EQUILIBRIA

Reversible reactions and equilibrium

Reversible reactions:
A reaction in which the products can react to re-form the original reactants is called a
reversible reaction.
Cont…
• The products react together to re-form reactants at the same time as
the reactants are forming products.
• This type of reversible reaction is called an equilibrium reaction.
• We use the sign ⇌ in equilibrium reactions to show that they are
reversible.
Characteristics of equilibrium
• An equilibrium reaction has four particular features under constant
conditions
i. it is dynamic ( means that the molecules or ions of reactants and
products are continuously reacting. Reactants are continuously being
changed to products and products are continuously being changed
back to reactants.
ii. the forward and reverse reactions occur at the same rate : At
equilibrium, the rate of the forward reaction equals the rate of the
backward reaction. Molecules or ions of reactants are becoming
products, and those in the products are becoming reactants at the
same rate.
iii. the concentrations of reactants and products remain constant at
equilibrium: The concentrations remain constant because, at equilibrium,
the rates of the forward and backward reactions are equal. The equilibrium
can be approached from two directions. For example, in the reaction:

• we can start by either:

using a mixture of colourless hydrogen gas and purple iodine vapour, or
using only colourless hydrogen iodide gas.
•V

The changes in the concentrations of reagents

as 5.00 × 10−3 mol of each of hydrogen and
iodine react to
form an equilibrium mixture with hydrogen
iodide in a vessel of volume 1 dm3.
• The changes in the concentrations of reagents as 5.00 × 10−3 mol of each
of hydrogen and iodine react to form an equilibrium mixture with
hydrogen iodide in a vessel of volume 1 dm3.
iv. it requires a closed system.: A closed system is one in which none of the
reactants or products escapes from the reaction mixture.
• In an open system some matter is lost to the surroundings.
Changing the position of equilibrium
Position of equilibrium
• The position of equilibrium refers to the relative amounts of products
and reactants present in an equilibrium mixture.
• If a system in equilibrium is disturbed (e.g. by a change in
temperature) and the concentration of products increases relative to
the reactants, we say that the position of equilibrium has shifted to
the right.
• If the concentration of products decreases relative to the reactants,
we say that the position of equilibrium has shifted to the left.
Le Chatelier’s principle
• If one or more factors that affect a dynamic equilibrium is changed,
the position of equilibrium moves to minimise this change
We can predict the effect of changing concentration and pressure by
referring to the stoichiometric
equation for the reaction. We can predict the effect of changing the
temperature by referring to the enthalpy change of the reaction.
How does change in concentration affect the position of
equilibrium?

• When the concentration of one or more of the reactants is increased:

the system is no longer in equilibrium
the position of equilibrium moves to the right to reduce the effect of the
increase in concentration of reactant
more products are formed until equilibrium is restored.
• When the concentration of one or more of the products is increased:
the system is no longer in equilibrium
the position of equilibrium moves to the left to reduce the effect of the
increase in concentration of product
more reactants are formed until equilibrium is restored.
• For example, look at the reaction:

• What happens when we add more ethanol?

