Characteristics of equilibrium

An equilibrium reaction has four particular features under constant

conditions:

1. it is dynamic
2. the forward and reverse reactions occur at the same rate
3. the concentrations of reactants and products remain
constant at equilibrium
4. it requires a closed system
 Reversible reaction
•In reversible reactions (⇌) the products can react to reform the
original reactants
 Dynamic equilibrium

•In a dynamic equilibrium the reactants and products

are dynamic (they are constantly moving)
•In a dynamic equilibrium the rate of the forward reaction is the
same as the rate of the backward reaction in a closed system, and
the concentrations of the reactants and products is constant
 Dynamic equilibrium
The concentration of the reactants and products does not change
anymore once equilibrium has been reached (equilibrium was
approached using reactants)
 Dynamic equilibrium
•A closed system is one in which none of the reactants or
products escape from the reaction mixture
•If the reaction involves gases, equilibrium can only be reached in
a closed system
 Dynamic equilibrium
•In an open system, matter and energy can be lost to the
surroundings
•When a reaction takes place entirely in solution, equilibrium can
be reached in open flasks as a negligible amount of material is lost
through evaporation
 Le Chatelier’s principle

•Le Chatelier’s principle says that If one or more factors that

affect an equilibrium is changed, the position of equilibrium
shifts in the direction that reduces (opposes) the change.
•The principle is used to predict changes to the position of
equilibrium when there are changes in temperature, pressure
or concentration
Effects of pressure
Effects of temperature
 Effects of catalysts

- A catalyst is a substance that increases the rate of a chemical

reaction (they increase the rate of the forward and reverse reaction
equally)
- Catalysts only cause a reaction to reach its equilibrium faster
 They have no effect on the position of the equilibrium once
this is reached
3 Equilibrium Constant
 Equilibrium Constant: Concentrations

•Solids are ignored in equilibrium expressions

•The Kc of a reaction is specific and only changes if
the temperature of the reaction changes
 2. Mole Fraction & Partial Pressure
1. Partial pressure
aA + bB ⇌ cC + dD

•For reactions involving mixtures of gases, the equilibrium constant Kp is

used as it is easier to measure the pressure than the concentration for
gases
•The partial pressure of a gas is the pressure that the gas would have if it
was in the container all by itself
•The total pressure is the sum of the partial pressure
 2. Mole Fraction & Partial Pressure

1. Mole fraction

2. Partial pressures of each gas

Equilibrium Constant: Concentrations (Kc)
Equilibrium Constant: Partial Pressures (Kp)

aA + bB ⇌ cC + dD
Industrial Processes
 Industrial Processes

1.The Haber process

The Haber process involves the synthesis of ammonia
2. Contact process
The Contact process involves the synthesis of sulfuric acid
 1. Haber process
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = -92 kJ mol-1

Effect of Temperature to maximize the ammonia yield

• Since the Haber process is an exothermic reaction, according to

Le Chatelier’s principle the equilibrium will shift to the right if the
temperature is lowered  maximize the ammonia yield
 1. Haber process
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = -92 kJ mol-1

Effect of Temperature to maximize the ammonia yield

• However, at a low temperature the gases won’t have enough kinetic

energy to collide and react and therefore equilibrium would not be
reached therefore compromise temperature of 400-450 oC is used
in the Haber process
• A heat exchanger warms the incoming gas mixture to give molecules
more kinetic energy such that the gas molecules collide more
frequently increasing the likelihood of a reaction
 1. Haber process
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = -92 kJ mol-1

Effect of Temperature to maximize the ammonia yield

Removing ammonia
• Removing ammonia by condensing it to a liquid causes the
equilibrium position to shift to the right to replace the ammonia
causing more ammonia to be formed from hydrogen and nitrogen
• The removed ammonia is stored at very low temperatures and
there is no catalyst present with the stored ammonia so the
decomposition reaction of ammonia to decompose back into
hydrogen and nitrogen will be too slow
 1. Haber process
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = -92 kJ mol-1
Effect of Pressure to maximize the ammonia yield
•An increase in pressure will result in the equilibrium shifting in the direction of the
fewest molecules of gas formed (the right) to reduce the pressure the yield of
ammonia increases
•An increase in pressure will cause the particles to be closer together and
therefore increasing the number of successful collisions leading to an increased
reaction rate
•Very high pressures are expensive to produce therefore a compromise
pressure of 200 atm is chosen
 1. Haber process
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = -92 kJ mol-1

