Unit 4 - Acid-Base Equilibria Notes 2023

Centre for Higher Secondary Education Department of Chemistry
TOPIC 14: ACID – BASE EQUILIBRIA

GRADE 12
SEMESTER 3/2022
Checklist
P
Students will be assessed on their ability to:
14.1 understand that a Brønsted–Lowry acid is a proton donor and a Brønsted–Lowry base is a proton
acceptor and that acid-base reactions involve proton transfer
14.2 be able to identify Brønsted–Lowry conjugate acid-base pairs
14.3 be able to define the term ‘pH’
14.4 be able to calculate pH from hydrogen ion concentration
14.5 be able to calculate the concentration of hydrogen ions in a solution, in mol dm-3, from its pH, using
the expression [H+] = 10-pH
14.6 understand the difference between a strong acid and a weak acid in terms of the degree of
dissociation
14.7 be able to calculate the pH of a strong acid

14.8 be able to deduce the expression for the acid dissociation constant, Ka, for a weak acid
14.9 be able to calculate the pH of a weak acid from Ka or pKa values, making relevant assumptions
Students will not be expected to solve quadratic equations.
14.10 be able to define the ionic product of water, Kw
14.11 be able to calculate the pH of a strong base from its concentration, using Kw or pKw
14.12 be able to define the terms ‘pKa’ and ‘pKw’
14.13 be able to analyse data from the following experiments:
i measuring the pH of a variety of substances, including equimolar solutions of strong and

weak acids, strong and weak bases, and salts
ii comparing the pH of a strong and weak acid after dilution 10, 100 and 1000 times
14.14 be able to calculate Ka for a weak acid from experimental data given the pH of a solution containing
a known mass of acid
14.15 be able to draw and interpret titration curves, using all combinations of strong and weak
monoprotic and diprotic acids with bases, and apply these principles to diprotic acids and bases
14.16 be able to select a suitable indicator for a titration, using a titration curve and appropriate data
14.17 know what is meant by the term ‘buffer solution’
Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 1 of 32

14.18 understand the action of a buffer solution
14.19 be able to calculate the pH of a buffer solution given appropriate data
14.20 be able to calculate the concentrations of solutions required to prepare a buffer solution of a given
pH
14.21 understand how to use a weak acid-strong base or strong acid-weak base titration curve to:
i demonstrate buffer action
ii determine Ka from the pH at the point where half the acid is neutralised/ equivalence point
14.22 understand the importance of buffer solutions in biological environments:
i buffers in cells and in blood (H2CO3/HCO3 - )
ii in foods to prevent deterioration due to pH change (caused by bacterial or fungal activity)
14.23 CORE PRACTICAL 11
Finding the Ka value for a weak acid.
Further suggested practicals:
i carry out the measuring of the pH of solutions mentioned in 14.13
ii obtain data to draw titration curves mentioned in 14.15 (which gives an opportunity to use
data loggers)
iii analysis of vinegar

14A 1 THE BRØNSTED – LOWRY THEORY SPECIFICATION

OBJECTIVE 14.2,
14.2 & 14.6
BrØnsted – Lowry acids and bases

This theory defines
• an acid as a substance consisting of molecules or ions which donates protons, (a proton

donor)
• a base as a substance consisting of molecules or ions which accepts protons (a proton
acceptor)
• A substance behaves as an acid if the hydrogen carries a slight positive charge (if it is bonded
to a highly electronegative element such as oxygen or halogen).
• A substance behaves as a base if it contains a lone pair of electrons to form a dative bond
with the proton.
• A proton is referred to a hydrogen ion, H+, since it consists of a single proton only.
• For example when ethanoic acid (CH3COOH) is dissolved in water, the following
equilibrium is set up:
CH3COOH + H2O ⇌ CH3COO- + H3O+
o In the forward reaction CH3COOH is acting as an acid because it donates a proton to
H2O which is acting as a base.
o In the reverse reaction the H3O+ ion acts as an acid, donating a proton to CH3COO─
which acts as base.
Note: Some substances like water, are amphiprotic, capable of acting as an acid or a base depending
upon conditions.
Conjugate acid-base pairs

• The following equation represents the equilibrium established when an acid dissolves in
water. Conjugate acid-base pair
HA + H2O ⇌ A- + H3O+
Conjugate acid-base pair
o In the forward reaction, the HA loses the proton (acid) it forms a base A-. These two
species are called conjugate acid-base pair.
o In the backward reaction, the H3O+ loses a proton (acid) and forms the base H2O.
These two species are called conjugate acid-base pair.

