated close
together.
Hazchem signs are used to
warn of risks
To protect workers
protective clothing is worn
and work areas are well
ventilated

Health and safety cont.

Risk
SO2 and SO3 in the air
are major contributors
to acid rain and the
gases themselves are
hazardous.
Oleum is a highly
corrosive oily liquid
that produces sulfur
trioxide fumes.

Controlled by
Strict guidelines are set for
emission of gases.
Authorities monitor levels
of SO2 in the air and
prosecute as needed.
Safety clothing, gloves,
eyewear is needed and SO3
fumes contained

Other safety measures

In case of accidental spillage, it must be possible
to trap the fumes and minimize risk to workers
and the environment.
Acid spills are contained with earth, clay or
sand, then slowly diluted with water and finally
neutralised with limestone (CaCO3) or sodium
carbonate otherwise direct neutralisation
would release dangerous amounts of heat.

Sample exam question H2SO4

A particular industrial process involves the following steps

VCAA Q6 Nov 2009

a) It is possible to alter the temperature and pressure at

which reaction 2 occurs.
Would the rate of
reaction 2 become
higher, lower or
remain
unchanged?

The temperature of
reaction 2 is lowered
to 150C.
The pressure
of reaction 2 is
increased to 5 atm
by pumping more
B(g) and C(g)
into the reaction
vessel, at constant
temperature.

Would the
equilibrium
yield of reaction 2
become higher,
lower or
remain unchanged?

Would the value

of the
equilibrium
constant,
K, of reaction 2
become
higher, lower or
remain
unchanged?

b) Heat energy is released by reaction 2. Describe how the

heat energy could be used within this industrial
process.
c) i) Describe one waste management strategy, other than
recycling heat, employed in the industrial production of
your selected chemical.
ii) The following table includes a selection of HAZCHEM
labels used to identify dangerous goods.
(See next slide)
iii) State two uses of your selected chemical.

Key Knowledge
application of equilibrium and rate
principles to the industrial production of
one of ammonia, sulfuric acid, nitric acid:
factors affecting the production of the selected
chemical
waste management including generation,
treatment and reduction
health and safety considerations
uses of the selected chemical.

Assessed by one SAC (not exam)

Uses of ammonia, NH3

Ammonia is a weak base, it is a polar
molecule which can take part in hydrogen
bonding and so is very soluble in water.
Nitrogen is an element
in demand by plants, so
ammonia is commonly
used to make fertilizers.
eg ammonium nitrate:
HNO3(aq) + NH3(g)
NH4NO3(aq)

 Other uses of ammonia include

Household cleaning (cloudy ammonia)
Commercial refrigeration
Used to make a number of economically
important chemicals such as
nitric acid;
fibres, such as nylon,
explosives, such as ammonium nitrate;
pharmaceuticals, such as sulfonamides.

Production of ammonia
The Haber process

Raw materials
Hydrogen, H2 depends on the plant, but may
be obtained by steam reforming of natural
gas, or by electrolysis of water (if energy is
easily obtainable)
Nitrogen, N2 is always obtained from the air

The reaction:
N2(g) + 3H2(g) 2NH3(g) H = - 92 kJ mol-1

Flow chart of the Haber process

Compromises related to the control

of the equilibrium

1. Excess of reactants will favour products,

so excess nitrogen - cheap reactant is
used.
2. Increased rate of reaction is achieved by
high temp
But it is an exothermic reaction more
products made at only moderate
temperatures (400-450 C)
So a catalyst is used (porous Fe pellets)

3. Gaseous reaction - greater rate at high

pressures
More products made at high pressures
But high pressure vessels are very
expensive
High pressures are used (200 atm)
4. Fe catalyst is used - not the most effective
catalyst, but catalysts can be poisoned and
other catalysts are too expensive. KOH is
added to increase its efficiency.
The porous pellets have a surface area
which also makes it more effective.

Waste Management
If the H2 required to make NH3 is obtained
from natural gas, there are waste
management issues related to sulfurcontaining compounds, nitrogen oxides, NOx
and carbon monoxide.
Carbon dioxide is also a waste and this can be
sold to the food industry.
Wastage of raw materials is minimised by
almost complete conversion into ammonia by
recycling unreacted gases back into the
converter for further passes over the catalyst.

 Promoting energy efficiency is another way to

minimise waste. This is done by
using heat released from exothermic
reactions to generate steam to drive
turbines, compressors and other machines
using waste heat to preheat reaction gas
mixtures
using cold gases from the refrigerator
section of the plant to cool gas mixtures
before compression
computer control of all plant operations.

Health and safety

Risk

Controlled by

Toxic gas
An extreme irritant to the
eyes, respiratory system
and other parts of the
body.
Liquid ammonia can cause
frost bite and severe
burning.

Work areas must be well ventilated,

and workers involved with liquid
ammonia storage and transport
wear impervious gloves, face shields,
and rubber boots and aprons.
Breathing apparatus must
be available, and employees are
drilled in emergency procedures

Ammonia spills can be

Ammonia is allowed to disperse and
dangerous to a community areas are evacuated until safe

Other safety considerations

Hydrogen is explosive, so plants where the
H2 is produced must be carefully controlled
Carbon monoxide (produced during
hydrogen reforming) is toxic, so exposure to
this must also be carefully monitored.
Modern ammonia plants pay careful
attention to operating, safety and
maintenance routines.