Effect of Catalysts to maximize the ammonia yield

• Adding an iron catalyst speeds up the rate of reaction

 2. Contact process
2SO2(g) + O2(g) ⇌ 2SO3(g) ΔHr = -197 kJ mol-1

Effect of Temperature to maximize the sulfuric acid yield

• An increase in temperature will result in the equilibrium shifting

in the direction of the fewest molecules of gas formed (the left)
to reduce the pressure the higher the temperature, the lower the
yield of sulfur trioxide
• A compromise temperature of 450oC is used
 2. Contact process
2SO2(g) + O2(g) ⇌ 2SO3(g) ΔHr = -197 kJ mol-1
Effect of Pressure to maximize the sulfuric acid yield
 An increase in pressure will result in the equilibrium shifting in the
direction of the fewest molecules of gas formed (the right) to
reduce the pressure  the yield of sulfuric acid increases
 In practice, the reaction is carried out at only 1 atm, because Kp for
this reaction is already very high meaning that the position of the
equilibrium is already far over to the right
• Higher pressures than 1 atm will be unnecessary and expensive
 2. Contact process
2SO2(g) + O2(g) ⇌ 2SO3(g) ΔHr = -197 kJ mol-1

Effect of Catalysts to maximize the sulfuric acid yield

The Contact process uses vanadium(V) oxide as a catalyst to

increase the rate of reaction
4 Brønsted–Lowry theory of acids and bases
1 Acids & Bases
 Common Acids
An acid is a substance that neutralizes a base forming
a salt and water

Acids are also substances that release hydrogen

ions when they dissolve in water
 Common Alkalis
 A base is a compound that neutralises an acid forming
a salt and water

A base is a substance that accepts hydrogen ions or a

compound that contains oxide or hydroxide ions
NaOH(s) + aq → Na+(aq) + OH-(aq)
base hydroxide ions

 A base that is soluble in water is called an alkali

2 Brønsted–Lowry
Theory
Brønsted–Lowry Theory
 Brønsted–Lowry Theory

•The Brønsted-Lowry Theory defines acids and bases in

terms of proton transfer between chemical compounds
•A Brønsted-Lowry acid is a species that gives
away a proton (H+)
•A Brønsted-Lowry base is a species that accepts a proton
(H+) using its lone pair of electrons
 Amphoteric

Species that can act both as acids and bases are called amphoteric
3 Acid & Base
Dissociation
1. Strong acids
 A strong acid is an acid that dissociates almost completely
in aqueous solutions
 The position of the equilibrium is so far over to the right that
you can represent the reaction as an irreversible reaction
1. Strong acids
•The solution formed is highly acidic due to the high
concentration of the H+/H3O+ ions
•Since the pH depends on the concentration of H+/H3O+ ions,
the pH can be calculated if the concentration of the strong acid
is known
2. Weak acids
 A weak acid is an acid that partially (or
incompletely) dissociates in aqueous solutions
 The position of the equilibrium is more over to the left and
an equilibrium is established
2. Weak acids
•The solution is less acidic due to the lower concentration of
H+/H3O+ ions

•To find the concentration of H+ ions, the acid dissociation

constant (Ka) should be used
Acid &
equilibrium
position
table
3. Strong bases
A strong base is a base that dissociates almost completely in
aqueous solutions
The position of the equilibrium is so far over to the right that you can
represent the reaction as an irreversible reaction

The solution formed is highly basic due to the high concentration of

the OH- ions
4. Weak bases
A weak base is a base that partially (or incompletely) dissociates in
aqueous solutions
The position of the equilibrium is more to the left and an equilibrium is
established

