University of Zambia

Department of Chemistry
CHE2219-Chemical Analysis

ACID BASE EQULIBRIA

Francis Kayamba
 Acids And Bases Theories
Lewis Theory
▪ Lewis acid: any substance that can accept a pair of
electrons to form a new bond. Also referred to as
electrophiles (electron pair loving or seeking)

▪ Lewis base; any substance that can donate a pair of

electrons to form a new bond Also, referred to as
nucleophiles (nucleus loving or seeking a positive nucleus.

▪ IN short, Lewis acid => electron acceptor

Lewis base => electron donor.

 The Lewis Theory of acids and bases

Potential Lewis acids

• All positive ions,

• Any compound in which the central atom has an

incomplete octet, e.g., BF3 or AlCl3,

Potential Lewis acids

• All negative ions Cl-, Br-, OH-

• Any molecule in which an atom has one or two unshared

(lone) pairs of electrons, example, NH3 or H2O,
 Acids And Bases Theories
Arrhenius Theories

✓ Arrhenius acid: any specie that produce an H+ ion

(proton)—in aqueous solution resulting into the increase
of concentration of H+. E,g HCl

✓ Arrhenius base: any species that produces hydroxide

ions, OH− in aqueous solution. Resulting into the increases
the concentration of hydroxide ions, OH−. Common
Arrhenius bases include other Group 1 & Group 2 hydroxides
Eg NaOH.
 Acids And Bases Theories
Arrhenius theory fails to account for
✓ acidic nature of substances like CO2 , SO2,SO3 etc which do
not have hydrogen

✓ basic nature of substances like CH3NH2, NH3, CaO, MgO etc

which do not have -OH group.

✓ acidic and basic behaviour of substances in solvents other

than water such as ammonia, alcohol or in gaseous state etc
✓ Why strong electrolytes like nitric acid (HNO3) are completely
ionized in aqueous solution whereas weak electrolytes like
acetic acid (CH3COOH) are ionized to a small extent only.
 Acids And Bases Theories
Bronsted-Lowry Acids And Bases

✓ Bronsted-Lowry Acids: Any substance that is a proton

donor (hydrogen ion, H+). i.e. contains hydrogen bonded to a

more electronegative element. For example
HCl ⇌ H+ + Cl-
H2SO4 ⇌ H+ + HSO4-
CH3COOH ⇌ H+ + CH3COO-
✓ Bronsted-Lowry Base: Any substance which can
behave as a proton acceptor. i.e. any species which has
a lone pair of electrons can thus behave as a base:
NH3 + H+ ⇌ NH4+
OH- + H+ ⇌ H2O
CO32- + H+ ⇌ HCO3-
 Conjugate acid-base pairs

✓ All Bronsted-Lowry acids-base reaction are reversible, an

acid ionize to give a proton and a base (proton acceptor).
Acid H+ + base
• Thus an acids ionizes to give a proton and base referred to
as a conjugated base and vice versa.
Acid H+ + base
Acid Conjugate base
Base + H+ Acid
Base Conjugate acid

Species related in this way are known as conjugate acid-

base pairs.
✓ Eg Cl- is the conjugate base of HCl; HCl is the conjugate acid of Cl-
✓ Eg NH3 is the conjugate base of NH4+; NH4+ is the conjugate acid of NH3
 Strength of acid-base
✓ The strength of an acid-base will be described using Arrhenius

theory. Strength of an is the degree of ionization when

dissolved in solvent.

✓ A strong acid-base completely ionizes (split complete (100%

ionization)). Examples; Mineral acids are strong acids such as

sulfuric, hydrochloric and nitric acid.

✓ A weak acid-base does not completely ionize, the parent acid

or base will still available in the solution. All mineral base are

strong acids, Commonly used mineral base Sodium Hydroxide

 Strength of acid-base
• Acids and bases can be ranked in order of decreasing strength; a
list of common acids and their conjugate bases ranked in such a
way is shown below
 Strength of acid-base

✓ The strongest acids are at the top; these have the weakest
conjugate bases.

✓ The strongest bases are at the bottom; these have the

weakest conjugate acids.

✓ Note that some species (eg H2O, HSO3-, HCO3- amongst

others) appear in both columns.

✓ Such species can behave as either acids or bases and are

said to be amphoteric.