Sample exam question NH3

A particular industrial process involves the following steps

VCAA Q6 Nov 2009

a) It is possible to alter the temperature and pressure at

which reaction 2 occurs.
Would the rate of
reaction 2 become
higher, lower or
remain
unchanged?

The temperature of
reaction 2 is lowered
to 150C.
The pressure
of reaction 2 is
increased to 5 atm
by pumping more
B(g) and C(g)
into the reaction
vessel, at constant
temperature.

Would the
equilibrium
yield of reaction 2
become higher,
lower or
remain unchanged?

Would the value

of the
equilibrium
constant,
K, of reaction 2
become
higher, lower or
remain
unchanged?

b) Heat energy is released by reaction 2. Describe how the

heat energy could be used within this industrial
process.
c) i) Describe one waste management strategy, other than
recycling heat, employed in the industrial production of
your selected chemical.
ii) The following table includes a selection of HAZCHEM
labels used to identify dangerous goods.
(See next slide)
iii) State two uses of your selected chemical.

Key Knowledge
application of equilibrium and rate
principles to the industrial production of
one of ammonia, sulfuric acid, nitric acid:
factors affecting the production of the selected
chemical
waste management including generation,
treatment and reduction
health and safety considerations
uses of the selected chemical.

Assessed by one SAC (not exam)

Uses of nitric acid

Nitrogen is an element in demand by plants,
so nitric acid is commonly used to make
fertilizers.
Reaction between nitric acid and ammonia
makes ammonium nitrate
HNO3(aq) + NH3(g)
NH4NO3(aq)

 Other uses of nitric acid include:

Explosives such as ammonium nitrate,
trinitrotoluene (TNT) and nitroglycerine
Production of Nitrate salts such as AgNO3
(silver plating and medicine), KNO3
(fertiliser), NaNO3(food additive), Sr(NO3)2
(fireworks)
Purification of precious metals
Production of dyes and perfumes
Production of paints, pigments, dyes
As a nitrating agent in organic synthesis.

Production of nitric acid

The Ostwald process
Nitric acid is made from ammonia in a 3
step process
NH3 NO NO2 HNO3

Step 1 Catalytic conversion of

ammonia to nitrogen(II) oxide

Preheated air is mixed with ammonia and

passed into a converter where oxygen
oxidises the ammonia to nitrogen(II) oxide,
NO
This stage uses a catalyst made up of layers of
a thin gauze woven from an alloy of 90%
platinum and 10% rhodium
High temperatures (820930C) and high
pressures (about 11 atm)

Step 2 Oxidation of nitrogen(II)

oxide

Nitrogen(II) oxide, NO, is oxidised by oxygen

to form nitrogen(IV) oxide, NO2
This is an exothermic equilibrium, so the
yield is increased by lower temperatures.
The temperatures used are low: below 30
C, since the rate of reaction actually
decreases with a decrease in temperature
(unusual)

Step 3 Absorption of nitrogen(IV)

oxide
Water is mixed with NO2 in an absorption
tower
Any NO formed in this reaction reacts with a
stream of air which is also introduced into
the tower. It is oxidised to nitrogen(IV)
oxide, (as in step 2) which then reacts with
water as above.

Points related to the control of the

equilibrium at stage 2

1. Low temperatures are used to maximize

equilibrium yield (does not reduce rate of
reaction actually increases it!)
2. This is a gaseous reaction - so has a greater
rate at high pressures
The equilibrium has less product particles
than reactants so high pressures favour the
forward reaction
But high pressure vessels are very expensive,
so the incoming gases are only sometimes
compressed.

Waste Management
The main emissions come from the
absorption tower - mainly NO and NO2
(NOx) and trace amounts of nitric acid.
Since these gases contribute to
photochemical smog there is further
treatment to reduce the levels that are
emitted into the atmosphere.

 Treatment includes:
heating these gases with a fuel such as
natural gas, or hydrogen, over a catalyst, so
that the NOx is reduced to N2.
Or the absorption tower may be modified
by increasing its size or operating pressure,
or an additional absorption tower may be
incorporated, this enables more NOx to be
converted into nitric acid.

Waste heat from the converter can be

used to heat incoming gases or generate
electricity.

Health and safety

Risk

Controlled by

HNO3 is corrosive, can

cause severe burns to
skin and eyes

Full protective equipment and

breathing apparatus must be available.
Acid spills are isolated with sand or
earth and carefully neutralised with
Ca(OH)2 or Na2CO3

Fumes are harmful if

inhaled

Careful monitoring in nitric acid plants

for leaks and spills, employees must be
familiar with appropriate procedures to
handle them if they do occur.

Further safety considerations

Risk

Controlled by

Relatively low concentrations

of NO2 may cause fluid in
the lungs and excessive
exposure may be fatal.

Levels of NO2 must be carefully

monitored

The mixture of ammonia to air

in the gas entering the
converter could become
explosive.

The ratio of ammonia to air in

the gas entering the converter
is continuously measured and
controlled.

Sample exam question HNO3

A particular industrial process involves the following steps

VCAA Q6 Nov 2009

a) It is possible to alter the temperature and pressure at

which reaction 2 occurs.
Would the rate of
reaction 2 become
higher, lower or
remain
unchanged?