WORKED EXAMPLE
Example 1
CH3COOH + H2O ⇌ CH3COO- + H3O+
Acid 1 Base 2 Base 1 Acid 2

2 2
Example 2
HCl + H2O ⇌ Cl- + H3O+
Acid 1 Base 2 Base 1 Acid 2

2 2
EXERCISE 1
Identify the conjugate acid-base pairs in the following reactions.

a. NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)
b. HNO3(aq) + H2SO4(aq) ⇌ H2NO3+(aq) + HSO4- (aq)
• Monoprotic acids have a single proton to donate. E.g. HCl. They have only one conjugate
base. Therefore, they are called monobasic acid.
• Diprotic acids have two protons to donate. E.g. H2SO4. They have two conjugate bases and
so are called dibasic acid.
• Triprotic acids have 3 protons to donate. E.g. H3PO4. They have three conjugate bases and
so are called tribasic acid.
o The dissociation of these acids occurs stepwise. Consider the dissociation of sulfuric
acid:
Step 1: H2SO4 + H2O → HSO4─ + H3O+
Step 2: HSO4─ + H2O → SO42─ + H3O+
• Similarly, some bases such as carbonate ion can accept more than one proton:
Step 1: CO32- + H+ → HCO3-
Step 2: HCO3- + H+ → H2CO3

Strong acids and weak acids

• A strong acid is defined as one that is almost completely dissociated in aqueous solution.
HCl(aq) → H+ (aq) + Cl- (aq)
Represented by single direction arrow
• A weak acid is defined as one that is partially dissociated (often less than 10%) in aqueous
solution.
Organic acids are examples of weak acids

Represented by reversible arrows
CH3COOH (aq) ⇌ CH3COO- (aq) + H+(aq)
14A 2 HYDROGEN ION CONCENTRATION AND THE SPECIFICATION

OBJECTIVE 14.3, 14.4,
pH SCALE 14.5, 14.6 14.7 14.8 14.9
& 14.12 PART
Strong acids and pH

§ Strong acids completely dissociate when dissolved in water. Therefore, the hydrogen
ion concentration is related directly to the concentration of the acid.
.
Example: a solution of HCl of concentration 0.100 moldm-3 will produce a hydrogen ion
concentration of 0.100 moldm-3.
[H3O+] = concentration of the strong acid.
§ Strength refers to the extent of dissociation of the acid into hydrogen ions.
§ Concentration refers to the number of moles of acid dissolved in a given volume of
water.
§ The pH value by itself is not a measure of the strength of an acid.
§ The pH is simply related to the hydrogen ion concentration in the solution.
• Definition: pH = ─ log10 [H3O+(aq)]

• The acidity of a solution depends on the concentration of the H3O+ ions (or for simplicity H+
ions) in the solution. This is measured on the pH scale.
• The negative sign in the definition means that the pH decreases as the concentration of H3O+
increases.

• The values of pH which are most used, range from 0 to 14. However, pH values of less than
0 and values greater than 14 are possible, being limited only by the solubility of the strongest
acid and the strongest base.
• A change of one unit on the pH scale corresponds to a tenfold change in the Hydrogen
concentration (log10 scale is used)
WORKED EXAMPLE 1
Example 1: Calculate the pH of aqueous solutions of the following monobasic strong acids. In
each case, assume that the acid is completely dissociated. Give your answers to 2 decimal places
a. 0.05 moldm-3 of HNO3
b. 0.150 moldm-3 HBr
Example 2: Calculate the pH of an aqueous solution of 10.00 moldm-3 of HCl. In this solution
the HCl is 55% dissociated. Give your answer to two decimal places.
Hydrogen ion concentration from pH

[H+ (aq)] = 10 -pH

WORKED EXAMPLE
Calculate the hydrogen ion concentration of a solution with a pH of 4.8
Weak Acids & Acid Dissociation Constant

• Weak acids do not ionize completely, hence the method used for strong acids cannot be
applied to calculate pH of weak acids.
• A weak acid is only partially ionized in solution. Therefore the [HA] is much greater than [H+].
• For a weak acid HA, the equation for dissociation in aqueous solution is:
HA (aq) + H2O (l) ⇌ H3O+ (aq) + A- (aq)
• The equilibrium constant, Kc, can be written as:
[H3O+ (aq)][A- (aq)]

Kc =
[HA (aq)][ H2O (l)]
• For a dilute weak acid the concentration of water is effectively constant because it is in large
excess, and it can be incorporated into the value of Kc so that Kc becomes a new constant
which is called the acid dissociation constant and is given the symbol Ka.
§ The Ka expression must not have [H2O]

[H3O+ (aq)][A- (aq)] in the denominator.
Ka = § Ka is temperature dependent as it is an
equilibrium constant.
[HA (aq)]
§ Ka has units of moldm-3.
• The value of Ka determines the position of equilibrium. The greater the value of Ka, the
stronger the acid, HA.
• The Ka values are only valid for solutions in water where the base is the same (i.e. H2O) no
matter which acid is dissolved in it. The strength of the acid will be different in other solvents.
• For polyprotic acids, a Ka value can be written for each stage of ionisation, called Ka1, Ka2, etc.
Weak Acids & pH

• Weak acids do not ionize completely, hence the method used for strong acids cannot be
applied to calculate pH of weak acids.

• A weak acid is only partially ionized in solution. Therefore the [HA] is much greater than
[H+].
• For weak acids, the pH is calculated using the Ka of that acid.
[H3O+ (aq)][A- (aq)]

Ka =
[HA (aq)]
• For a weak acid, HA, in solution [H3O+] = [A-]. Hence,
• If the value of Ka and [HA] are known

[H3O+ (aq)]2
Ka = then we can find the value of [H3O+]
[HA (aq)] and hence the pH of the acid.