•
pH scale
 Calculating the pH of strong acids:

✓ The [H3O+] in a 0.10 moldm-3 solution of HCl is 0.10 moldm-

3. The pH of 0.10 moldm-3 HCl is thus 1.

✓ The [H3O+] in a 0.05 moldm-3 solution of HCl is 0.05 moldm-

3. The pH of 0.05 moldm-3 HCl is thus 1.3.

✓ The [H3O+] in a 2 moldm-3 solution of HCl is 2 moldm-3. The

pH of 2 moldm-3 HCl is thus -0.3.
 The Ionic Product for Water, Kw
Water can undergo auto ionization to produce a hydroxonium
ion and a hydroxide ion

You may well find this equilibrium written in a simplified form:

The ionic product of water

The activity of water molecule is normally constant and it is

considered to be a unity. It can be left out when writing an
ionization constant for water or any other reaction.
 The Ionic Product for Water, Kw

The pH of pure water

In pure water =

Converting that into pH:

Referred as neutral
 The Ionic Product for Water, Kw

In log terms
-log = -log

-log + -log = 14 + -log1

pH + pOH = 14
Example
The variation of the pH of pure water with temperature

According to Le Chatelier, if you increase the temperature of

the water, the equilibrium will move to lower the temperature
by absorbing the extra heat added into the reaction system. A
forward reaction will be favoured, and more hydrogen ions
and hydroxide ions will be formed. Thus increase in
temperature results into increases the value of Kw
 pKa Value
Used to describe the acidity or alkalinity of an substance
 Acidic and alkaline solutions
✓ Any solution which contains more H3O+ ions than OH- ions is
said to be acidic.

✓ The resulting solution contains an excess of OH- ions. Any

solution which contains more OH- ions than H3O+ ions is
said to be alkaline.
 Calculating the pH of weak acids

✓ The H3O+ concentration can be calculated by the following

method:

HA(aq) + HO(l) ⇌ H3O+(aq) + A-(aq)

C-x x x

Ka = [H3O+][A-]

[HA]

✓ Ignoring the H3O+ present due to the auto-ionisation of

water, the H3O+ and A- concentrations can be assumed to be
the same. Therefore [H3O+][A-] = [H3O+]2.
 Calculating the pH of weak acids

• If the degree of dissociation of HA is assumed to be small,

then the molarity of the HA can be assumed to be the same as
that of the solution (assume C-x is approximately equal to C).

Ka = [H3O+]2

[HA]

so [H3O+]2 = Ka[HA]

and [H3O+] =√ Ka[HA]

Example
 Calculating the pH of weak bases

✓ Weak bases do not dissociate fully in water.

✓ They behave in a similar way to weak acids.

Base ionization constant Kb

• When bases interact with water they do so by removing a

hydrogen ion creating hydroxide ions in solution
 Calculating the pH of weak bases

• Weak bases only partially accept protons from the solvent

and are characterized by a base dissociation constant, Kb.
Consider acetate ion:
 Relationship between Ka and Kb

The weaker the acid the stronger the conjugate base (salt) and
ionization shifts to the right favoring formation of HOAc. HOAc
formed does not affect the pH because it is unionized.
Ionization constant (KH) of the equation or basicity constant(Kb)
of the salt
 Relationship between Ka and Kb

Therefore, ionisation constant for acetate ion will be

Relationship between Ka and Kb
Calculate the pH of 0.10 M solution of Sodium acetate
 Determination of Ka for weak acid

✓ Consider a simple method for determining value for Ka at

298 K for benzenecarboxylic acid (benzoic acid) C6H5COOH
(monobaisc acid). Calculate the Ka value of benzoic acid
solution prepared by dissolving 0.5 g into 250 mL with pH
3.

C6H5COOH (aq) = H+(aq) + C6H5COO-(aq)

Ka = [H+][C6H5COO-]

[C6H5COOH ]
 Determination of Ka for weak acid
Method (Procedure)
✓ A small quantity of acid weighed & dissolved in small
amount of water-warm water used and allowed to cool

✓ Then diluted with water in a volumetric flask to make

standard solution

✓ Mass of acid, volume & its Mr are known-hence conc can be

determined.

✓ Next-we ensure the solution is mixed completely and take a

sample of it and measure its pH-use a calibrated pH meter

✓ From the pH reading, conc of H+ is determined

 Determination of Ka for weak acid
n= 0.5/122=0.0041 mol

Volume=250 mL= 25 dm3

Conc= 0.0164 M

pH= 3.0

Remember [H+]= [C6H5COO-]= 1.0 x 10-3 M

Ka = [H+][C6H5COO-]

[C6H5COOH ]

= (1.0 x 10-3 M)2 /0.0164 M = 6.1 x 10-5 M

Look up this value in data books and you will find that it’s the
value for benzanoic acid!
 BUFFER SOLUTIONS

✓ A buffer solution is a solution which can resist

changes in pH on addition of small quantities of acid
or alkali or on dilution.
Note that
✓ The mixture cannot be a mixture of a strong acid and a
strong alkali, eg a mixture of NaOH and HCl would react with
each other and thus not behave as an effective buffer.:the
two can react with each other
✓ If the acid and alkali in the buffer are too weak, however,
they will not react effectively with the acid or alkali that are
added.
 BUFFER SOLUTIONS

✓ A suitable mixture is one which contains a mixture of acid

and alkali strong enough to react with H3O+ and OH-, but
weak enough not to react with each other.