The temperature of
reaction 2 is lowered
to 150C.
The pressure
of reaction 2 is
increased to 5 atm
by pumping more
B(g) and C(g)
into the reaction
vessel, at constant
temperature.

Would the
equilibrium
yield of reaction 2
become higher,
lower or
remain unchanged?

Would the value

of the
equilibrium
constant,
K, of reaction 2
become
higher, lower or
remain
unchanged?

b) Heat energy is released by reaction 2. Describe how the

heat energy could be used within this industrial
process.
c) i) Describe one waste management strategy, other than
recycling heat, employed in the industrial production of
your selected chemical.
ii) The following table includes a selection of HAZCHEM
labels used to identify dangerous goods.
(See next slide)
iii) State two uses of your selected chemical.

Key Knowledge
comparison of the renewability of energy
sources including coal, petroleum, natural
gas, nuclear fuels and biochemical fuels

Definition
Fossil fuels are a non-renewable energy
source we use them at a greater rate
than they are being supplied.
Fossil fuels include coal, petroleum and
natural gas
They are carbon compounds which have
been formed over millions of years from
fossilized deposits of plants and animals.

Why do we need to use less fossil fuels?

Their supply is dwindling we will run
out
Burning fossil fuels produces CO2
greenhouse gas
They are needed for other chemical
processes, such as production of polymers
and paints
The use of non-renewable resources such
as fossil fuels and uranium conflicts with
the aims of sustainability

Coal
Coal is used in Victoria to fuel electricity
generating power stations.
The coal is burnt, heating water to its
boiling point. The steam then turns a
turbine which operates the generator and
electricity is made.
Electricity can be made in a similar way by
burning other fuels.

Crude oil - Petroleum

Crude oil is a mixture of a number of
different hydrocarbons (alkanes)
One part of this mixture is petroleum
Others include kerosene, diesel and
liquefied petroleum gas (LPG).
The parts of the mixture are separated
according to their boiling points
using fractional distilllation.

Natural gas
Made up mainly of methane but also
includes other hydrocarbons such as
ethane and propane
Used for home heating and cooking
Some power stations (eg Newport) use
gas to generate electricity

Nuclear fuels
Uranium is a nuclear fuel which is non-renewable.
All the uranium we will ever have is in the
earth or being mined now. There is no way
to make more uranium.
Uranium is mined in
only a small number of
countries

 Nuclear fission occurs when a large

nucleus, such as a Uranium nucleus (235U)
is bombarded by high energy neutrons.
The nucleus splits and two new nuclei are
formed while more neutrons and a large
amount of energy are released.
The large amount of energy from this
nuclear reaction can be used to heat the
water in a nuclear power plant to make
steam, drive turbines and generate
electricity.

Advantages and disadvantages of nuclear

power
Advantages:
No air pollution
Chance to conserve fossil fuels for other use
1 kg of Uranium produces as much electrical
energy as 2500 tonne of Coal
Disadvantages:
Accidental release of radioactive substances
Problem of storing wastes
Long construction time, limited working life.

Nuclear fusion
Occurs in the Sun
Small nuclei come together to make a larger
nucleus and releasing lots of energy

Not possible to control currently, but would be

very useful if it could be.
This could be classified as a renewable energy
source

Renewable energy sources

Renewable energy sources are those that
are constantly being replaced by natural
processes
Improvements in technology are making
these more viable as time goes on.
Biochemical fuels such as biodiesel and
ethanol (see Unit 3) are renewable energy
sources.

Sample exam question - fuels

Most of Victorias electricity is generated by burning fossil
fuels such as coal and natural gas. Alternative methods of
generating electricity are currently being developed.
(e) Biochemical fuels are an alternative fuel for generating
electricity
(i) Name one biochemical fuel, other than methyl
palmitate, and the raw material used in its
production.
(f) Some countries rely on nuclear fission for the largescale production of electricity.
(i) state one disadvantage of using nuclear fission
VCAA Q4 Nov 2009

Key Knowledge
application of calorimetry to measure
energy changes in chemical reactions in
solution calorimetry and bomb calorimetry,
including calibration of a calorimeter and
the effects of heat loss.

Specific heat capacity

Specific heat capacity is a physical
property of a substance.
It is the amount of energy required to
raise the temperature of 1 g of a
substance by 1 C.
Water has a specific heat capacity of
4.18 J g-1 C-1 (unusually high)

Finding energy change using specific

heat capacity

To calculate an energy change in a substance

use
E = mc T
where m = mass of substance being heated(g)
If the substance is water then = volume of
water (mL), since density of water is 1gmL-1
c = specific heat capacity of the substance
T = change in temperature of the
substance( C or K)

 This equation is most useful when a pure

substance (with a measureable specific
heat capacity) is being heated
eg calculate the energy required to heat
150 mL of water to boiling point if the
initial water temperature is 15 C.
E = mc T
= 150 4.18 (100 15)
= 53295 J
= 53.3 kJ

Calorimetry
A calorimeter is an instrument that is used
to measure the change in temperature
during a chemical reaction.
Reactions in solution (eg neutralisation) are
carried out in a solution calorimeter.
Combustion reactions and other gaseous
reactions are carried out in a bomb
calorimeter.

A solution
calorimeter

The change in
temperature of the
water surrounding the
reaction is measured
to obtain Trxn
The calorimeter is
insulated to prevent
heat escaping
(or entering).