• If the pH value and the molarity of
• If [HA] = C moldm -3
the weak acid are known then the
[H3O+] = √(Ka x C) value of Ka can be calculated.
Assumption:
o The equilibrium concentration, [HA], is equal to the initial concentration of the

weak acid, [weak acid]. However, the actual [HA] would be:
[HA] = [weak acid] – [H3O+]
but since [H3O+] is very small, the approximation used is valid.
o For a weak acid, HA, in solution [H3O+] = [A-].
WORKED EXAMPLE
Calculate the pH of ethanoic acid of concentration 0.05 moldm-3. The value of Ka for ethanoic
acid is 1.74 x 10 -5 moldm-3 at 298K.

EXERCISE 2
1. The weak acid, CH3COOH has a Ka value of 1.74 x 10-5moldm-3 at 300K. Calculate the pH
of a 0.1 M solution of this acid at this temperature.
2. A 0.1 M solution of a weak acid, HA, has a pH value of 2.50. Calculate the value for the
acid dissociation constant, Ka.

Ka and pK a
• Since Ka values can be extremely large for strong acids and extremely small for weak acids,
it is more convenient to compare the acid strength using pKa values.
• pKa bears exactly the same relationship to Ka as pH does to the [H+]
• Definition: pKa = ─ log10Ka
• Lower the value of pKa the stronger the acid.
• For weaker acid, pKa is a more useful tool than pH since it is independent of the
concentration.
EXERCISE 3
1. 0.01M solution of a weak acid X has pH of 3.37 at 200K. Calculate the pKa value for X at
this temperature.
2. Calculate pH pf a 0.1M solution of a weak acid given that it has a pKa value of 4.76 at
298K.

CHECKPOINT QUESTIONS PAGE 85

1. Calculate the pH of a mixture of 20.0 cm3 of 1.00 moldm-3 HCl (aq) and 5 cm3 of 1.00
moldm-3 NaOH (aq)
2. The pH of an aqueous solution of a weak acid, HA, of concentration 0.0305 moldm-3 is
4.97. Calculate the dissociation constant, Ka, for this weak acid.
14A 3 IONIC PRODUCT OF WATER, KW SPECIFICATION

14.10 14.11 & 14.12
PART
Dissociation of water
• Although pure water is essentially covalent, it self-ionises to a small extent through an acid
base reaction.
H2O(l) + H2O(l) ⇌ H3O+(aq) + OH- (aq)
• For the ionization above, the equilibrium constant, Kc, can be written as:
[H3O+(aq)][OH- (aq)]
Kc =
[H2O (l)] [H2O (l)]
• The denominator [H2O]2 is effectively constant, hence when incorporated into the value of
Kc gives a new constant called the ionic product and is given the symbol Kw.
Kw = [H3O+] [OH-]
• Note that:
§ Kw is temperature dependent.
§ Kw has units of mol2dm-6.
§ Its numerical value is 1 x 10-14 mol2dm-6 at 298K.
§ In pure water the concentration of H3O+ is the same as that of OH- ions. Therefore,
the H3O+ concentration can be worked out and hence the pH.
At 298K, [H+] = 1.00 x 10 -7
pH = -log[H+]
=7
§ pKw = ─ log10Kw

pH of water at different temperatures

• Increasing the temperature increases the concentration of H+ ions (because dissociation of
water is endothermic). Therefore, Kw increases and hence pH decreases.
• pH falls as temperature increases. But this does not mean that water becomes more acidic
at high temperature. It changes the neutral point on the pH scale.
• When an acid or alkali is dissolved in water there will be different concentrations of H3O+ and
OH- ions. However, the product of these two concentrations is always equal to the value of
Kw at that temperature.
• All aqueous solutions contain H+ and OH- ions. The proportion of these ions in solution is
determined by pH.
In water [H+] = [OH-]

In acidic solution [H+] > [OH-]
In alkaline solution [H+] < [OH-]
pH of aqueous solutions of strong bases

• It is assumed that all strong bases are completely ionised.
• Therefore, [OH─] = concentration of the base.
Kw
+
[H ] =
[OH- (aq)]
pH = -log[H+]
• An alternative method for calculating pH of alkali at 298K is to use the expression;
pH + pOH = 14
WORKED EXAMPLE
Calculate the pH, at 298 K, of an aqueous solution of potassium hydroxide of concentration 0.02
moldm-3.
Kw (298K) = 1.00 x 10-14 mol2dm-6

EXERCISE 4
At 338K the pH of pure water is 6.

a. Calculate Kw at this temperature
b. Hence calculate the pH of 0.01 mol dm-3 of NaOH at 338K
14A 4 ANALYSISNG DATA FROM pH MEASUREMENTS SPECIFICATION

14.13(i) 14.13(ii) &
14.14 CP11
Strong acids and weak acids

The relative strengths of different acids can be determined by measuring the pH of equimolar
aqueous solutions of the acid at the same temperature.
Formula of the acid
HCl CHCl2COOH CH2ClCOOH HCOOH CH3COOH CH3CH2COOH
pH of 0.1 M
aqueous solution 1.00 1.14 1.93 2.38 2.87 2.93
Decreasing acid strength