✓ An ideal mixture for this purpose is a mixture of a

weak acid and its conjugate base. For example CH3COOH
and CH3COONa, or NH4Cl and NH3.

✓ The acids and bases in these mixtures will react with OH-
and H3O+ respectively but not with each other.
Types of buffers
 How does a buffer work?
a) Resisting pH change on addition of acid and alkali. These
mixtures will react with acid and alkali as follows:
✓ Consider an acetic/acetate buffering system
✓ When OH- added to buffering system it reacts with
CH3COOH(aq) initiating a forward reaction to product more
CH3COO-
CH3COOH(aq) + OH-(aq) → CH3COO-(aq) + H2O(l)
✓ When H3O+ added to buffering system it reacts with CH3COO-
(aq) initiating a backward reaction to product more CH3COOH
CH3COO-(aq) + H3O+(aq) → CH3COOH(aq) + H2O(l)
More examples;
NH4+(aq) + OH-(aq) → NH3(aq) + H2O(l)
NH3(aq) + H3O+(aq) → NH4+(aq) + H2O(l)
How does a buffer work?
 How does a buffer work?
a) Resisting pH change on addition of acid and alkali. These
mixtures will react with acid and alkali as follows:
✓ Consider an acetic/acetate buffering system
✓ When OH- added to buffering system it reacts with
CH3COOH(aq) initiating a forward reaction to product more
CH3COO-
CH3COOH(aq) + OH-(aq) → CH3COO-(aq) + H2O(l)
✓ When H3O+ added to buffering system it reacts with CH3COO-
(aq) initiating a backward reaction to product more CH3COOH
CH3COO-(aq) + H3O+(aq) → CH3COOH(aq) + H2O(l)
More examples;
NH4+(aq) + OH-(aq) → NH3(aq) + H2O(l)
NH3(aq) + H3O+(aq) → NH4+(aq) + H2O(l)
 Other buffer solutions

• A buffer does not have to a mixture of a weak acid

and its conjugate base; any mixture of a weak acid
and a weak base will have the same effect.
• Substances which can behave as both weak acids
and weak bases can also behave as buffers.
• One important example is sodium
hydrogencarbonate; the HCO3- ion can behave as
either an acid or a base:

HCO3-(aq) + H3O+(aq) → CO2(g) + 2H2O(l)

HCO3-(aq) + OH-(aq) → CO32-(aq) + H2O(l)
 buffering capacity
✓ The amount of acid or base that can be added to the buffer
solution without causing a large change to pH is called
buffering capacity.
✓ he higher the concentration of the ration the more tolerant
the solution Buffering also called buffer index or intensity is
given by

he buffering capacity is always a positive.

The bigger is β the
more the resistance. For weak acid/
conjugate
 buffering capacity
The buffering capacity is always a positive. The bigger is β the
more the resistance. For weak acid/ conjugate

For example, If you have a mixture of 0.10 M acetic and 0.10 M

sodium acetate, the buffering capacity will be
buffering capacity
 Other buffer solutions
• Amino acids can also behave as buffers:
Eg CH3CH(NH2)COOH - 2-aminopropanoic acid

CH3CH(NH2)COOH(aq) + OH-(aq) → CH3CH(NH2)COO-(aq) + H2O(l)

CH3CH(NH2)COOH(aq) + H3O+(aq) → CH3CH(NH3+)COOH(aq) + H2O(l)

 Calculating the pH of buffer solutions

❑ Henderson–Hasselbalch equation
• Equation showing the relationship between a buffer’s pH &
the relative amounts of the buffer’s conjugate weak acid and
weak base.