A bomb calorimeter

The effects of heat loss in

calorimetry

When heat from a reaction

is transferred to a container of
water without any attempt to
insulate the equipment, heat
is lost to the surrounding air,
the container and any other
equipment that are in contact with the water.
This will result in a lower calculated value for
the enthalpy of reaction, since not all the energy
generated is transferred to the water which is
used for calculations: E = mc T.

Calibration of calorimeters
A calorimeter is calibrated to determine
how the temperature of the water in the
calorimeter responds to the input of a
given amount of energy.
A fixed amount of energy is put into the
water of the calorimeter and the
maximum temperature change (increase)
is measured.

Electrical calibration
In this case the fixed amount of energy is
added directly into the water of the
calorimeter using an electrical heater.
Electricity is passed through the heater and
energy is calculated using
E = VIt
where V = voltage, I = current and
t = time for which the current is passed.

Chemical calibration
A reaction of known H can be used to
calibrate a calorimeter.
A known amount (in mol) of the reactants
are allowed to react in the calorimeter and
Tcalibration is measured.
Energy added during calibration is
calculated using H for the reaction and
n(reactants)
E=n H

Calculating and using a calibration

factor
Calibration gives us a calibration factor (cf)
with units J C-1
Energy added
cf =
Tcalibration
The calibration factor (cf)can then be used
to find out how much energy has been given
out or absorbed by a reaction using
Erxn = cf Trxn

Why is calibration needed?

A calibration factor is specific to a
particular calorimeter.
Whereas using E = mc T does not
consider insulation and absorption of
heat energy by other materials in the
calorimeter, a calibration factor takes
these into consideration, so gives a more
accurate value for E and hence H

Calculations involving calorimetry

Examples of actual calculations and
applications of calorimetry will be covered
in Calorimetry part 2

Formulas used so far

Energy when no calibration has occurred:
E = mc T
Energy added during electrical calibration
E = VIt
Energy added during chemical calibration
E=n H
Energy added
Calibration factor cf =
Tcalibration
Energy of reaction
Erxn = cf Trxn

Example electrical calibration

A bomb calorimeter was calibrated by
passing 1.82 A through the electric heater
for 60.5 s at a potential difference of 5.50V.
The temperature of the water in the
calorimeter rose by 0.375 C. Calculate the
calibration factor of this calorimeter.

V = 5.50V
I = 1.82 A
t = 60.5 s
T = 0.375 C
E = VIt
= 5.50 1.82 60.5
= 605.605 J (keep in calculator)

E
cf = T

605.605
=1.61 kJC-1
0.375

Heat of combustion and heat of

neutralisation

The heat of combustion is the energy

released when a specified quantity
(1 mole, 1 g, 1 L) of a compound burns
completely in oxygen.
Note that the equation for the combustion of
a compound may not involve one mole of the
compound, so Hrxn may differ to Hc
The heat of neutralisation is the energy
released when 1 mole of an acid or a base is
neutralised.

Example chemical calibration

The heat of combustion of benzoic acid
(C6H5COOH, M = 122.13) is -3227 kJ mol-1.
In the calibration of a bomb calorimeter,
0.244g of benzoic acid was combusted and
the change in temperature was 4.13 C.
Calculate the calibration factor of this
calorimeter.

0.244
122.13

0.00200 mol
n(C6H5COOH) =
Eadded = H n
= 3227 0.00200
= 6.45 kJ

E add
cf =
T

6.45
-1
=1.56 kJC
4.13

Finding H from calorimetry

A calibrated calorimeter is used to
measure the amount of energy released or
absorbed by a chemical reaction (Erxn)
occurring in that calorimeter.
For this to occur, the amount of reactants
must be known and the change in
temperature during the reaction, Trxn
The enthalpy of reaction ( H) must relate
to the equation

 Recall that the enthalpy of reaction changes

according to the amount of reactants in the
equation eg:
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l);
H = -3120 kJ mol-1
Recall that Erxn = cf Trxn

H E rxn
To find H use
=
n1
n2
where n1 is the amount of reactant in the
equation and n2 is the amount used in the
reaction for which the energy released was
Erxn

Example finding H using a

calibrated calorimeter
A bomb calorimeter with a calibration factor
of 1.56 kJ C-1 was used for the combustion of
methane gas.
Calculate H for the equation
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
if the temperature in the calorimeter rose
from 20.187 to 20.900 C when
1.25 10-3 mol of methane was burnt.

 Trxn = 20.900 20.187 = 0.713 C

n(CH4) = 1.25 10-3 mol
Erxn = cf Trxn
= 1.56 0.713
= 1.11 kJ

H E rxn
=
n1
n2
H
1.11
=
-3
1
1.2510
For the reaction:

890 kJ mol

-1

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

H = -890 kJ mol-1 (note the ve sign!)