Strong and weak bases

Formula of the
NH3 CH3NH2 (CH3 )2NH CH3CH2NH2 CH3CH2CH2NH2 NaOH
acid
pH of 0.1 M
11.13 11.82 11.83 11.84 11.86 13.00
aqueous solution
Increasing base strength
Salts
Formula of the acid NaCl KNO3 CH3COONa NH4Cl CH3COONH4
pH of aqueous
7.00 7.00 8.88 5.13 7.00
solution
• The pH of NaCl is 7.00 because the salt is made from a strong acid (HCI) and a strong base
(NaOH).
• The same is true for KN03, which is a product of the strong acid HN03 and the strong base
KOH.
• An aqueous solution of CH3C00Na is alkaline because it is the product of a weak acid
(CH3COOH) and a strong base (NaOH).
• An aqueous solution of NH4Cl is acidic because it is the product of a strong acid (HCI) and a
weak base (NH3).
• An aqueous solution of CH3COONH4 is neutral (pH = 7.00) because it is the product of a weak
acid (CH3COOH) and a weak base (NH3), and the relative strengths of the acid and base are
the same. This is shown by their dissociation constants:
CH3COOH: Ka = 1.74 x 10-5 mol dm-3
NH3: Kb = 1.74 x 10-5 mol dm-3
SALT OF A STRONG ACID AND A STRONG BASE pH = 7 (solution is neutral}

SALT OF A WEAK ACID AND A STRONG BASE pH > 7 (solution is alkaline)
SALT OF A STRONG ACID AND A WEAK BASE pH < 7 (solution is acidic)
SALT OF A WEAK ACID AND A WEAK BASE pH depends on relative strengths of acid
and base;
if Ka = Kb, pH = 7
if Ka > Kb, pH < 7
if Ka < Kb, pH > 7

Effect of dilution oh the pH of aqueous solutions of acids

Strong acids
The table below shows the pH of five aqueous of hydrochloric acid. In each case the acid has been
diluted by a factor of 10. All the solutions are at 298 K.
Concentration
1 0.1 0.01 0.001 0.0001
/moldm-3
pH 0.00 1.00 2.00 3.00 4.00
pH increases by a factor of one unit for each 10-fold decrease in concentration
Weak acids
The table below shows the pH of five aqueous of ethanoic acid. In each case the acid has been
diluted by a factor of 10. All the solutions are at 298 K.
Concentration
1 0.1 0.01 0.001 0.0001
/moldm-3
pH 2.38 2.88 3.38 3.88 4.38
pH increases by a factor of 0.5 unit for each 10-fold decrease in concentration
CHECKPOINT QUESTION PAGE 90

Calculate the Ka for chloroethanoic acid from the following data:
1.89 g of chloroethanoic acid was dissolved in 50 cm3 of water and the solution was diluted to 250
cm3 in a volumetric flask. The pH of this solution was 1.99.

14B 1 ACID-BASE TITRATIONS, pH CURVES &

SPECIFICATION
14.15 & 14.16
INDICATORS
End point and equivalence point

• A titration is a quantitative technique in which the volume of one solution required to
completely react with a known volume of another solution is accurately measured. In an
acid-base titration, the two solutions are an acid and a base.
• Normally acid of known concentration is added from the burette into the alkali of an
unknown concentration in a flask.
• Visual indicators are used to determine the end point.
• The end point is the point where the indicator changes the colour.
• The equivalence is the point where the solutions have been mixed in exactly the right
proportions according to the stoichiometric equation.
pH curves
• The change in pH during an acid-base titration can be followed using a pH meter to measure
the pH after each addition of acid or base.
• The graph of pH against volume of acid or base added is called a pH curve or a titration curve.
• The shape of the curve obtained is dependent to some extent on the strength of the acids
and bases used.
1. Initial pH : this may be the pH of acid

4
or base depending upon whether the
acid is added to the base or vice
versa.
5 3 2. The volume of acid or base required
to reach equivalence point.
3. The pH at equivalence point
1
4. The final pH.
2 5. The pH range at equivalence

1. Strong acid – strong base

HCl+ NaOH → NaCl + H2O
Running alkali into acid Running acid into alkali
• Both base and acid are fully dissociated.

• If the addition of base to an acid is considered
o Initially proportion of H+ removed by the base is quite small compared to the total
amount of H+ present. Therefore, increase in pH is small.
• The pH change becomes greatest near the equivalence point so the curve is steepest.
• Equivalence point is at 7 because salt ios Na+ and Cl- have no acid base properties.
• pH range at equivalence is 3-11 or 3.5-10.5.
• Initial pH is 1 and final pH is 13.
2. Weak acid with strong base

CH3COOH(aq) + NaOH(aq) ⇌ CH3COO-(aq) + H2O (aq)

• pH curve starts at higher pH value since weak acid is slightly dissociated.