The solution is less basic due to the lower concentration of OH- ions
Base & equilibrium position table
 Strength of Acids & Bases

 The stronger the acid, the greater the concentration of

H+ and therefore the lower the pH
 Strong and weak acids can be distinguished from each other
by their:
1. pH value (using a pH meter or universal indicator)
2. Electrical conductivity
3. Reactivity
 Reactivity

•Strong and weak acids of the same concentrations react

differently with reactive metals
•This is because the concentration of H+ is greater in strong
acids compared to weak acids
•The greater H+ concentration means that more H2 gas is
produced
 Neutralisation Reactions

 A neutralisation reaction is one in which an

acid (pH <7) and a base/alkali (pH >7) react
together to form water (pH = 7) and a salt
4 pH Scale
 Determine pH

•Determine which substance is in the conical flask

• If it is a strong acid the initial pH is about 1 or 2
• If it is a weak acid the initial pH is about 2-3
• If it is a strong alkali the initial pH is about 13-14
• If it is a weak alkali the initial pH is about 11
 pH Scale

• The values on the pH scale go from 1-14

• All acids have pH values of below 7, all alkalis have pH values above 7
• The lower the pH then the more acidic the solution is
• The higher the pH then the more alkaline the solution is
 pH of water

• pH of water = 7
• Kw (ionic product of water)
= Kc x [H2O] = 10-14 mol2 dm-3 at 298K
 pH of acids

• Acidic solutions (strong or weak) always have more H+ than OH- ions
• Since the concentration of H+ is always greater than the concentration
of OH- ions, [H+] is always greater than 10-7 mol dm-3
• Using the pH formula, this means that the pH of acidic solutions is
always below 7
• The higher the [H+] of the acid, the lower the pH
 pH of bases

• Basic solutions (strong or weak) always have more OH- than H+ ions
• Since the concentration of OH- is always greater than the
concentration of H+ ions, [H+] is always smaller than 10-7 mol dm-3
• Using the pH formula, this means that the pH of basic solutions is
always above 7
• The higher the [OH-] of the base, the higher the pH
5 pH Titration Curves
 What is titration?
 Titration is a technique used in neutralisation reactions between
acids and alkalis to determine the concentration of the unknown
solution
 What are pH titration curves
• A titrant of known concentration from a burette
• An analyte of unknown concentration
• Indicator will change colour at the endpoint of the titration

Label titrant,
analyte, indicator, Titrant
(known
endpoint for this concentration)
picture?

Analyte
(unknown concentration)
 What are pH titration curves

 The endpoint is the point at

which equal number of moles
of titrant and analyte react
with each other
 The equivalence point is this
is the point at
which neutralisation takes
place
Equivalence point → moles of
alkali = moles of acid The diagram shows a pH titration curve where the
(same conc., same volumne) equivalence point is the point at which equal number of
moles of titrant and analyte have reacted
6 Indicators used in
Titration
 Indicators

 The two most common indicators that

are used in titrations are methyl
orange and phenolphthalein
• Methyl orange change colour over a
specific pH range from 3.1-4.4
• Phenolphthalein change colour over
a specific pH range from 8.3-10
 Choosing indicators for titrations

1. Strong acid and strong alkali

•The colour change for both

indicators takes place at a pH
range that falls within the
vertical region of the curve
•Therefore, methyl
orange or phenolphthalein
can be used
 Choosing indicators for titrations

2. Strong acid and weak alkali

•Only methyl orange will

change colour at a pH close to
the equivalence point and within
the vertical region of the curve
 Choosing indicators for titrations

3. Weak acid and strong alkali

• Only phenolphthalein will

change colour at a pH close
to the equivalence point and
within the vertical region of
the curve
•The pH range at which
methyl orange changes
colour falls below the curve
 Choosing indicators for titrations

4. Weak acid and weak alkali

•Neither indicator is useful,

and a different method
should be considered