Sample exam questions - calorimetry

A foam cup calorimeter containing 100 mL of water is
calibrated by passing an electric current through a small
heater placed in the solution. Assuming that all
measurements are accurate, which one of the following is the
most likely calibration factor (in J C-1) for the calorimeter
and contents?
A. 120
B. 240
C. 480
D. 960
VCAA Q14 Nov 2008

Potassium hydroxide and hydrochloric acid react in

aqueous solution according to the following equation
KNO(aq) + HCl(aq) KCl(aq) + H2O(l)
A 50 mL solution containing 0.025 mol of KOH was mixed
rapidly in an insulated vessel with a 50 mL solution
containing 0.025 mol of HCl. The temperature increased
by 3.5 C. Assuming that the specific heat capacity of the
solution is the same as that of the water, the enthalpy
change, H, of this reaction , in kJ mol-1, is closest to
A. -29
B. -59
C. -2.9 104
D. -5.9 104
VCAA Q10 Nov 2009
Also look at VCAA Nov 2010 Q4 (chemical calibration and
2009 Q4(a-d) (electrical calibration)

Key Knowledge
use of the electrochemical series in
predicting the products of redox reactions
and deducing overall equations from
redox half equations
limitations of predictions made using the
electrochemical series, including the
determination of maximum cell voltage
under standard conditions

Galvanic cells (revision of basics)

Zn(s) + CuSO4(aq)

Cu(s) + ZnSO4(aq)

H ve

This is a redox reaction the zinc loses

electrons (reductant) and the Cu2+ gains
electrons (oxidant)
If the reductant and oxidant are separated
from each other, the energy is released as
electrical energy instead of heat energy,
creating a galvanic cell.

The Daniell cell

Construction of a galvanic cell

Each half cell contains an oxidant and a
reductant (conjugate redox pair)
The reductant may be the electrode OR an
inert electrode is used and the reductant
is in solution

 Reductants are usually metals or nonmetal ions

Occasionally a transition metal ion may
be a reductant.
Oxidants are usually non-metals (gases
or in solution) or metal ions.
Oxidation occurs at the anode (the
negative electrode)
Reduction occurs at the cathode (the
positive electrode)

 The salt bridge completes the circuit

Only ions move through the salt bridge.
Positive ions move away from the anode half
cell and negative ions move towards the
anode half cell.

Using the electrochemical series

An electrochemical series reflects the
relative ability of reductants to lose
electrons
The best reductants (bottom RHS) are
those metals that react vigorously eg
magnesium, sodium
The best oxidants (top LHS) are those
non-metals that react vigorously eg
fluorine

Data book p4

 In the electrochemical series all the half

cells are compared to the hydrogen half cell:
H2/H+
The E0 value (standard electrode potential)
is the potential difference between the half
cell and H2/H+
These are measured at standard conditions:
25 C, gas pressures of 1 atm, and solution
concentrations of 1 M

Using the electrochemical series with a

galvanic cell
When two half cells are connected, the cell
with the better reductant will contain the
negative electrode.

The Cu electrode in the Cu/Cu2+ half cell is a

stronger reductant than the reductant in the
Cl2/Cl- half cell, (Cl-).
So Cu is the negative electrode and the inert
electrode in the Cl2/Cl- half cell is the positive
electrode.
Half equations:
Anode: Cu(s) Cu2+ (aq) + 2eCathode: Cl2(g) + 2e- 2Cl-(aq)
Overall equation:
Cu(s) + Cl2(g) Cu2+ (aq) + 2Cl-(aq)

Predicting the flow of electrons

eg Ag/Ag+//Zn2+/Zn
Ag+(aq) + e- Ag(s) Eo = 0.80 V
Zn2+(aq) + 2eZn(s) Eo = - 0.76 V

Calculating the maximum cell

voltage

Under standard conditions, the maximum

cell voltage can be calculated using the
standard electrode potentials (E0 values)
Cell voltage = Eo(oxidant cell)
Eo(reductant cell)
Eg Under standard conditions, the voltage of
Ag/Ag+//Zn2+/Zn would be
0.80 (-0.76) = 1.56V

Predicting products of direct redox

reactions
A reductant can only react with oxidants
that have a more positive Eo value than itself
ie oxidants high on the left hand side of the
electrochemical series only react with
reductants that are lower on the right hand
side.
This knowledge is used to predict whether a
reaction will occur between a pair of
reactants

example
If a piece of Pb was placed in FeCl3 predict
whether there would be a reaction, and if so
write the equation for the reaction.
Fe3+(aq) + e- Fe2+(aq) Eo = +0.77 V
Pb2+(aq) + 2e- Pb(s) Eo = -0.13 V

The oxidant has a more positive Eo than the

reductant, so there will be a reaction
2Fe3+(aq) + Pb(s) 2Fe2+(aq) + Pb2+(aq)

Limitations
While the electrochemical series
accurately predicts the possibility of a
reaction, it gives no indication of the rate
of that reaction.
Eg hydrogen peroxide
Also the predictions only apply under
standard conditions, if the conditions are
different the voltage may differ, or even
the order of reactivity.

Sample exam question electrochemical

series

VCAA Q18 Nov 2008

Key Knowledge
the chemical principles, half-equations
and overall equations of simple primary
and secondary galvanic cells

Primary cells
A primary cell cannot be recharged
They go flat when the cell reaction reaches
equilibrium.
Most primary cells utilize electrolytes that
are contained within absorbent or
separating material (i.e. no free or liquid
electrolyte), and so are called dry cells.
Cells are named according to
the electrolyte used
eg acid cells, alkaline cells,
lithium ion cells

Zinc-carbon dry cell

Anode is zinc (this is the case)
Oxidation reaction: Zn(s) Zn2+ (aq) + 2eCathode is a carbon rod in middle of cell
Reduction reaction:
2MnO2(s) + 2NH4+(aq) + 2e- Mn2O3(s) + 2NH3(aq) + H2O(l)

Voltage is 1.5V, but this will drop with prolonged

use.
Overall reaction
Zn(s) + 2MnO2(s) + 2NH4+(aq)
Zn2+(aq) + Mn2O3(s) + 2NH3(aq) + H2O(l)

 Electrolyte is a
paste of powdered
carbon and
manganese dioxide.

