Module 5

Equilibrium
and
Acid Reactions
 Outcomes
• A student:
• selects and processes appropriate qualitative and quantitative data and
information using a range of appropriate media CH11/12-4
• analyses and evaluates primary and secondary data and information
CH11/12-5
• solves scientific problems using primary and secondary data, critical thinking
skills and scientific processes CH11/12-6
• communicates scientific understanding using suitable language and
terminology for a specific audience or purpose CH11/12-7
• explains the characteristics of equilibrium systems, and the factors that
affect these systems CH12-12
 Content Focus
• Chemical systems may be open or closed. They include physical changes and chemical
reactions that can result in observable changes to a system.
• Students study the effects of changes in temperature, concentration of chemicals and
pressure on equilibrium systems, and consider that these can be predicted by applying Le
Chatelier’s principle.
• Students also analyse the quantitative relationship between products and reactants in
equilibrium reactions to determine an equilibrium constant. From this calculation, they
predict the equilibrium position, either favouring the formation of products or reactants in
a chemical reaction.
• This module also allows students to understand that scientific knowledge enables scientists
to offer valid explanations and make reliable predictions. Students make reliable
predictions by comparing equilibrium calculations and equilibrium constants to determine
whether a combination of two solutions will result in the formation of a precipitate.
 Working Scientifically
• In this module, students focus on processing data to determine patterns and
trends that enable them to solve problems and communicate scientific
understanding of ideas about equilibrium reactions. Students should be
provided with opportunities to engage with all the Working Scientifically skills
throughout the course.
 5.1

Static and Dynamic

Equilibrium

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

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

example:
– cobalt(II) chloride hydrated and dehydrated

– iron(III) nitrate and potassium thiocyanate

– burning magnesium

– burning steel wool (ACSCH090)

• model static and dynamic equilibrium and analyse the differences between open and closed
systems (ACSCH079, ACSCH091)
analyse examples of non-equilibrium systems in terms of the effect of entropy and enthalpy,
for example:
– combustion reactions

– photosynthesis

• investigate the relationship between collision theory and reaction rate in order to analyse
chemical equilibrium reactions (ACSCH070, ACSCH094)

•
 Enthalpy and energy - revision
• There are two major drives, enthalpy and entropy, in determining whether a
chemical reaction will occur spontaneously (or not).
• A reaction will be favoured if:
• 1. There is greater movement towards greater randomness. This is indicated by a
positive entropy ∆S value.

• 2. There is a release of energy. This is indicated by a negative change in enthalpy

∆H
 Enthalpy and energy – Spontaneous or NOT spontaneous
• A reaction will be spontaneous if it has a:
• Positive entropy change ∆S and a

• Negative enthalpy change ∆H

• The reaction will continue to occur until one (or both of) the reactants is
completely used up.
• Then it will STOP and there will be no further reaction.
• BUT….

• A reaction will not be spontaneous if

• if the reaction does not favour the movement towards greater randomness and

• if it also requires a continual input of heat energy.

• (that is, it has a negative ∆S and a positive ∆H)

 Enthalpy and energy - revision
• Situations difficult to predict about whether they will occur spontaneously, are when:

• 1. ∆H is positive (requires energy input) and ∆S (tends to greater randomness) is also positive or when

• 2. ∆H is negative (releases heat energy) and ∆S (doesn’t tend to greater randomness ) is also

negative

• To determine which driver has the greater impact, and whether a reaction will
spontaneously occur for a given temperature,

• the Gibbs Free energy equation is applied:

• ∆G = ∆H - T ∆S (where T is temperature in Kelvin)
• When ∆G is:
• Negative- the reaction will occur spontaneously
• Positive – the reaction WILL NOT occur spontaneously
 Revision: open and closed systems
• Systems and surroundings
• The system is the actual chemicals taking part in a reaction.

