Chapter 5

Titrimetric methods of analysis

Titration is a common laboratory method of quantitative chemical
analysis that is used to determine the unknown concentration of a
known reactant. Because volume measurements play a key role in
titration, it is also known as Volumetric analysis.

Volume measurements play a key role in titration, it is also known as

volumetric analysis.

Volumetric Titrimetry
Quantitative chemical analysis which determines volume of a solution
of accurately known concentration required to react quantitatively
with the analyte (whose concentration to be determined).
 Definition of terms
Standard solution: A reagent solution of accurately known
concentration is called a standard solution.

Standardization: A process to determine the concentration of a

solution of known concentration by titrating with a primary
standard.

Titrant: A reagent, called the titrant or titrator is prepared as a

standard solution.

Indicators are often added to the analyte solution to give an observable

physical change (the end point). Typical indicator changes include the
appearance or disappearance of a color, a change in color.

A known concentration and volume of titrant reacts with a solution of

analyte or titrant to determine concentration.
End point

– The point at which the reaction is observed to be completed

is the end point

– The end point in volumetric method of analysis is the signal

that tells the analyst to stop adding reagent and make the
final reading on the burette.

– Endpoint is observed with the help of indicator

Equivalent point

– The point at which an equivalent or stoichiometric amount

of titrant is added to the analyte based on the stoichiometric
equation
 Equipment
• Volumetric analysis involves a few
pieces of equipment:
Pipette – for measuring accurate
and precise volumes of solutions
Burette – for pouring measured
volumes of solutions
Conical flask – for mixing two
solutions
Wash bottles – these contain distilled
water for cleaning equipment
Funnel – for transfer of liquids without
spilling
Volumetric flasks – a flask used to
make up accurate volumes for solutions
of known concentration
 The Process - Preparation

• Two solutions are used:

– The solution of unknown concentration;
– The solution of known concentration – this is also known
as the standard solution

• Write a balanced equation for the reaction between your

two chemicals.

• Clean all glassware to be used with distilled water. The

pipettes and burettes will be rinsed with the solutions you
are adding to them.
 Process – The Setup

• The burette is attached to a clamp stand

above a conical flask.
• The burette is filled with one of the
solutions.
• A pipette is used to measure an aliquot
of the other solution (in this case a
purple solution of unknown
concentration) into the conical flask
• Prepare a number of flasks for repeat
tests.
• Last, an indicator is added to the
conical flask
 Process – The Titration

• Read the initial level of liquid in the burette

• Turn the tap to start pouring out liquid of
the burette into the flask. Swirl the flask
continuously. When the indicator begins to
change colour slow the flow.

• When the colour changes permanently, stop

the flow and read the final volume. The
volume change needs to be calculated (and
written down). This volume is called a titre.

• Repeat the titration with a new flask now

that you know the ‘rough’ volume required.
Repeat until you get precise results.
 Classification of Volumetric Analysis
(1) Acid/Base titrations:
Examples: Acid content in wine, milk. Acid content in ketchup.

(2) Precipitation titrations :

Examples: Salt content in crisps, ketchup and food; Sulfate content in
mineral water

(3) Redox titrations :

Examples: Content of copper, chromium and nickel in electroplating
baths

(4) Complexometric titrations:

Examples: Total hardness of water (Mg and Ca); Calcium content in
milk and cheese.
 Primary Standard Substances
• Substances that are high pure (at least 99.99 %) that the amount of
substance, in mole, can be calculated accurately from their mass
are called primary standard substances.

• A primary standard should:

– Be readily obtainable in pure form

– Have a known formula
– Be easy to store without deteriorating or reacting with the
atmosphere
– Have a high molecular mass to minimise the effect of errors
with weighing
A solution with an accurately known concentration is called a
standard solution.
 Calculation of concentration systems
There are a number of different ways of expressing solute
concentration that are commonly used. Some of these are listed below.