Alkaline cells
Anode central steel rod
Powdered zinc around the rod reacts
Zn(s) + 2OH-(aq) Zn(OH)2(s) + 2eCathode outer steel case
Manganese dioxide is reduced
2MnO2(s) + H2O(l) + 2e- Mn2O3(s) + 2OH-(aq)

Half equations and overall equations

Just as the oxidation and a reduction half
equation go together to give the overall equation
for a cell, the overall equation can be used to
derive the two half equations.
eg The overall equation for the reaction in a zincsilver button cell is
Zn(s) + Ag2O(s) + H2O(l) Zn(OH)2(s) + 2Ag(s)
Write the oxidation and reduction half equations:

Rechargeable cells and batteries

A battery is a collection of cells joined in
series.
eg car battery is made up of 6 cells
A rechargeable cell is also called a
secondary cell.
When a cell is recharged, the products are
converted back to reactants.
For this to be possible they must remain
in contact with the electrodes.

Lead acid battery a secondary cell

This is the battery most commonly found in
cars

During discharge (giving out electricity):

Anode reaction (oxidation) at negative
electrode:

Pb(s) + SO42-(aq) PbSO4(s) + 2e-

Cathode reaction (reduction) at positive electrode:

PbO2(s) + SO42-(aq) + 4H+(aq) + 2e- PbSO4(s) + 2H2O(l)

Overall equation:
Pb(s) + PbO2(s) + 2SO42-(aq) + 4H+(aq)
2PbSO4(s) + 2H2O(l)

Lead(II) sulfate is the product of both

reactions

During recharge (using electricity)

Reactions are reversed
Negative terminal is connected to the
negative of a power supply, so reduction
occurs
PbSO4(s) + 2e- Pb(s) + SO42-(aq)
Oxidation occurs at the positive terminal
PbSO4(s) + 2H2O(l) PbO2(s) + SO42-(aq) + 4H+(aq) + 2e-

Overall equation:
2PbSO4(s) + 2H2O(l)
Pb(s) + PbO2(s) + 2SO42-(aq) + 4H+(aq)

Sample exam question primary and

secondary cells
A vanadium redox battery is used to store electrical
energy generated at a wind farm in Tasmania. The battery
supplies electricity to the power grid as required through
a control switch. The diagram shows the structure of a cell
in a vanadium redox battery. The reactants are dissolved
in an acidic solution, stored in large tanks and pumped
through the cell. The cell is recharge using electricity
generated by the wind turbines. A polymer membrane
allows the movement of particular ions.

VCAA Q5 Nov 2009

The two relevant half equations for the vanadium redox

battery are
VO2+(aq) + 2H+(aq) + e- VO2+ (aq) + H2O(l) E0 = +1.004 V
V3+(aq) + e- V2+(aq)
E0 = -0.255 V
a)State the polarity of each electrode as the battery is
discharged
b)Write a balanced overall equation for the reaction that
occurs when the cell is being recharged.
c)Write a balanced overall equation to show why iron would
be an unsuitable material to use as electrode B in the
vanadium redox cell.

Solution
VO2+(aq) + 2H+(aq) + e- VO2+ (aq) + H2O(l) E0 = +1.004 V
V3+(aq) + e- V2+(aq)
E0 = -0.255 V

a)V2+ is the reductant for the cell and VO2+ is

the oxidant. So electrode B is the negative
and electrode A is the positive
b)Discharge equation is
V2+(aq) + VO2+(aq) + 2H+(aq) V3+(aq) + VO2+(aq) + H2O(l)

So recharge equation is
V3+(aq) + VO2+(aq) + H2O(l) V2+(aq) + VO2+(aq) + 2H+(aq)

c) V3+(aq) + e- V2+(aq)

E0 = -0.255 V

From data book:

Fe2+ (aq) + 2e- Fe(s)
E0 = -0.44 V
If an electrode made of Fe was placed in the
V3+/V2+ solution, the Fe, being a stronger
reductant, would react with the V3+ rather
than allowing the V2+ to act as the cell
reductant.

Key Knowledge
the chemical principles, half-equations
and overall equations of fuel cells;
advantages and disadvantages of fuel cells
compared to conventional energy sources

What are Fuel cells?

Reactants are supplied continuously
Use oxidation of a fuel to produce
electricity from chemical energy directly
(compare to multiple steps in coal-fired
power stations)
Oxygen, O2, is always
the oxidant
Fuel may be hydrogen,
methane, methanol etc

Alkaline fuel cell

At the anode (oxidation fuel reacts)
H2(g) + 2OH-(aq) 2H2O(l) + 2e Hydroxide ions come from the electrolyte
(alkaline)
At the cathode (reduction of oxygen)
O2(g) + 2H2O(l) + 4e- 4OH Overall equation:
O2(g) + 2H2(g) 2H2O(l)

 We cannot tell from overall reaction

whether it is alkaline or acidic electrolyte
need more information in question.