• The surrounds (which may include water or air) are what exists around the system.
• In some cases water takes part in the reaction (and is part of the system ), in others, it
doesn’t (and is part of the surroundings )
• Closed and Open systems

• A closed system is one where all the chemicals in the reaction are contained within
a certain space.
• An open system is one which allows substances to be either added or removed.

• An example of an open system when a gas is produced in an acid/metal reaction

and there is no lid on the container to capture and keep the hydrogen.
 Gibbs Free energy implications
• In situations when ∆G is negative, then reaction will be spontaneous. Combustion
reactions and respiration are examples.
• Photosynthesis, the reverse reaction of respiration, has a positive ∆G value and is
not spontaneous. It requires light energy as an input, to occur.

• Some reactions where ∆G is close to zero, are particularly important.

This situation indicates that reactants products could occur at the same time
products reactants. That is, if all species are present. The system must be closed.
 Non-equilibrium systems
• Combustion reactions and photosynthesis are both examples of non-equilibrium
reactions.
• Combustion: e.g. Methane + oxygen water + carbon dioxide
• All combustion reactions are exothermic, where the energy of the products is less than
the energy of the reactants.
• Exothermic reactions are spontaneous.
• The other condition for spontaneity is an increase in entropy or state of disorder.
• In a combustion of propane for example C3H8(g) + 5O2(g)→3CO2(g) + 4H2O(g)
• The number of gas molecules increases on the product side, indicating an increase in
entropy.
• If heat flows into the surroundings (i.e., when a reaction is exothermic) the random
motions of the molecules in the surroundings increase. Thus, the entropy of the
surroundings increases.
Using Gibbs Free energy equation, the spontaneity of the reaction can be proved

-1038

-1038 -966 kJ/mol

 Photosynthesis is a chemical reaction which requires an energy input. It is
endothermic. Endothermic reactions will only be spontaneous if the entropy is high
enough to make the Gibbs free energy value negative.
 Reversible reactions and the Collision Theory
• All Physical changes are reversible, but only some chemical reactions are
reversible.
• The Collision Theory states that, for a reaction to occur:
• The reactant particles
• 1. must collide
• 2. have sufficient energy to break the bonds, &
• 3. have the appropriate orientation to allow the bonds to break.

• The amount of energy required to break bonds in the reactants is called the
activation energy.
• This value is the difference in enthalpy between the activated complex and the
reactants.
Reversible reactions and the Collision Theory

Activated
complex
 Reversible reactions and the Collision Theory
• The size of the activation energy for both the forwards and backwards reaction
must be considered. If forwards is low, the reaction will proceed.
 Reversible reactions and the Collision Theory
• The size of the activation energy is responsible for whether some reactions will
occur or not, and whether they will be reversible:

• If the activation energy is high, the reactant particles may not have enough energy
to break the bonds, and therefore products will not form.
• If the activation energy is low, then more particles will have enough energy to
break bonds and form products.

• IMPORTANT!!
For a reaction to be reversible, the activation energies for both the forward and
the reverse reactions must be low enough for sufficient particles to have enough
energy for a successful collision.
Reversible reactions and the Collision Theory
 Reversible or not reversible?
• Here are four chemical reactions: two are reversible, two are not:

Cobalt chloride

Burning steel
Burning wool
magnesium
 Equilibrium reactions
• Most reactions studied so far have been

• in one direction and

• go to completion.
• i.e. REACTANTS PRODUCTS
• and the reverse seems impossible.
e.g. methane + oxygen carbon dioxide + water
• However:
• A system will reach equilibrium if it:
• Is a closed system and it

• Involves a reversible reaction

 Chemical equilibrium
• Reversible in closed systems involve reactants and products that are in
equilibrium:
• REACTANTS PRODUCTS
• Initially, reactants combine to form products, but then products ‘undo’ to
form the reactants

• Double sided arrows are used in equilibrium equations to indicate the

reaction can be approached from either side

 What are static and dynamic equilibrium?
In chemistry, ‘equilibrium’ refers to a state of a chemical reaction where there are no
macro changes.
• Macro changes are changes in the composition of the reactant and the product
mixture that cannot be perceived from an external point of view. Examples are:
• the colour will remain constant,

• the mass of the solid will remain the same.