The concentration of ethanol is increased.
According to Le Chatelier’s principle, some of the ethanol must be removed to
reduce the concentration of the added ethanol.
The position of equilibrium shifts to the right.
More ethanol reacts with ethanoic acid and more ethyl ethanoate and water
are formed.
• What happens when we add more water?
The concentration of water is increased.
According to Le Chatelier’s principle, some of the water must be removed to
reduce the concentration of the added water.
The position of equilibrium shifts to the left.
So more water reacts with ethyl ethanoate and more ethanoic acid and
ethanol are formed.
• What happens when we remove some water?
The concentration of water is decreased.
According to Le Chatelier’s principle, some water must be added to increase
its concentration.
The position of equilibrium shifts to the right.
So more ethanoic acid reacts with ethanol and more water and ethyl
ethanoate are formed.
The effect of pressure on the position of equilibrium
• Change in pressure only affects reactions where gases are reactants or
products.
• The molecules or ions in solids and liquids are packed closely together
and cannot be compressed very easily.
• In gases, the molecules are far apart
• For example, consider the reaction:
2SO2(g) + O2(g) ⇌ 2SO3(g)
• There are three moles of gas molecules on the left of the equation and
two on the right.
• What happens when we increase the pressure?
The molecules are closer together, because the pressure is higher.
According to Le Chatelier’s principle, the reaction must shift in the
direction that reduces the number of molecules of gas.
The position of equilibrium shifts to the right.
So more SO2 reacts with O2 to form SO3.
• What happens when we decrease the pressure?
The molecules are further apart, because the pressure is lower.
According to Le Chatelier’s principle, the reaction must shift in the direction
that increases the number of molecules of gas.
The position of equilibrium shifts to the left.
So more SO2 and O2 molecules are formed by the decomposition of SO3
molecules.
• Note that:
• if there are equal numbers of molecules of gas on each side of the equation,
the position of equilibrium is not affected by a change in pressure.
• in a reaction involving gases and solids (or liquids), it is only the molecules of
gases that count when determining how pressure affects the position of
equilibrium.
Summary on effect of pressure
The effect of temperature on the position of equilibrium
• The decomposition of hydrogen iodide is an endothermic reaction.
2HI(g) ⇌ H2(g) + I2(g) ΔHr = +9.6 kJ mol−1
• The effect of temperature on the equilibrium concentration of hydrogen
iodide and hydrogen at equilibrium for the forward reaction is shown in
• As the temperature increases, the concentration of product increases.
The position of equilibrium shifts to the right. We can explain this using Le
Chatelier’s principle:
an increase in temperature increases the energy of the surroundings
according to Le Chatelier’s principle, the reaction will go in the direction
that opposes the increase in energy
the reaction will go in the direction in which energy is absorbed, which is
the endothermic reaction the position of equilibrium shifts to the right,
producing more H2 and I2.
• If an increase of temperature favours an endothermic reaction, a decrease
of temperature favours an exothermic reaction. This means that:
a decrease in temperature decreases the energy of the surroundings
according to Le Chatelier’s principle, the reaction will go in the direction
that opposes the decrease in energy
so the reaction will go in the direction in which energy is released, which
is the exothermic reaction
Summary:
Do catalysts have any effect on the position
of equilibrium?
• A catalyst is a substance that increases the rate of a chemical
reaction.
• Catalysts reduce the time taken to reach equilibrium, but they have
no effect on the position of equilibrium once this is reached.
• This is because they increase the rate of the forward and reverse
reactions equally.
 Equilibrium expressions and the equilibrium
constant, Kc
• The equilibrium constant, Kc, is the ratio of the equilibrium concentrations of
products over the equilibrium concentrations of reactants each raised to the
power of their stoichiometric coefficients
Writing an expression for Kc

If you allow this reaction to reach equilibrium

and then measure the equilibrium
concentrations of everything, you can
combine these concentrations into an
expression known as an equilibrium constant
The equilibrium constant always has the same
value
• Remember that the concentrations of products go at the top of an equilibrium
expression and the concentrations of the reactants go at the bottom.
• Solids and liquids that appear in the balanced equation are NOT included in
the equilibrium expression.

• Consider the table below:

What are the units of Kc?
• In the equilibrium expression, each figure within a square bracket
represents the concentration in mol dm−3.
• The units of Kc therefore depend on the form of the equilibrium expression.
• Examples:
1. Write an expression for Kc:
• N2(g) + 3H2(g) ⇌ 2NH3(g)
 2. Write an expression for Kc:
• 2SO2(g) + O2(g) ⇌ 2SO3(g)

3. State the units of Kc for the reaction:

• H2 + I2 ⇌ 2HI

4. State the units of Kc for the reaction:

• 2SO2(g) + O2(g) ⇌ 2SO3(g)
 Some examples of equilibrium calculations
1.