• pH at equivalence point is higher than pH 7 (approximately 9) because of the hydrolysis of
the salt.
• The straight vertical section of the graph is shorter than that for a titration of strong acid
with strong bases.
• pH range at equivalence is 7.5-10.5.
3. Strong acid with weak base

HCl(aq) + NH3(aq) ⇌ Cl-(aq) + NH4+(aq) + H2O (aq)
• Initially titration follows the pattern of a strong acid.

• But equivalence point is at less than pH 7 (approximately 5.5) because of the hydrolysis of
salt.
• The straight vertical section of the graph is shorter than that for a titration of strong acid
with strong bases.
• pH range at equivalence is 3.5-7.5.

4. Weak acid with weak base

• The variation of pH with volume of
titration is more gradual and not
possible to detect the accurate
equivalence point.
• pH at equivalence point is
approximately 7. But is will always
depend on dissociation constant.
• No straight vertical section on
graph.
Vertical pH range
• There is a large change in pH for a very small addition of acid around the end point of the
titration in all cases except that for weak acids or weak bases.
• The pH change at the endpoint is around 7 units for strong acid + strong base titrations but
only about 4 units for weak acid/strong base and for strong acid/weak base.
• The small change in pH in the later cases is because the solution just before or just after the
end point consists of a buffer solution which resists changes in pH.
o Weak acid + strong base titration: the buffer solution forms before the end point.
o Strong acid + weak base titration: the buffer solution forms after the end point.
• The weak acid and weak base titration contain a buffer solution both before and after the
end point of the titration. Thus, a large change in pH does not occur.
End-point pH
• The pH at the end point of the titration is not always 7 due to salt hydrolysis reactions.
• For weak acid + strong base titration the weak acid produces a strong conjugate base which
is capable of reacting with water to generate the acid. In this solution [OH-] is greater than
[H3O+]. Thus, pH is greater than 7.
• For example, in a titration between ethanoic acid and sodium hydroxide, the salt sodium
ethanoate is formed.
• It hydrolyses as follows:
o CH3COONa(aq) + H2O(l) ⇌ CH3COOH(aq) + NaOH (aq)
OR
o CH3COO-(aq) + H2O(l) ⇌ CH3COOH(aq) + OH-(aq)

• For a strong acid + weak base titration, the weak base produces a strong conjugate acid
which will undergo hydrolysis producing hydrogen ions. In this solution [H3O+] is greater than
[OH-]. Thus the pH is less than 7.
• For example in a titration between hydrochloric acid and ammonia titration, the salt formed
is ammonium chloride.
• It hydrolyses as follows:
NH4+(aq) + H2O(l) ⇌ NH3(aq) + H3O+(aq)
Summary of pH curves
Equivalence
Initial pH pH range Final pH
point
Strong
1 3.5 – 10.5 7 13
acid/strong base
Strong 1
3.5 – 7.5 <7 11
acid/weak base
Weak
3 7.5- 10.5 >7 13
acid/strong base
Weak acid/weak
3 - 7 11
base
Acid-base indicators
• Indicators are weak organic acids or weak bases.
• Most common indicators are weak acids (HIn). For an indicator that is a weak acid, it’s
dissociation in aqueous solution can be represented as:
HIn (aq) ⇌ H+ (aq) + In-(aq)
o The molecule HIn and its conjugate base, In-, have different colours in aqueous
solution. For methyl orange, the colours are red and yellow respectively.
HIn (aq) ⇌ H+ (aq) + In-(aq)
Red yellow
o When [H+] is sufficiently large the equilibrium will shift far enough to the left for the
red colour to predominate. If [H+] is very low then the equilibrium will lie far over to
the right and the yellow colour predominates. Therefore, the indicator changes
colour according to the pH of the solution.

• The strength of an indicator on an acid depends on the Ka value for the indicator which is
called the Indicator dissociation constant, KIn. The KIn expression for the above indicator is:
[H3O+] [In-]
KIn =
[HIn]
• The indicator will show an intermediate colour when [HIn] = [In-].
• In this situation,
KIn = [H3O+]
-log10KIn= -log10[H3O+]
pKIn= pH
• The indicator will show its intermediate colour at a pH value which is determined by the pKIn
value for the indicator. Since all indicators have different pKIn values, they will change colour
at different pH values.
• The complete colour change from colour 1 to colour 2 or vice versa requires a change of
about 1.5 to 2 units of pH. This range is called the working range or pH range of the indicator.
pH range of acid-base indicators

Table below shows the pKIn and pH ranges with its colours for some common indicators.
Indicator pKIn pH range Colour
Methyl orange 3.70 3.10 – 4.40 Red Yellow
Bromophenol blue 4.00 2.80 – 4.60 Yellow Blue
Bromothymol blue 7.00 6.00 – 7.60 Yellow Blue
Phenol red 7.90 6.80 – 8.40 Yellow Red
Phenolphthalein 9.30 8.20 – 10.00 Colourless Red

Choice of indicators
• For use in a titration:
o the pH range of the indicator must overlap with the vertical pH range of the titration
curve.
o The colour change must be sharp rather than gradual.
o the indicator must give a distinct colour.
Strong acid-strong base titration Weak acid-Strong base titration
Strong acid-Weak base titration Weak acid-Weak base titration