• There are two types of equilibrium:

• static and

• dynamic
 What is static and dynamic equilibrium?
• This difference decides the differences between static and dynamic equilibrium:
• dynamic equilibrium is a position where the rate of reactants turning into
products and the rate of products turning into reactants are equal and greater
than zero whereas .

• static equilibrium is a point where the reaction has come to a stop; here, the
reactants no longer turn into products nor the products turn into reactants. The
forwards and backwards reactions are also equal, but in this case, zero.

• The main difference between static and dynamic equilibrium can be identified
as the motion of productions and reactions.
 What is static and dynamic equilibrium?
• However, analysing what happens inside the mixture gives an idea of what is
happening. Two situations are possible
• 1.change takes place at an equal rate from either side making it seem that change
is not occurring.
Liquid water is evaporating at the
same rate that water vapour is
condensing
Liquid gas
Gas liquid
No MACRO
(detectable )changes
• This is dynamic equilibrium

• OR….

• 2. change actually doesn’t take place. This is static equilibrium

 What is static equilibrium?
• In the case of a static equilibrium, as in a dynamic equilibrium, the number of
reactants and the number of products remain the same. However, the reactions
itself has come to a STOP without any more reactants converting into products
and vice versa. This gives the idea of a static condition as the name implies.
• For example, imagine that reaction started with several reactant molecules and
few product molecules. After some time, the reaction will come to a stop. This
means that the composition remained the same actually without any interchanges
within the mixture.
• A classic example of static equilibrium, is carbon as diamond in equilibrium with
carbon as graphite.
 Static equilibrium explained
In dynamic equilibrium , the rates of opposing processes are equal.
Static equilibrium occurs when there is no exchange between reactants and products.
An example of static equilibrium is diamond turning into graphite.
C(diamond) ⇌ C(graphite)
Graphite is more stable than diamond, but the activation energy is so high that you must heat diamond to
about 2000 °C before you'll see any diamond converting to graphite.
The estimates are that, at room temperature, the process will take millions or billions of years.
The process is essentially in static equilibrium , because the reaction rates cannot be detected, are essentially,
zero
If you have a reaction that can occur in only one direction, you can reach equilibrium once you have used up
the limiting reagent .
Since the forward and reverse reactions stop occurring , you are at static equilibrium.
This defines the difference between dynamic and static equilibria.
In both cases, the rates of the forward and reverse reactions are the same.
The difference is: in static equilibrium, the rates of the forward and reverse reactions are zero.
 What are the differences- A summary
• Definition
• Dynamic equilibrium is an equilibrium where reactants are converted to products
and products are converted to reactants at an equal and constant rate greater
than zero.
• Static equilibrium is an equilibrium that occurs when all particles in the reaction
are at rest, and there is no motion between reactants and products. The rate is
constant, but, zero.
• Changes
• In a dynamic equilibrium, changes occur within the mixture, keeping the total
composition the same.
• In a static equilibrium, there are no further changes taking place within the
mixture.
 What are the differences?
• Reaction rates
• In a dynamic equilibrium, the rate of the forward reaction is equal to the
backward reaction.
• In a static equilibrium, both forward and backward reactions have come to a halt.

• External view of the mixture

• A dynamic equilibrium will not resemble the exact situation taking place in the
system.
• In contrast, a static equilibrium will represent the exact situation in the mixture.

• Application

• Dynamic equilibriums are more often discussed within a chemical context.