4.03 (to 3 significant figures)

2. In this example we are only given the initial concentrations of the reactants
and the equilibrium concentration of the product.
• Propanone reacts with hydrogen cyanide as follows:

• A mixture of 0.0500 mol dm−3 propanone and 0.0500 mol dm−3 hydrogen
cyanide is left to reach equilibrium at room temperature. At equilibrium the
concentration of the product is 0.0233 mol dm−3. Calculate Kc for this
reaction.

Kc = 32.7 dm3 mol−1

3. In this example we are given the initial and equilibrium concentrations of the
reactants but not the products.
• Ethyl ethanoate is hydrolysed by water:

• 0.1000 mol of ethyl ethanoate are added to 0.1000 mol of water. A little acid
catalyst is added and the mixture made up to 1 dm3 with an inert solvent. At
equilibrium 0.0654 mol of water are present. Calculate Kc for this reaction.

Kc = 0.288.
•How Kc is affected by changing

Concentration
Pressure
Temperature
 Kc and concentration changes
• If all other conditions remain constant, the value of Kc does not change when
the concentration of reactants or products is altered.
• Take the example of the decomposition of hydrogen iodide.
2HI ⇌ H2 + I2
• The equilibrium constant at 500 K for this reaction is 6.25 × 10−3.
• When more hydrogen iodide is added to the equilibrium mixture, the
equilibrium is disturbed.
• The ratio of concentrations of products to reactants in the equilibrium
expression decreases.
• To restore equilibrium, both [H2] and [I2] increase and [HI] decreases.
• Equilibrium is restored when the values of the concentrations in the
equilibrium expression are such that the value of Kc is once again 6.25 × 10−3.
Kc and pressure changes
• Where there are different numbers of gas molecules on each side of a
chemical equation, a change in pressure alters the position of
equilibrium.
• It is shifted in the direction that results in fewer gas molecules being
formed.
• However, if all other conditions remain constant, the value of Kc does
not change when the pressure is altered.
 Kc and temperature changes
• We have seen that for an endothermic reaction, an increase in temperature
shifts the reaction in the direction of more products.
• So for the endothermic reaction:
2HI ⇌ H2 + I2
The concentrations of H2 and I2 increase as the temperature increases
The concentration of HI falls as the temperature increases.
• Look at how these changes affect the equilibrium expression:
• We see that the equilibrium constant must increase with increasing
temperature. This is because [H2] and [I2] are increasing and [HI] is decreasing.
Table shows how the value of Kc for this reaction changes with temperature.

• For an exothermic reaction, an increase in temperature shifts the reaction in

favour of more reactants.
• Now look at the exothermic reaction:
2SO2 + O2 ⇌ 2SO3
 2SO2 + O2 ⇌ 2SO3

The concentrations of SO2 and O2 increase as the temperature increases.

The concentration of SO3 falls as the temperature increases.
• How do these changes affect the equilibrium expression?

• We see that the equilibrium constant must decrease with increasing

temperature. This is because [SO2] and [O2] are increasing and [SO3] is
decreasing.
 Equilibria in gas reactions: the equilibrium
constant, Kp
Partial pressure
• For reactions involving mixtures of gases, it is easier to measure the pressure
than to measure concentrations. The total pressure in a mixture of gases is
due to each molecule bombarding the walls of the container.
• At constant temperature, each gas in the mixture contributes to the total
pressure in proportion to the number of moles present.
• The pressure exerted by any one gas in the mixture is called its partial
pressure.
• The total pressure of a gas equals the sum of the partial pressures of the
individual gases.
pTotal = pA + pB + pC … where pA, pB, pC are the partial pressures of
the individual gases in the mixture.