• Can be used to estimate the pH of buffer solutions, it is

derived by rearranging the acid dissociation expression for
the conversion of a weak acid (HA) into its conjugate base
(A-) so that the expression is interms of pH.
pH=Pka + log[A-]
[HA]
 Buffers:Keeping the pH Constant (or Nearly So)

In logarithm terms

Rewritten as
 Example
• Example: An aqueous buffer for analyzing the various ions in rain water is
prepared and has equilibrium concs. Of 5.0x10-5 M boric acid and 2.0x10-5
M borate (conjugate base of boric acid). Using th H-H equation, estimate the
pH of this solution at 25oC.
Solution:
Ka1 for boric acid is 5.79 x 10-10, Pka=9.237,
pH=PKa+ log[A-] = 9.237+log(2.0X10-5)/(5.0X10-5)=pH=8.84
[HA]
 Example
• Calculate the pH of a buffer prepared by
adding 10 mL of 0.10 M acetic acid to 20
mL of 0.10 M sodium acetate.
• the amount of acid dissociated is very small,
particularly in the presence of the added salt
(ionization suppressed by the common ion
effect), and can be neglected.
• Hence, we can assume the added
concentrations to be the equilibrium
concentrations:
 Buffer pH calculation example
• eg, a mixture containing 0.2 moldm-3
CH3COOH (Ka = 1.7 x 10-5 moldm-3) and 0.1
moldm-3 CH3COONa
This solution has a [H3O+] concentration of
1.7 x 10-5 (0.2/0.1) = 3.4 x 10-5 moldm-3.
Therefore the pH of the solution is 4.5.
 Salts
• A salt is an ionic compound containing an anion other
than OH- or O2-.

• Almost all salts dissolve completely in water at

concentrations commonly used in biological research.

• A salt consists of ions both when in the solid form and

when dissolved in water.
 Salts
• Product of neutralization reactions eg NaCl.

• They are also strong electrolytes.

• One mole of NaCl will generate one mole of sodium

ions and one mole of chloride ions.

• Salts from weak acids and weak bases will also

ionize completely when placed in aqueous solution.
 Salts

• For many salts dissolved in water, one of the

ions react with water to form significant
amounts of either H3O+ or OH-, i.e, the ions
act as weak acids or bases or both.
• The reaction is termed a hydrolysis.

• eg, when NH4Cl is dissolved in water the

ions, NH4+ & Cl- react with water.
 Salts
• A small fraction of the NH4+ reacts as
follows:

• Although only a small fraction reacts, it

is sufficient to make the solution acidic.

• Cl- does not react to any significant

extent.
 Salts
• Solutions of salts are very common in
chemistry, biological systems,
environmental matrices, etc.

• We can now predict in a qualitative sense

(and in some cases quantitatively) the pH
of solutions of acids, bases & salts.
 Salts

• Salts of strong acids/strong bases

 Salts

• Salt of Strong Acid/Weak Base

 Salts
• Salt of Weak Acid/Strong Base
 Salts of Weak Acids & Bases—They Aren’t Neutral

• The salt of a weak acid, eg, NaOAc, is a strong

electrolyte, like (almost) all salts, & completely
ionizes.
• the anion of the salt of a weak acid is a
Brønsted base, which will accept protons.
OAc- = CH3COO-
• It partially hydrolyzes in water (a Brønsted
acid) to form OH- & the corresponding
undissociated acid. eg,
 Salts of Weak Acids & Bases—They Aren’t Neutral

• The HOAc here is undissociated and therefore

does not contribute to the pH.

• This ionization is also known as hydrolysis of

the salt ion.

• Because it hydrolyzes, sodium acetate is a

weak base (the conjugate base of acetic acid).
 Salts of Weak Acids & Bases—They Aren’t Neutral

• We can write an equilibrium constant:

• KH is called the hydrolysis constant of the salt

and is the same as the basicity constant.
• We will use Kb to emphasize that these salts
are treated the same as for any other weak
base
 Salts of Weak Acids & Bases—They Aren’t Neutral

• The value of Kb can be calculated from Ka of

acetic acid and Kw

• The product of the acid dissociation constant

of any acid and the base dissociation constant
of its conjugate base is Kw.
 Salts of Weak Acids & Bases—They Aren’t Neutral

• For any salt of a weak acid HA that

hydrolyzes in water,
 Salts of Weak Acids & Bases—They Aren’t Neutral

• The pH of such a salt (a Brønsted base) is

calculated in the same manner as for any
other weak base.
• When the salt hydrolyzes, it forms an equal
amount of HA and OH−.
• If the original concentration of A− is CA−,
then
 Salts of Weak Acids & Bases—They Aren’t Neutral

• The quantity x can be neglected compared

to CA−
….if CA− > 100Kb, which will generally be the
case for such weakly ionized bases. we can
solve for the OH− conc using Eq
• This equation holds only if CA− > 100Kb, and
x can be neglected compared to CA−.