• Static equilibriums are often applied in a mechanical context rather than a
chemical context.
 static Vs dynamic equilibrium: A summary
• STATIC DYNAMIC
 Steady State
Systems that have constant properties are said to be in a steady state.
• All systems at dynamic equilibrium must be in a steady state since their
properties will remain constant.
• The same cannot be said about the reverse. Not all systems in a steady state will be
equilibrium since a steady state may be achieved without a reversible reaction or a
closed system. An example of this is: if reactants are added to a reaction mixture
at the same rate that products are removed, then a steady state will be achieved,
even though the system will not be at equilibrium.
 Dynamic Equilibrium -features
• Some features of reactions in equilibrium:

• *the reaction is reversible and can be approached from either side,

• forwards or backwards

• i.e. Forwards: A + B AB or

• Backwards AB A + B
 Equilibrium -features
• all species in the equation are present

• A + B C + D
• Therefore
• The system must be closed or lidded if gases are present

If the system is not lidded

(closed) products or reactants
are lost from the system
 What is dynamic equilibrium?
• In most reactions, initially only reactant molecules are present
• These reactants react to produce products.

• This is the forward reaction

• The rate is initially fast, but slows down

Slope is
steeper
initially
 What is dynamic equilibrium?
• As products are produced, a backwards or reverse reaction begins:
• Products are breaking down, forming reactants.

• This is the reverse or backwards reaction

Slope is
steeper
initially
 What is dynamic equilibrium?
• Eventually, the rate of the forward reaction equals the
• rate of the reverse, or backwards reaction.

• At this point, equilibrium is achieved.

• Reactants are forming products at the same rate that products form reactants

Equilibrium achieved when the

lines meet
When the rate of the forward reaction = the rate of the reverse reaction,

dynamic equilibrium is reached.

Modelling equilibrium
 Equilibrium -features
• concentrations of all species are constant when equilibrium is reached
• On a graph, this is seen as parallel lines
•

The product concentration is initially zero , The product concentration is initially zero ,
but when equilibrium is reached, it surpasses and remains less than the reactants once
the reactant concentration. equilibrium is reached.
 Chemical equilibrium
• Identify the times that the system is in equilibrium.
• Hint: when are the lines parallel?

0-4 mins, 8-10 min, 12-14 mins, 16-18 mins

 Features of dynamic equilibrium: a summary

• A chemical system will reach equilibrium IF it:

• it is a closed system
• involves a reversible reaction

• At equilibrium

• all species will be present

• the rate of the forward reaction will equal the rate of the reverse reaction

• the concentrations of all species will remain constant

• macroscopic properties are constant

 An example of a system in equilibrium
• The contents of a bottle of soda water is a system in equilibrium

• Soda water is carbonic acid which has the formula H2CO3(aq)

• It is made by dissolving carbon dioxide (under pressure) , in water

• CO2(g) + H2O(l) H2CO3(aq) + heat

• The system is only in equilibrium while the system is closed.

• The equation ( as written), is exothermic. If the reaction is reversed, it will be

endothermic.
 Soda water a system in equilibrium
• If the bottle is opened, the carbon dioxide is able to escape, making the soda
water ‘go flat’.
 The Haber Process and equilibrium
• The production of ammonia from the gases hydrogen and nitrogen is a system in
equilibrium:
• 3H2(g) + N2(g) 2NH3(g) + heat
• All species; both reactants and the product are gases, so the system must be
lidded, to ensure the system is closed.
• The production of ammonia from these gases is difficult because the equilibrium
lies well to the left.
• In 1904, the German chemist, Fritz Haber discovered an efficient method for the
production of ammonia.
An example of a system in equilibrium
• Although calcium carbonate is considered insoluble, in reality a very small amount
is able to dissolve.
• This reaction is reversible , so, for the solid to form, the system must be at
equilibrium, and therefore a saturated solution is needed.
• If the solution is not saturated, then the reverse reaction, (as written above) is
favoured, and thus any solid formed simply dissolves to form ions again.
• It may seem unlikely that a saturated solution is able to be achieved in an ocean.

• However, since calcium carbonate has such a low solubility, it does not occur.
• Any excess ions will be able to form the solid calcium carbonate needed for the
shells, coral and skeletons of aquatic organisms.