Titration curves with diprotic acids

• Diprotic acids have two protons which can be successfully replaced in what are effectively
separate acid-base titrations.
• The titration curve for such a reaction shows two vertical portions.
An example for the titration of ethanedioic acid with NaOH is given below.
o H2C2O4(aq) + NaOH(aq) ⇌ NaHC2O4(aq) + H2O(l) Step 1
o NaHC2O4(aq) + NaOH(aq) ⇌ Na2C2O4(aq) + H2O(l) Step 2
• If indicator 1 is used, the equation for step 1 only is appropriate. If indicator 2 is used, then
the equations for step 1 and 2 must be added together
./'
%&'(#)#./0#!#*+,(-'&'#
1/02*.&+3#!#
second equivalence point
1/02*.&+3#)# %&'(#)#*+,(-'&'#
First equivalence point
!"########################################"$# !"#$%&'"(')*+&','-%!'


1. The equation for the reaction between hydrochloric and ammonia is:
HCl(aq) + NH3(aq) →NH4Cl(aq)
A 25.0 cm sample of 0.0200 mol dm-3 HCl(aq) was placed in a conical flask. Aqueous ammonia
3
was added gradually from a burette and the pH was measured after each addition, until the pH
no longer changed.
The pH curve for this titration is shown below.
(a) State how the curve suggests that ammonia is a weak base.
(b) Use the information given to calculate the concentration of the ammonia solution.
(c) The pH ranges for three indicators are:
Thymol blue: 1.2 to 2.8
Methyl red: 4.2 to 6.3
Thymolphthalein: 9.3 to 10.5
Explain which of these three indicators is the most suitable for this titration.
2. (a) Calculate the pH at 298 K of an aqueous solution of CH3COOH of concentration 0.100 mol
dm-3. [Ka = 1.74 x 10-5 mol dm-3 at 298 K]
(b) Sketch the pH titration curve for the addition of 50.0 cm3 of 0.100 mol dm-3 NaOH(aq) to
25.0 cm3 of 0.100 mol dm-3 CH3COOH(aq).
(c) State two differences in the pH curve that would be obtained if the titration were repeated
using 25.0 cm3 of 0.0500 mol dm-3 CH3COOH(aq) instead of 25.0 cm3 of 0.100 mol dm-3
CH3COOH(aq).

14B 2 BUFFER SOLUTIONS SPECIFICATION

14.17, 14.18, 14.19,
14.20 & 14.22
• Buffer solutions are solutions of known pH which have the ability to resist changes in pH
when a small amount of acid or alkali is added.
• These consist of an acid/base conjugate pair.
• An acidic buffer consists of a weak acid and its strong base salt.
Example: ethanoic acid and sodium ethanoate
• An alkaline buffer consists of a weak base and its strong acid salt.
Example: ammonia and ammonium chloride.
• To be able to resist pH changes, the concentration of both the acid and the conjugate base
must be similar.
Buffer from weak acid and its conjugate base

• Consider a buffer of ethanoic acid and sodium ethanoate. The salt is fully ionized as follows:
CH3COONa(aq) → CH3COO-(aq) + Na+ (aq)
• The weak acid is partially ionized as follows:

CH3COOH(aq) ⇌ CH3COO-(aq) + H+ (aq)
• The CH3COO- ions from the salt suppress most of the ionization of the acid, so both
[CH3COOH(aq)] and [CH3COO-(aq)] are large.
• If H+ (an acid) is added to the solution, almost all of them are removed by the reaction with
the large reservoir of CH3COO- ions from the salt as follows:
CH3COO- (aq) + H+ (aq) → CH3COOH (aq)
• If OH- (an alkali) is added, almost all of them are removed by the reaction with the large
reservoir of CH3COOH molecules of the weak acid as follows:
CH3COOH(aq) + OH- (aq) → CH3COO-(aq) + H2O (l)
• Since the ratio of [acid]:[salt] hardly changes pH will hardly change. Therefore, pH is
maintained almost constant.

WORKED EXAMPLE
a. 25 cm3 of 1.00 moldm-3 of ethanoic acid is mixed with 25 cm3 of 1.00 moldm-3 sodium
ethanoate at 298K. calculate the pH of this buffer solution.
b. Calculate the change in pH of the buffer solution if 0.01 mol of HCl is added.