• If this is not the case, then the quadratic

formula must be solved as for other bases in
this situation.
 Example

• Calculate the pH of a 0.10 M solution of

sodium acetate. If Ka for acetic acid is 1.75 x
10-5
Salts of Weak Acids & Bases—They Aren’t Neutral
 ACID-BASE EQUILIBRIA IN
AQUEOUS SOLUTIONS

Mixtures of Salts of Weak Acids and Bases and buffer systems

 Mixtures of Salts of Weak Acids and Bases and buffer systems

• A salt is a product of the reaction of a base and

an acid. The anion of the salt of a weak acid is a
B-L base.

• Consider acetate(OAc-) ion from (NaOAc; Na

ethanoate or acetate, a salt of a weak acid
CH3COOH).

• Mixtures of salts of weak acids & bases or acids

& their conjugate base form buffer systems.
 Buffers:Keeping the pH Constant (or Nearly So)

• A buffer is a solution that resists changes in

pH when small amount of acid or base are
added to it when the solution is diluted.
pH changes during Acid Base
Titrations
 Introduction: Titrimetric Analysis
❖ Term refers to quantitative chemical analysis carried out
by determining the volume of a solution of accurately
known concentration..

❖ … which is required to react quantitatively with a

measured volume of a solution of a substance to be
determined.

❖ The solution of accurately known concentration is called

standard solution.

74
 Introduction: Titrimetric Analysis

❖ The term volumetric analysis was used for this form of

quantitative determination but it has now been replaced by
titrimetric analysis.
❖ In titrimetric analysis..
❖… the reagent of known concentration is called titrant &
the substance being titrated is termed the titrand.
❖ The standard solution is usually add from a long graduated
tube called burette.
❖ The process of adding the standard solution until the
reaction is just complete is termed titration.

75
Introduction: Titrimetric Analysis

❖ The point at which this occurs is called equivalence

point or the theoretical (or stoichiometric) end point.

❖ The completion of the titration is detected by some

physical change,..
❖ .. produced by the standard solution itself or,..

❖ ..more usually, by the addition of an auxiliary reagent,

known as an indicator

76
Introduction: Titrimetric Analysis

❖ After the reaction between the substance & the

standard solution is practically complete,..

❖… the indicator should give a clear visual change (either

a color change..

❖ ..or the formation of turbidity) in the liquid being

titrated.

77
 Introduction: Titrimetric Analysis
❖ Point at which this occurs is called the end point of the
titration.

❖ In the ideal titration the visible end point will coincide

with the stoichiometric or theoretical end point.

❖ In practice, however, a very small difference usually

occurs this represents the titration error.

❖ The indicator & experimental conditions should be so

selected that the difference between the visible end point
and equivalence point is as small as possible

78
 Division of volumetric analysis
methods
1) Neutralization analysis – reaction takes place in
presence of water as solvent.
• Most popular.
• Involves transfer of a proton from the acid to
the base. eg Acids in wine by titration with
standard NaOH solution .
• a) acidimetry -we titrate an alkali solution with an
acid (HCl more preferable to H2SO4 in the titration
of compounds that yield precipitate , Sulfuric Acid
– preferable in hot titrations since HCl will
volatilize)
79
 Division of volumetric analysis
methods
• b) alkalimetry -we titrate an acid solution by
an alkali solution to determine the acid.
• KOH, NaOH, Ba(OH)2 frequently used
standards & should frequently be
restandardized.

80
 Division of volumetric analysis
methods
• 2) Precipitation methods- Involves removal of the
analyte as a precipitate.
❖ It includes the methods where the reacting
substance and standard solution react to yield a
precipitate..
❖… or a slightly soluble salt as the primary reaction
product.
❖ NaCl, KBr, AgNO3 is used as standards.
❖Eg analysis of salt levels by precipitation of
chloride using standard silver nitrate solution.

81
 Division of volumetric analysis
methods
• 3 ) Complexometric titrations: It includes all the
methods where in the reacting substance and the
standard solution react to form a soluble but very
slightly dissociated complex substance.
❖ Metal ions form complex by bonding to ligands
which have pairs of unbonded electrons.
❖In other words, it is based on complex formation
reaction mainly EDTA titrations.
❖ Eg determination of water hardness by titration
with EDTA .
82
 ACID-ALKALI TITRATIONS
• A reaction between an acid and an alkali is
known as a neutralisation.
• The concentration of an acid can be determined
by titrating it against a standard alkali solution
using a suitable indicator, and the concentration
of an alkali can be determined by titrating against
a standard acid solution.
 Acid-base titrations
• If solution A is titrated against solution B, it
means that solution A is in the conical flask
and solution B is in the burette.
• The behaviour of acid-alkali mixtures during
titrations depends on whether the acids and
bases are strong or weak.
 Acid-base titrations

➢An acid/base titration is a procedure used in

quantitative chemical analysis,.. in order to
determine the concentration of either an acid
or a base.
 Carrying out a titration

❑ Theconcentration of an acid or alkali can be calculated

by carrying out an experiment called a titration.
❑ You should be able to identify the apparatus needed to
carry out a simple acid-alkali titration, and to describe
how it is done.