Acidic fuel cell

eg phosphoric acid electrolyte
At anode (oxidation of fuel)
H2(g)
2H+(aq) + 2e At cathode (reduction of oxygen)
O2(g) + 4H+(aq) + 4e2H2O(l)
Overall:
O2(g) + 2H2(g) 2H2O(l)

Uses of fuel cells

Space craft as early as Apollo 11 (1969). Still
used in space shuttle
Trial of buses in Perth (2004-2007) powered
by hydrogen fuel cells
Small scale electricity generation
Powering small appliances
Proposed for cars

Other points
Low voltage, but cells can be connected
in series as a stack
Only byproducts are water and heat
(both can be used)
Electrodes behave as catalysts for the
reaction surface area is important.

Advantages and Disadvantages

More efficient energy
conversion
Water as byproduct
Will continue as long
as fuel is available (no
need to recharge)
Variety of fuels
Useful for onsite
electricity generation
Quiet operation

Expensive
Require constant fuel
supply
Difficult to produce,
store and distribute
H2
Fuel cells are very
large (not v. portable)
Generates DC (not
AC) power

Differences between primary and

secondary cells and fuel cells
Fuel cell

Primary and secondary cells

Reactants are delivered

continuously, so the supply
of electricity is continuous.

Once the reactants have been

consumed the device is either
discarded or recharged.

Electrodes are porous and

usually contain a catalyst

The anode may react as the

reductant in the cell, or
electrodes may be inert.

All products of the reaction Products remain in the cell. In a

in a fuel cell are removed
primary cell their build up slows
during operation
the operation of the cell. In
secondary cell the products can
be changed back to reactants.

Sample exam question fuel cells

A fuel cell that can provide power for buses is the
phosphoric acid fuel cell, PAFC. The electrolyte is
concentrated phosphoric acid and the reactants are
hydrogen and oxygen gases.
A simplified sketch of a phosphoric acid fuel cell is given
below.

VCAA
Q8 Nov 2008

a) Give the equation for the half reaction that takes place
at the i) anode and ii) cathode

b) On the diagram of the fuel cell, draw an arrow to show

the direction in which the H2PO4- ion moves as the cell
delivers an electrical current.
c) Describe one advantage and one disadvantage of such
a fuel cell compared with a petrol-driven car engine.

Key Knowledge
the chemical principles, half-equations
and overall equations of simple
electrolytic cells; comparison of
electrolytic cells using molten and
aqueous electrolytes, and inert and noninert electrodes

 Electrolysis is used to force nonspontaneous reactions to occur by the

addition of electrical energy.
It is the opposite process to that
occurring in a galvanic cell

Electrolysis of molten salts

A molten ionic compound (salt) is made up
on only one type of positive ion and one
type of negative ion.
The negative ion loses electrons (is
oxidized) at the anode
The positive ion gains electrons (is
reduced) at the cathode

eg electrolysis of molten KBr

When molten potassium bromide is
electrolysed, the electrode reactions are:
Cathode: K+(l) + eK(l)
Anode: 2Br-(l)
Br2(l) + 2e-

Aqueous electrolysis
In an aqueous solution, water is present at
both electrodes, in addition to the ions
Water is able to act as an oxidant or a
reductant
O2(g) + 4H+(aq) + 4e- 2H2O(l) E0 = +1.23 V
2H2O(l) + 2e- H2(g) + 2OH-(aq) E0 = -0.83 V

 Water is a stronger oxidant than Al3+, Mg2+,

Na+ and Ca2+, so in aqueous solution, water
will always react in preference to these ions.
Water is a weak reductant, but it is a
stronger reductant than Cl- and F-.

This is most important in 1M solutions. If

the conditions are not standard, Cl- may
react in preference to the water anyway.

eg The electrolysis of aqueous

copper(II) sulfate

1) With carbon electrodes

Carbon electrodes will conduct electricity but
will not react. (inert)
Consider the ions/polar molecules present in
solution and which electrodes they will be
attracted to.
Identify the strongest oxidant at the-ve
electrode and the strongest reductant at the
+ve electrode +ve electrode -ve electrode
SO42H2O

Cu2+
H2O

Half equations:
At Cathode: Cu2+ (aq) + 2e- Cu
(reduction)
At Anode:
2H2O(l) O2(g) + 4H+(aq) + 4e(oxidation)

eg The electrolysis of aqueous

copper(II) sulfate continued

2) With copper electrodes

The copper electrodes will conduct electricity
and may also react, since copper is a
reductant.
Consider the ions/polar molecules and
electrodes present in solution and which
electrodes they will be attracted to.
Identify the strongest oxidant present at theve electrode and the strongest reductant at
the +ve electrode

+ve
electrode

-ve
electrode

SO42H2O
Cu

Cu2+
H2O
Cu

Half equations:
At Cathode:
Cu2+(aq) + 2e- Cu(s)
(reduction)
At Anode:
Cu(s) Cu2+(aq) + 2e(oxidation)

Another example
Predict the reactions and hence the products at
each electrode if a solution of sodium nitrate is
electrolysed using carbon electrodes
Species present:
+ve electrode
NO3H2O

-ve electrode
Na+
H2O

Note that the electrodes are inert, so cannot react.