Henderson-Hasselbalch Equation
• The Henderson-Hasselbalch equation can be used to calculate the pH of buffer solution.
• Consider a buffer solution made from a weak acid, HA, and its sodium salt, NaA.
• The acid is partially ionized as follows:
HA(aq) ⇌ A-(aq) + H+ (aq)
• The acid dissociation constant, Ka, for the acid is:
[H+ (aq)][A- (aq)]

Ka =
[HA (aq)]
but in this situation, [A-] and [H+] are NOT equal, since the salt has been added to the
solution.
• Two assumptions are made when calculating the pH of a buffer solution:

o The [A-] = [salt], because the salt is assumed to be 100% ionized and the anion
concentration from the acid is very small compared to that from the salt.
o The [HA] = [weak acid], because the presence of excess anion from the salt suppress
the ionization of the acid to such a low level that it can be considered negligible.
• Thus, the Ka expression can be modified as follows:
[H+ (aq)][Salt (aq)]
Ka =
[HA (aq)]
• The [H+] can worked using expression below, if all the others are known. Hence the pH can
be calculated.
[HA]
+
[H (aq)] = Ka x
[salt]
Take logarithm to both side and we get:
[Salt]
pH = pKa + log
[Acid]

Buffer from weak base and its conjugate acid

• Consider a buffer of ammonia and ammonium chloride. The salt is fully ionized as follows:
NH4Cl(aq) → NH4+(aq) + Cl- (aq)
• The weak base is partially ionized as follows:

NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)
• The NH4+ions from the salt suppress most of the ionization of the base, so both [NH3(aq)]
and [NH4+(aq)] are large.
• If H+ (an acid) is added to the solution, almost all of them are removed by the reaction with
the large reservoir of NH3 ions from the weak base as follows;
NH3 (aq) + H+ (l) ⇌ NH4+ (aq)
• If OH- (an alkali) is added, almost all of them are removed by the reaction with the large
reservoir of NH4+as follows:
NH4+ (aq) + OH- (aq) → NH3 (aq) + H2O (l)
• Since the ratio of [base]:[salt] hardly changes pH will hardly change. Therefore, pH is
maintained almost constant.
How to make a buffer solution with a required pH

WORKED EXAMPLE 1
Calculate the proportion of ethanoic acid of concentration 0.575 moldm-3 and sodium ethanoate
of concentration 1.00 moldm-3 needed to make a buffer solution with pH 5.00 at a temperature
of 298K. (Ka of ethanoic acid = 1.74 x10-5 moldm-3)

WORKED EXAMPLE 2
In what proportion should 0.1 moldm-3 of ammonia and ammonium chloride be mixed to form a
buffer solution with pH 9.80? ( Ka = 5.62 x 10 -10)
CHECKPOINT QUESTIONS PAGE 99

1. (a) Explain what is meant by the term 'buffer solution'.
(b} Explain how an aqueous solution containing a mixture of methanoic acid, HCOOH, and
potassium methanoate, HCOOK, acts as a buffer.
(c) A buffer solution contains equal concentrations of methanoic acid and potassium
methanoate.
Explain the effect on the pH of this solution of adding some solid potassium methanoate.
(d) Calculate the pH, at 298 K, of a buffer solution made by mixing equal volumes of 1.00 mol
dm-3 methanoic acid and 0.500 mol dm-3 potassium methanoate.
[Ka(HCOOH} = 1.79 x 10-4 mol dm-3]
2 . A student prepares two solutions.
Solution A is prepared by mixing 50 cm3 of 0.100 mol dm-3 CH3COOH(aq) with 25 cm3 of 0.100
mol dm-3 NaOH(aq).
Solution B is prepared by mixing 25 cm3 of 0.200 mol dm-3 CH3COOH(aq) with 50 cm3 of 0.100
mol dm-3 NaOH(aq).
Explain why solution A is a buffer solution but solution B is not.
3. Calculate the pH of a buffer solution containing 12.20 g of benzoic acid (C6H5COOH) and 7.20
g of sodium benzoate (C6H5COONa) in 1.00 dm3 of solution.
[pK.(C6H5COOH} = 4.20]

Controlling pH of blood
• The human body works within a narrow range of pH values.
Example: arterial blood plasma needs to be in the range 7.35 to 7.45.
• The pH of blood cells is controlled by a mixture of buffers. The most common is carbonic
acid-hydrogen carbonate buffer mixture.
o In this mixture the carbonic acid acts as the weak acid and the hydrogen carbonate
is its conjugate base.
o The equilibrium that exists is represented as:
H2CO3 (aq) ⇌ HCO3 – (aq) + H+ (aq)
o An increase in the hydrogen ion concentration in blood (due to formation of lactic
acid in muscles) results in the equilibrium to shift to the left.
• A variety of respiratory and metabolic factors can also cause the pH of the blood to rise.
Example, overuse of diuretics increases the amount of urine excretion from the body.
o If the urine contains large amount of acids, then the pH of the blood will increase.
Hence the equilibrium shifts to the right as the carbonic acid molecules ionize to
increase the H+ concentration and restore the pH to the normal level.
• Carbonic acid is not stable, and in aqueous solution it decomposes to form carbon dioxide
and water.
H2CO3 (aq) ⇌ CO2 (aq) + H2O (aq)
o The respiratory system is responsible to remove carbon dioxide from the body. Aqueous
carbon dioxide is in equilibrium with gaseous carbon dioxide.
CO2 (g) ⇌ CO2 (aq)
o Combining the equations gives:
CO2 (g) + H2O (aq) ⇌ CO2 (aq) + H2O (aq) ⇌ H2CO3 (aq) ⇌ HCO3 – (aq) + H+ (aq)
When these equilibria shift to the left because of increase in [H+], the concentration of carbon
dioxide in the blood increases. The carbon dioxide leaves the blood in the lungs and is then exhaled,
thus maintaining the normal pH of the blood.
Buffers in food
• A combination of various factors such as light, oxygen, heat, humidity and/or many kinds of
microorganisms can spoil food
• Spoilage of food by microorganisms depends greatly on the pH value of the food.
• Most microorganisms thrive when the pH of their surrounding is between pH 6.6 – 7.5. most
bacteria’s can survive at a pH as low as 4.4 and as high as 9.0.