Equilibrium expressions involving partial pressures

• We write equilibrium expressions in terms of partial pressures in a similar
way to equilibrium expressions in terms of concentrations.
• But there are some differences:
 we use p for partial pressure
 the reactants and products are written as subscripts after the p
the number of moles of particular reactants or products is written as a power
after the p
square brackets are not used we give the equilibrium constant the symbol Kp
(the equilibrium constant in terms of partial pressures).
• For example, the equilibrium expression for the reaction
What are the units of Kp?
• The units of pressure are pascals, Pa. The units of Kp depend on the
form of the equilibrium expression.
• Although the standard unit of pressure is the pascal, many chemists in
industry use the atmosphere as the unit of pressure.
• 1 atmosphere = 1.01 × 105 Pa. Using ‘atmospheres’ as units simplifies
calculations because the numbers used are not as large.
Examples
1. Deduce the units of Kp for the following reaction:
N2O4(g) ⇌ 2NO2(g)
2. Deduce the units of Kp for the following reaction:
2SO2(g) + O2(g) ⇌ 2SO3(g)
3. The reaction below was carried out at a pressure of 10.00 × 104 Pa and at
constant temperature.
N2(g) + O2(g) ⇌ 2NO(g)
• The partial pressures of nitrogen and oxygen are both 4.85 × 104 Pa.
• Calculate the partial pressure of the nitrogen(II) oxide, NO(g), at equilibrium.
4. In this example we are given the partial pressure of each gas in the mixture.
• In the reaction: 2SO2(g) + O2(g) ⇌2SO3(g)
• the equilibrium partial pressures at constant temperature are SO2 = 1.0 × 106
Pa, O2 = 7.0 × 106 Pa,SO3 = 8.0 × 106 Pa. Calculate the value of Kp for this
reaction.

5. In this calculation we are given the partial pressure of two of the three gases
in the mixture as well as the total pressure.
• Nitrogen reacts with hydrogen to form ammonia: N2(g) + 3H2(g) ⇌ 2NH3(g)
• The pressure exerted by this mixture of hydrogen, nitrogen and ammonia at
constant temperature is 2.000 × 107 Pa. Under these conditions, the partial
pressure of nitrogen is 1.490 × 107 Pa and the
• partial pressure of hydrogen is 0.400 × 107 Pa. Calculate the value of Kp for this
reaction.
 Partial pressure and mole fractions
• The number of moles of gas is proportional to the volume of the gas at constant
temperature. So it follows that the partial pressure of a gas is proportional to its
concentration.
• The mole fraction of a gas is given by the relationship:

• So the mole fraction of ammonia in a mixture containing 0.5 mol ammonia, 0.9
mol hydrogen and 0.6 mol of nitrogen is:
• The partial pressure is related to the mole fraction by the relationship:
• partial pressure = mole fraction × total pressure (of all the gases in the mixture)
• We can therefore use the number of moles of each reactant and product in a
mixture together with the total pressure to calculate a value for Kp.
NOTE:
• Note that the sum of the mole fractions should add up to 1.00 and that the sum
of the partial pressures should add up to the total pressure.
Equilibria and the chemical industry
• An understanding of equilibrium is important in the chemical industry.
Equilibrium reactions are involved in some of the stages in the large-scale
production of ammonia, sulfuric acid and many other chemicals.
1. Equilibrium and ammonia production
• The synthesis of ammonia is carried out by the Haber process. The equilibrium
reaction involved is:
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = −92 kJ mol−1
• We can use Le Chatelier’s principle to show how to get the best yield of
ammonia.
• At high temperatures, when the reaction is faster, the position of equilibrium is
to the left because the reaction is exothermic (ΔH is negative).
 What happens if we increase the pressure?
• When we increase the pressure, the reaction goes in the direction that results
in fewer molecules of gas being formed.
• The equilibrium shifts in the direction that reduces the pressure.
• In this case there are four molecules of gas on the left-hand side and two on
the right-hand side. So the equilibrium shifts towards the right.
• The yield of ammonia increases.
 What happens if we decrease the
temperature?
• A decrease in temperature decreases the energy of the surroundings.
• The reaction will go in the direction in which energy is released.
• Energy is released in the exothermic reaction, in which the position of
equilibrium favours ammonia production.
• This shifts the position of equilibrium to the right.
• The value of Kp increases.
What happens if we remove ammonia by condensing it to a liquid?