 Best reductant present at +ve (anode): H2O

Best oxidant present at -ve (cathode): H2O

Reaction at anode:
2 H2O(l)
O2(g) + 4H+(aq) + 4e Reaction at cathode:
2 H2O(l) + 2eH2(g) + 2OH-(aq)

 Note that when these reactions occur:

gas is produced at both electrodes (twice as
much hydrogen as oxygen per mole of
electrons through the circuit)
the pH around the positive electrode
decreases as H+ is produced and
the pH around the negative electrode
increases as OH- is produced.
This can be detected experimentally using
universal indicator and the gases can be
collected and tested (pop test and glowing
splint)

Sample exam question - electrolysis

When comparing the electrolysis of molten NaF and that
of a 1.0 M aqueous solution of NaF, which one of the
following statements is correct?
A. The product at the anodes is the same in both cells and
the product at the cathodes is the same in both cells.
B. The product at the anodes is the same in both cells but
the products at the cathodes are different.
C. The product at the cathodes is the same in both cells
but the products at the anodes are different.
D. The products at the cathodes of the cells are different
and also the products at the anodes are different.
VCAA Q16 Nov 2008

Key Knowledge
application of Faradays laws in
electrochemistry

Relating amount of product to charge

passed through a circuit
The amount of electricity that is needed to
deposit one mole of a metal depends on the
charge on the metal ion
eg Na+ + eNa
Cu2+ + 2eCu
Cr3+ + 3eCr
The greater the charge on the ion, the smaller
the amount of metal that can be deposited when
one mole of electrons passes through the circuit.

Charge and current

Electrons carry charge
One mole of electrons carries 96500 Coulomb of
charge (This is called Faradays constant, F)
Charge is calculated using the relationship
Q=It
where Q is charge (coulombs), I is current (amps)
and t is time (seconds)
When current and/or time increases, the amount
of charge (electrons) passing through the circuit
increases.

Relating mole of electrons to charge

Since one mole of electrons carries 96500
C of charge:

Q
n(e) =
96500

It
F

V
m
(Note similarity to n = M and n = VM )

Relating mole of element to charge

We saw earlier that as the charge on an ion
increases, the amount of metal that can be
deposited by a fixed amount of electrons
decreases.
So, considering the half equation for the
production of the element M:
Mx+ + xe- M
1
n(M) =
n(e)
x

1
OR n(element) =
x

It
96500

Using this formula

The mass of a metal that is deposited at a cathode
during electrolysis can be calculated using

1
m(element) =
x

It
M(element)
96500

Where x = number of mole of electrons required to

deposit one mole of the element (always write out the
half equation)
and M(element) depends on the formula of the
element eg Pb, or Cl2

example
eg Find (a) the mass of lead deposited and
(b) the volume of oxygen gas produced at STP when
molten PbO is electrolysed using a current of 5.00 A
for 3.00 minutes.
(a) From the formula, the reaction at the cathode is:
Pb2+ + 2e- Pb
1
It
m(element) =
M(element)

m(Pb) =

96500

1 5.00 (3.00 60)

207
2
96500

0.965g

(b) The reaction at the anode is

2O2- O2 + 4e(note that equations for non-metals must show
the formation of a molecule see
electrochemical series for reminder)
V(O2) = n VM
1 5.00 (3.00 60)
22.4
4
96500
0.0522 L

= 52.2 mL

Linking these formulas to fuel cells

Recall from the calorimetry section that
E = VIt
Now we know that Q = It
Q
and n(e) =
F
So, substituting into the Energy equation:
E = VQ
and Q = n(e) F
so E = V n(e) F

example
A particular fuel cell operates at 0.92V.
How much energy, in kJ, is delivered per
mole of hydrogen used in this fuel cell?
At anode: H2 2H+ + 2e E = V n(e) F
= 0.92 2 96500
= 177560 J
= 1.8 102 kJ

Sample exam question Faradays laws

A series of electrolysis experiments is conducted using the
apparatus shown below.

An electric charge of 0.030 faraday was passed through

separate solutions of 1.0 M Cr(NO3)3, 1.0 M Cu(NO3)2 and
1.0 M AgNO3. In each case the corresponding metal was
deposited on the negative electrode.
VCAA Q18 Nov 2011

The amount, in mol, of each metal deposited is

Amount, in mol,
Amount, in
Amount, in mol,
of chromium
mol, of copper
of silver
deposited
deposited
deposited
A.

0.030

0.030

0.030

B.
C.
D.

0.010
0.090
0.030

0.015
0.060
0.020

0.030
0.030
0.010

Sample exam question fuel cell energy

calculations
A ceramic fuel cell delivers a current of 0.500 A
for 10.0 minutes at a potential of 0.600 V
a) How much electrical energy, in joules, would
be provided by the cell?
b) Calculate the charge, in coulomb, produced by
the cell.
c) If this particular cell operated at 60.0%
efficiency, what amount of hydrogen gas, H2,
in mole, would be consumed by the fuel cell?
VCAA Q5 Nov 2006

a) E = VIt
= 0.600 0.500 (10.0 60)
= 180 J
b) Q = It
= 0.500 (10.0 60)
= 300 C

c) H2(g) 2H+(aq) + 2en(e-)

Q
=
96500

300
96500

0.00311 mol

n(H2) = n(e-)
= 0.00311 = 0.00155 mol
Operating at 60% efficiency:
100
0.00155 0.00259 mol
n(H2) =
60