86
Materials

❖ pipette to accurately measure a certain volume of acid or

alkali
❖ pipette filler to use the pipette safely

❖ conical flask to contain the liquid from the pipette

❖ burette to add small, measured volumes of one reactant

to the other reactant in the conical flask

87
Titrimetric Analysis

88
89
Standard Solutions

❑A standard solution=Solution of known concentration

❑ Two types
❑ Primary and secondary!

90
Primary Standards

❑ahighly purified compound that serve as a reference

material in all volumetric method.
❑ Theaccuracy of method is critically dependent on the
properties of this compound.
❑ Important requirements for primary standard are:
1- High purity.
2- Stability toward air.
3- Absence of hydrated water.

91
 Primary standard properties

4- Ready availability at modest cost.

5- Reasonable solubility in titration medium.
6- Reasonably large molar mass so that the relative error
associated with weighing the
standard is minimized.
❑ Compound that meet or even approach these criteria are
very few , and only a limited number of primary standard
substances are available to the chemist.

92
Secondary standard

❖a compound whose purity has been established by

chemical analysis…
❖… & serves as the reference material for titrmetric
method of analysis.

❖ Compound such as NaOH or HCl cannot be considered

as primary standard since their purity is quite variable.

93
Secondary standard
❖ For instance NaOH solution must be standardized
against potassium hydrogen phthalate (primary
standard),which is available in high purity.

❖ The standardized sodium hydroxide solution

(secondary standard) may be used to standardize
solutions.

94
 Standard solution

❑reagent of exactly known concentration that is

used in titrimetric analysis.

❑Standard solutions play a central role in all

titrimetric method of analysis.

❑Therefore we need to consider the desirable

properties for such solutions, how they are
prepared and how their concentration are
expressed.
95
 Desirable properties of standard solutions

1- be sufficiently stable so that it is only necessary to

determine the concentration once.
2- react rapidly with the analyte so that the time required
between additions of reagent is minimized .
3- react more or less completely with the analyte so that
satisfactory end points are realized.
4- Undergo a selective reaction with the analyte that can be
described by simple balanced equation.
Few reagents meet all these ideal perfectly.

96
 Titrimetric Analysis Procedure

1. Use the pipette and pipette filler to add 25 cm3 of alkali to

a clean conical flask.

2. Add a few drops of indicator and put the conical flask on a

white tile (so you can see the colour of the indicator more
easily).

3. Fill the burette with acid (standard solution) and note the
starting volume.

97
Titrimetric Analysis Procedure

4. Slowly add the acid from the burette to the alkali in the
conical flask, swirling to mix.

5. Stop adding the acid when the end-point is reached

(the appropriate colour change in the indicator
happens). Note the final volume reading

6. Repeat steps 1 to 5 until you get consistent readings

❑ The same method works for adding an alkali to an acid
- just swap around the liquids that go into the conical
flask and burette.

98
 The titre

❖ Thedifference between the reading at the start & the final

reading gives the volume of acid (or alkali) added.
❖ This volume is called the titre.

❖ For example, if the reading at the start is 1.0 cm3 and the
final reading is 26.5 cm3,

❖ then the titre is 25.5 cm3 (26.5 – 1.0).

❖ Note that the titre will depend upon the volume of liquid in
the conical flask, and the concentrations of the acid and
alkali used.
99
 The titre

❖ Itis important to repeat the titration several times to check

that your titre value is consistent so that your calculations
are reliable.

❖a single indicator like litmus or phenolphthalein gives a

sharp end-point where the colour changes suddenly.

100
 Definition of some terms

❑ Titration

process in which the standard reagent is added to a

solution of an analyte until the reaction between the
analyte and reagent is complete.
❑ Equivalence point & End point
The equivalence point of a titration is a theoretical point
that can not be determined experimentally.
Instead, we can only estimate its position by observing
some physical change associated with the condition of
equivalence.
This change is called the end point for titration.