• We can do this because ammonia has a much higher boiling point

than hydrogen and nitrogen.
• The position of equilibrium shifts to the right to replace the ammonia
that has been removed.
• More ammonia is formed from hydrogen and nitrogen to keep the
value of Kp constant.
2. Equilibrium and the production of sulfuric acid
• The synthesis of sulfuric acid is carried out by the Contact process. The main
equilibrium reaction involved is:
2SO2(g) + O2(g) ⇌ 2SO3(g) ΔHr = −197 kJ mol−1
• We can use Le Chatelier’s principle to show how to get the best yield of sulfur
trioxide.
What happens when we increase the pressure?
• When we increase the pressure, the reaction goes in the direction that results
in fewer molecules of gas being formed, to reduce the pressure.
• There are three molecules of gas on the left-hand side and two on the right-
hand side, so the equilibrium shifts towards the right.
 What happens if we decrease the
temperature?
• Decreasing the temperature shifts the position of equilibrium to the right.
• A decrease in temperature decreases the energy of the surroundings so the
reaction will go in the direction in which energy is released.
• This is the exothermic reaction, in which the position of equilibrium favours
SO3 production. The value of Kpincreases.
• SO3 is removed by absorbing it in 98% sulfuric acid. The SO3 reacts with the
solution and eventually more H2SO4 is formed.
• Although the SO3 is absorbed in a continuous process, this does not affect the
equilibrium significantly because the position of equilibrium is already far over
to the right.
Acid–base equilibria: pH values and neutralisation
pH values
• We can use universal indicator or a pH meter to deduce whether a substance is
acidic, alkaline or neutral.
acids have pH values below pH 7
alkalis have pH values above pH 7
a neutral solution has a pH value of exactly 7.

Neutralisation
A neutralization reaction is a reaction that yields salts and water when acids
and bases react.
Some simple definitions of acids and bases
• A very simple definition of an acid is that it is a substance that neutralises
a base. A salt and water are formed.

• The equation above also shows us a very simple definition of a base. A

base is a substance that neutralizes an acid.
• A base is a compound that contains oxide or hydroxide ions and reacts
with an acid to form a salt and water. Alkalis are bases which are
soluble in water.
The Brønsted–Lowry theory of acids and bases
• This theory is based on the idea that in an acid–base reaction, a proton is
transferred from an acid to a base (a hydrogen ion, H+, is a proton).
An acid is a proton (hydrogen ion) donor.
A base is a proton (hydrogen ion) acceptor.
• When hydrochloric acid is formed, hydrogen chloride gas dissolves in water
and reacts to form hydroxonium ions, H3O+, and chloride ions. You can see that
the water is involved in the reaction.

• Hydrochloric acid is an acid because it donates a proton to water. This means

that water is acting as a Brønsted–Lowry base. The water is accepting a proton:
• Water can also act as an acid. When ammonia reacts with water, it accepts a
proton from the water and becomes an NH4+ ion

• Substances like water, which can act as either acids or bases, are described as
amphoteric.
• Brønsted–Lowry acids and bases do not have to involve aqueous solutions. For
example, when chloric(VII) acid (HClO4) reacts with ethanoic acid (CH3COO) in
an inert solvent, the following equilibrium is set up:
Quiz
 Strong and weak acids and bases
Strong acids
• When referring to acids and bases remember that weak and strong have to
do with degree of dissociation and not concentration. Concentration is to do
with the number of moles per dm3. The words to use here are ‘concentrated’
and ‘dilute’.
• A strong acid is one which is virtually 100% ionises in solution.