• One important factor in the spoilage of food is its buffer capacity.

o Buffer capacity is the measure of the amount of acid or base required to change
the pH of the food significantly. The more protein there is in the food, the higher
its buffer capacity.
o This is because the amino acid present have both acidic and basic properties.
Hence, it takes longer for the pH of the food to change enough for the bacteria
to start multiplying.
14B 3 BUFFER SOLUTIONS AND pH CURVES SPECIFICATION

14.17, 14.18, 14.19,
14.20 & 14.22
• For weak acid and strong base titration, a

buffer range can be seen. In the region
marked ‘buffer range’, the change in pH as
the base added is gradual.
• At this range there is a considerable
concentration of both acid and the
conjugate base molecules
Ka from pH titration curves

When half of the acid is neutralized
(when x/2 cm3 of base is added),
[HA] = [A-]
Then Ka = [H+]
And pKa = pH = y
pH = pKa at half equivalence value


1 A student carried out a titration by adding hydrochloric acid to ammonia solution. A sketch graph
of pH against volume of hydrochloric acid added is shown below.
(a) Name the type of solution formed in the region ringed on the sketch graph. {b) Explain how
you deduced your answer to part (a).
2 The diagram shows the titration curve for a weak acid.
Use the curve to determine the pKa. value for the acid. Explain how you arrived at your answer.

Unit 4 - Acid-Base Equilibria Notes 2023

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Centre for Higher Secondary Education Department of Chemistry

TOPIC 14: ACID – BASE EQUILIBRIA

14.2 be able to identify Brønsted–Lowry conjugate acid-base pairs

14.3 be able to define the term ‘pH’

14.4 be able to calculate pH from hydrogen ion concentration

14.7 be able to calculate the pH of a strong acid

Students will not be expected to solve quadratic equations.

14.10 be able to define the ionic product of water, Kw

14.12 be able to define the terms ‘pKa’ and ‘pKw’

14.13 be able to analyse data from the following experiments:

i measuring the pH of a variety of substances, including equimolar solutions of strong and

14.17 know what is meant by the term ‘buffer solution’

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 1 of 32

14.19 be able to calculate the pH of a buffer solution given appropriate data

i demonstrate buffer action

14.22 understand the importance of buffer solutions in biological environments:

i buffers in cells and in blood (H2CO3/HCO3 - )

ii in foods to prevent deterioration due to pH change (caused by bacterial or fungal activity)

14.23 CORE PRACTICAL 11

Finding the Ka value for a weak acid.

Further suggested practicals:

i carry out the measuring of the pH of solutions mentioned in 14.13

iii analysis of vinegar

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 2 of 32

14A 1 THE BRØNSTED – LOWRY THEORY SPECIFICATION

BrØnsted – Lowry acids and bases

• an acid as a substance consisting of molecules or ions which donates protons, (a proton

Conjugate acid-base pairs

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 3 of 32

CH3COOH + H2O ⇌ CH3COO- + H3O+

Acid 1 Base 2 Base 1 Acid 2

HCl + H2O ⇌ Cl- + H3O+

Acid 1 Base 2 Base 1 Acid 2

Identify the conjugate acid-base pairs in the following reactions.

b. HNO3(aq) + H2SO4(aq) ⇌ H2NO3+(aq) + HSO4- (aq)

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 4 of 32

Strong acids and weak acids

Organic acids are examples of weak acids

14A 2 HYDROGEN ION CONCENTRATION AND THE SPECIFICATION

Strong acids and pH

[H3O+] = concentration of the strong acid.

• Definition: pH = ─ log10 [H3O+(aq)]

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 5 of 32

b. 0.150 moldm-3 HBr

Hydrogen ion concentration from pH

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 6 of 32

Weak Acids & Acid Dissociation Constant

[H3O+ (aq)][A- (aq)]

§ The Ka expression must not have [H2O]

Weak Acids & pH

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 7 of 32

[H3O+ (aq)][A- (aq)]

• If the value of Ka and [HA] are known

[HA (aq)] and hence the pH of the acid.

o The equilibrium concentration, [HA], is equal to the initial concentration of the

[HA] = [weak acid] – [H3O+]

but since [H3O+] is very small, the approximation used is valid.

o For a weak acid, HA, in solution [H3O+] = [A-].

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 8 of 32

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 9 of 32

Grade 11/Unit 4.14- Acid-Base Equilibria /2022/semester 3 Page 10 of 32

CHECKPOINT QUESTIONS PAGE 85

14A 3 IONIC PRODUCT OF WATER, KW SPECIFICATION