101
Definition of some terms

❑ Titration error
The difference between the observed end point and the
true equivalence point in a titration.
❑ Indicators

added to analyte solution in order to give an observable

physical change (end point) at or near the equivalence
point.

In other wards indicator is a compound having a

physical property (usually color) that changes abruptly
near the equivalence point of a chemical reaction.

102
Equivalence point & End point

▪ Normally, a visual indicator is used in order to help

determine the equivalence point by noticing the
exact point at which the colour of the solution
changes.

▪ The point when the colour changes is the end point

of the titration.

103
Equivalence point & End point

• If the indicator is chosen correctly the end point and the

equivalence point are the same.

• A pH meter, or conductimetric method, can also be used

to determine the equivalence point in an acid/base
titration.

104
 Titration Curves

❖ To find the end point we monitor some property of the

titration reaction that has a well defined value at the
equivalence point.
❖ For example, the equivalence point for a titration of HCl
with NaOH occurs at a pH of 7.0.
❖ We can find the end point, therefore, by monitoring the
pH with a pH electrode or by adding an indicator that
changes color at a pH of 7.0.

105
Titration Curve Example

106
Titration Curve

107
 1. pH changes during strong acid -
strong alkali titrations
• If 0.1 moldm-3 NaOH is added dropwise to 20 cm3 of 0.1
moldm-3 HCl (2 x 10-3 moles), the change in pH of the solution
can be calculated by considering the reaction taking place.
• Before the addition of NaOH, the pH of the solution is 1.0.
• After the addition of 10 cm3 (1 x 10-3 moles) of 0.1 moldm-3
NaOH:
NaOH + HCl → NaCl + H2O
• Before: 1 x 10-3 2 x 10-3 -
• After: - 1 x 10-3 1 x 10-3 Total volume = 30 cm3.
[H3O+] = 1 x 10-3 = 0.033 moldm-3 pH = 1.5
• 0.03
 . pH changes during strong acid -
strong alkali titrations
• After the addition of 19.95 cm3 (1.995 x 10-3 moles) of
0.1 moldm-3 NaOH: (ie 1 drop before the equivalence
point)
NaOH + HCl → NaCl + H2O

Before: 1995 x 10-3 2 x 10-3 -

After: - 5 x 10-6 1.995 x 10-3 Total volume = 39.95 cm3.

[H3O+] = 5 x 10-6 = 1.25 x 10-4 moldm-3 pH = 3.9
0.03995
• After the addition of 20.0 cm3 of 0.1 moldm-3 NaOH (ie at the equivalence
point)
• [H3O+] = [OH-] = 1 x 10-7 M so pH = 7.0
•
• After the addition of 20.05 cm3 (2.005 x 10-3 moles) of 0.1 moldm-3 NaOH: (ie 1
drop after the end-point)
• NaOH + HCl → NaCl + H2O
Before: 2.005 x 10-3 2 x 10-3 -
After: 5 x 10-6 - 2 x 10-3 Total volume = 40.05 cm3.

• [OH-] = 5 x 10-6 = 1.25 x 10-4 moldm-3, so [H3O+] = 8.0 x 10-11 moldm-3 pH = 10.1
0.04005

• The pH of the solution during a strong acid - strong alkali

titration therefore changes from around 4 to 10 over two drops
at the equivalence point.
A titration curve for a strong acid - strong alkali titration can
be sketched as follows:
 2. pH changes during weak acid - strong alkali
titrations

• If 0.1 moldm-3 NaOH is added dropwise to 20 cm3 of 0.1 moldm-3

CH3COOH (2 x 10-3 moles), the change in pH of the solution can be
calculated by considering the reaction taking place.
• Before the addition of NaOH, the pH of the solution is 2.9.
• After the addition of 10 cm3 (1 x 10-3 moles) of 0.1 moldm-3 NaOH:
NaOH + CH3COOH → CH3COONa +
H2O
• Before: 1 x 10-3 2 x 10-3 -
• After: - 1 x 10-3 1 x 10-3
Total volume = 30 cm3.
 weak acid - strong alkali titrations
• The solution now contains a mixture of a weak
acid (CH3COOH) and its conjugate base
(CH3COO-).
• It thus behaves as a buffer solution.
• The pH of the mixture can thus be calculated by
considering the relative concentrations of the
CH3COOH and CH3COO.