Weak acids
A weak acid is one which doesn't ionise fully when it is dissolved in water.
 Strong bases
• Bases that dissociate almost completely in solution are called strong bases.

• The position of equilibrium is far over to the right

• The Group 1 metal hydroxides are strong bases.
Weak bases
Bases which dissociate to only a small extent in solution are called weak
bases.
The position of equilibrium is well over to the left.
Distinguishing a weak acid from a strong acid
• We can distinguish between a strong and weak acid by their pH
values, electrical conductivity and reactivity. When making these
comparisons, we must use dilute solutions of strong and weak acids
of the same concentration.
1. pH values
• Dilute solutions of a strong acids have lower pH values than those of
weak acids of the same concentration.
• This is because the concentration of hydrogen ions is greater in strong
acids.
• We can determine pH by;
Dipping a pH electrode into a solution of the acid: a pH meter connected to
the pH electrode shows the pH value.
Dipping universal indicator paper into a solution of the acid and noting the
colour change. We then compare the colour with that on a chart which
shows the colours at different pH values.
2. Electrical conductivity
• Dilute solutions of a strong acids have greater electrical conductivity than
those of weak acids of the same concentration.
• This is because the concentration of hydrogen ions (and other ions) is greater
in strong acids.
3. Reaction with reactive metals
• Dilute solutions of weak and strong acids of the same concentration have
different reactivity with reactive metals such as magnesium.
• When a piece of magnesium ribbon is added to a strong acid, a steady stream
of hydrogen bubbles is observed.

• When we add a piece of magnesium ribbon to a weak acid of the same

concentration, only a few bubbles are observed. This is because the
 Indicators and acid–base titrations
• We learned that indicators are used to detect the end-point in acid–alkali
titrations. You may also have used indicators such as litmus to test whether a
substance is acidic or alkaline.
• In this section, we shall look more closely at how specific indicators are used in
titrations involving strong and weak acids and bases.
 Introducing indicators
• An acid–base indicator is a dye or mixture of dyes that changes colour over a
specific pH range.
• In simple terms, many indicators can be considered as weak acids in which the
acid (HIn) and its conjugate base (In−) have different colours.

• Adding an acid to this indicator solution shifts the position of equilibrium to the
left. There are now more molecules of colour A.
• Adding an alkali shifts the position of equilibrium to the right. There are now
more ions of colour B.
• The colour of the indicator depends on the relative concentrations of HIn and
In−.
• The colour of the indicator during a titration depends on the concentration of
• Indicators usually change colour over a pH range of between 1 and 2 pH units.
In the middle of the range there is a recognisable end-point where the
indicator has a colour in between the two extremes of colour.
• For example, bromothymol blue is yellow in acidic solution and blue in alkaline
solution. The colour change takes place between pH 6.0 and pH 7.6. The end-
point, which is a greyish-green colour, occurs when the pH is 7.0.
 pH (TITRATION) CURVES
Sorting out some confusing terms
1. When you carry out a simple acid-base titration, you use an indicator to tell
you when you have the acid and alkali mixed in exactly the right
proportions to "neutralise" each other. When the indicator changes colour,
this is often described as the end point of the titration.
2. The colour change would happen when you mix the two solutions together
in the correct proportions according to the equation (often just called
"equation proportions"). That particular mixture is known as
the equivalence point. For example, if you were titrating sodium hydroxide
solution with hydrochloric acid, both with a concentration of 1 mol dm-3, 25
cm3 of sodium hydroxide solution would need exactly the same volume of
the acid - because they react 1 : 1 according to the equation.
• In this particular instance, this would also be the neutral point of the titration,
because sodium chloride solution has a pH of 7.
• But that isn't necessarily true of all the salts you might get formed.
• For example, if you titrate ammonia solution with hydrochloric acid, you
would get ammonium chloride formed. The ammonium ion is slightly acidic,
and so pure ammonium chloride has a slightly acidic pH.
• That means that at the equivalence point (where you had mixed the solutions
in the correct proportions according to the equation), the solution wouldn't
actually be neutral. To use the term "neutral point" in this context would be
misleading.
• Similarly, if you titrate sodium hydroxide solution with ethanoic acid, at the
equivalence point the pure sodium ethanoate formed has a slightly alkaline
pH because the ethanoate ion is slightly basic.
Titration curves for strong acid - strong
base
• Figure shows how the pH changes when 0.100 mol dm−3 sodium hydroxide (a
strong base) is titrated with 0.100 mol dm−3 hydrochloric acid (a strong acid)
in the presence of bromothymol blue indicator.
These results show:
 a sharp fall in the graph line between pH 10.5 and
pH 3.5; in this region tiny additions of H+ ions
result in a rapid change in pH
 a midpoint of the steep slope at pH 7
 the midpoint of the sharp fall corresponds to the
point at which the H+ ions in the acid have exactly
reacted with the OH− ions in the alkali; this is the
end-point of the titration
 bromothymol blue indicator changed from blue to
yellow over the range 7.6 to 6.0 where the slope is
steepest.
• Because there is a sharp change in pH over the region pH 3.5 to 10.5 we can
use other indicators that change colour within this region. For example,
phenolphthalein changes colour in the pH range 8.2 to 10.0
• Because the sharp pH change occurs over such a wide pH range, there are
many indicators that can be used to determine the end-point of the reaction of
a strong acid with a strong base.
 Titration curves for strong acid - weak
base
• Figure shows how the pH changes when 0.100 mol dm−3 aqueous
ammonia (a weak base) is titrated with 0.100 mol dm−3 nitric acid (a
strong acid).
These results show:
 a sharp fall in the graph line between pH 7.5 and pH 3.5
 that the midpoint of the steep slope is at about pH 5.
 Because there is a sharp change in pH over the region 3.5 to 7.5, we
can use methyl red as an indicator for this titration.
 This is because methyl red changes colour between pH 4.2 and pH
6.3, values that correspond with the region of sharpest pH change.
 Phenolphthalein would not be a suitable indicator to use because it
only changes colour in alkaline regions (pH 8.2–10) that do not
correspond to the sharp pH change.
Titration curves for weak acid - strong base
• Figure shows how the pH changes when 0.100 mol dm−3 aqueous
sodium hydroxide (a strong base) is titrated with 0.100 mol dm−3 benzoic
acid (a weak acid).
These results show:
 a sharp fall in the graph line between pH 11 and pH 7.5
 that the midpoint of the steep slope is at about pH 9.
• Because there is a sharp change in pH over the region pH
7.5 to 11 we can use phenolphthalein as an indicator for
this titration. This is because phenolphthalein changes
colour between pH 8.2 and pH 10, values that correspond
with the region of sharpest pH change.
• Methyl orange would not be a suitable indicator to use
because it only changes colour in acidic regions that do
not correspond to the sharp pH change.
Titration curves for weak acid - weak base
• Figure shows how the pH changes when 0.100 mol dm−3 aqueous ammonia
(a weak base) is titrated with 0.100 mol dm−3 aqueous benzoic acid (a weak
acid).
• These results show that there is no sharp fall in the
graph line. No acid–base indicator is suitable to
determine the end-point of this reaction.
• In the example shown, bromothymol blue:
 starts changing colour when 19.50 cm3 of acid have
been added
 finishes changing colour when 20.50 cm3 of acid
have been added.
Such a gradual colour change on addition of acid is not
good enough when you need to be able to read the
end-point to the nearest 0.05 cm3.
END OF AS-LEVEL

START OF A-LEVEL
 Further aspects of equilibria
21.1 Conjugate acids and conjugate bases
21.2 pH calculations
21.3 Weak acids: using the acid dissociation constant, Ka
21.4 Buffer solutions
21.5 Equilibrium and solubility
21.6 Partition coefficients