Ka = [H3O+][CH3COO-] so [H3O+] = Ka[CH3COOH] = 1.7 x 10-5 moldm-3, pH = 4.8

[CH3COOH] [CH3COO-]
 weak acid - strong alkali titrations
• After the addition of 19.95 cm3 (1.995 x 10-3 moles) of 0.1
moldm-3 NaOH:(ie 1 drop before the equivalence point)
NaOH + CH3COOH → CH3COONa + H2O
Before: 1.995 x 10-3 2 x 10-3 -
After: - 5 x 10-6 1.995 x 10-3
Total volume = 39.95 cm3.

[H3O+] = Ka x (5 x 10-6/0.3995) pH = 7.4

(1.995 x 10-3/0.03995)
 weak acid - strong alkali titrations
• After the addition of 20.05 cm3 (2.005 x 10-3 moles) of 0.1
moldm-3 NaOH:(ie 1 drop after the equivalence point)
NaOH + CH3COOH → CH3COONa + H2O
Before: 2.005 x 10-3 2 x 10-3 -
After: 5 x 10-6 - 2 x 10-3
Total volume = 40.05 cm3.
[OH-] = 5 x 10-6 = 1.25 x 10-4 moldm-3,
0.04005
so [H3O+] = 8.0 x 10-11 moldm-3 pH = 10.1
➢ The pH of the solution during a weak acid - strong alkali
titration therefore changes from around 7 to 10 over two
drops at the equivalence point.
Strong Acid-Strong Base Titrations
❑Here is an example of a titration curve,
produced when a strong base is added to a
strong acid.
❑This curve shows how pH varies as 0.100 M
NaOH is added to 50.0 mL of 0.100 M HCl.

116
 Titrations Involving a Weak Acid or
Weak Base

Here, 0.100 M
NaOH is being
added to 50.0 mL
of 0.100 M acetic
acid.

117
Titration curve of a weak base being titrated by a strong acid:

Here, 0.100 M HCl is being added

to 50.0 mL of 0.100 M ammonia
solution.

118
 ACID-BASE INDICATORS

1. Theory of indicators
• An acid-base indicator is a weak acid which
dissociates to give an anion of a different colour.
Consider a weak acid HIn: HIn(aq) + H2O(l) ⇌H3O+(aq) + In-(aq)
Colour 1 Colour 2

• HIn & its conjugate base In- are different colours.

• The colour of the solution depends on the relative
concentrations of the two species.
 ACID-BASE INDICATORS

• If the solution is strongly acidic, the above equilibrium will be

shifted to the left and Hin will dominate…
…Colour 1 will thus dominate.

• If the solution is strongly alkaline, the above equilibrium will

shift to the right and In- will dominate…
….Colour 2 will thus dominate.
 ACID-BASE INDICATORS

• The colour of the indicator thus depends on the pH of

the solution.
• The colour will not change suddenly at a certain pH,
but will change gradually over a pH range.
• The colour of the indicator depends on the ratio of
[HIn] to [In-].
 Use of indicators

➢ Indicators are used in acid - alkali titrations in

order to find the equivalence point of the
titration.

• If they are to determine the equivalence point

accurately, they must undergo a complete colour
change at the equivalence point.
 Use of indicators

• This means that the pH range of the colour change (ie

the end-point of the indicator) must fall completely
within the pH range of the equivalence point.

• Not all indicators can therefore be used for all

titrations, and indicators must be chosen carefully so
that the end-point of the indicator matches the pH
range at the equivalence point.
 Use of indicators

✓ In strong acid - strong alkali titrations, the pH changes from

4 to 10 at the equivalence point so a suitable indicator must
change colour within this range.
Methyl red, litmus and phenolphthalein are suitable
indicators for these titrations.
 Use of indicators

✓In weak acid - strong alkali titrations, the pH

changes from 7 to 10 at the equivalence point
so a suitable indicator must change colour
within this range.

➢ Phenolphthalein is only suitable indicator

for weak acid - strong alkali titrations that is
widely available.
 Use of indicators
• In strong acid - weak alkali titrations, the pH
changes from 4 to 7 at the equivalence point so a
suitable indicator must change colour within this
range.
Methyl red is the most suitable indicator for these
titrations.
However methyl orange is often used since it
shows a significant enough colour change at the
equivalence point and is more widely available
than methyl red.
 Use of indicators
• In weak acid -weak alkali titrations, there is no sudden pH change at
the equivalence point and thus there are no suitable indicators for
these titrations
The equivalence points of these titrations cannot be easily determined.
Summary
• When carrying out these titrations, only one or two drops of indicators
should be used since they are themselves acidic and will themselves
influence the equivalence point if too much is added.

• An indicator is suitable for a titration if its end-point falls within

the pH change at the equivalence point of the titration.