Molarity, M = moles solute/liter of solution

Normality, N = equivalents of solute/liter of solution

Molality, m = moles of solute/mass of solvent

Mole fraction, χ = moles of solute/total moles

Weight %, Wt % = (mass of solute/mass of solution) x 100%

Parts per million, ppm = (mass of solute/mass of solution) x 106

Mass per volume, mg/L = mass of solute/liter of solution

 Strength of solution
Amount of solute present in one litre solution.

Mass of solute
Strength 
Volume of solution (in litre)

Strength  Molarity  Molecular mass

Strength  Normality  Equivalent mass

Concentration in terms of percentage

Mass of solute
% by mass   100
Volume of solution
W
 %
w

Volume of solute
% by volume   100
Volume of solution
V
 %
v
Dilution is the process of preparing a less concentrated
solution from a more concentrated one.

moles of solute before dilution = moles of solute after dilution

Dilution is the procedure for preparing a less concentrated solution
from a more concentrated solution.
Process of adding solvent, usually water, to lower the concentration of
a solution

Dilution

Add Solvent

Moles of solute Moles of solute

before dilution (i) = after dilution (f)

MiVi = MfVf
 Exercise

If 32 mL stock solution of 6.5 M H2SO4 is diluted to a volume of

500 mL. What would be the resulting concentration?

M1 x V1 = M2 x V2

(6.5M) x (32 mL) = M2 x (500.0 mL)

6.5 M x 32 mL
M2 = 500 mL

M2 = 0.42 M
 ACID-BASE TITRATIONS
 An acid-base titration is a procedure used in quantitative chemical
analysis to determine the concentration of either acid or a base.
• Equivalence point: The equivalence of an acid-base titration is the
point at which there are equal amounts (in moles) of H3O+ and OH-
in titration flask.
 End point: the point in a titration at which the indicator changes
colour.
 Titrant:
The known solution added to the solution of unknown
concentration.
 Titration Curve:
The plot of pH vs. volume.
 Types of acid-base reactions
Types of acid- base Example
reactions
Strong acid with strong base HCl and NaOH

Strong acid with weak base HCl and NH3

Weak acid with strong base CH3COOH and NaOH

Weak acid with weak base CH3COOH and NH3

 Acid-Base indicators

Colour change
Indicator pKHln pH range
Acid Alkali

Methyl orange 3.7 3.2-4.2 Red Yellow

Bromothymol blue 7.1 6.0-7.6 Yellow Blue
Phenolphtalein 9.3 8.2-10.0 Colorless Pink
 pH of acid base reaction at its
equivalent point
Acid Base pH at equivalence Indicators
point

Strong Strong = 7 (neutral) Methyl orange

Phenolphthalein

Strong Weak < 7 (acidic) Methyl orange

Weak Strong > 7 (basic) Phenolphthalein
Weak Weak pH depend on Ka and -
Kb of acid & base
concentration
 Titration of
Strong Acid with Strong Base

NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

Base at the
end of the
titration
Acidic at the
start of the
titration
This diagram shows the change in pH as a solution of strong acid is
slowly added to a solution of strong base.

Strong acid-strong base titrations usually have an equivalence

point around 7.
This is due to the fact that in solution, strong acids and strong bases
will both completely dissociate, so there is an approximate 1:1 ratio
of moles of acid to moles of base at the equivalence point.

Strong base-strong acid titrations are just like the strong acid-strong
base titrations: the pH at the equivalence point is around 7.
 Titration of
Weak Acid with Strong Base
CH3COOH(aq) + NaOH(aq) CH3COONa (aq) + H2O (l)
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)
At equivalence point (pH > 7):

Excess
Hydroxide
Ions
At the beginning, the weak acid is in equilibrium with itself. Thus, the
beginning pH is higher than that of a strong acid.
More moles of the weak acid are required to completely react with
the amount of strong base present, because the acid is not entirely
dissociated.
For every mole of base, there is less than one mole of acid able to
react: there is an excess of base.
The initial change in pH is steeper because there is excess base.
Weak acid-strong base titrations reach their equivalence point at a
pH greater than 7.
 Titration of
Weak Base with Strong Acid
HCl (aq) + NH3 (aq) NH4Cl (aq)
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)
At equivalence point (pH < 7):
At the beginning, the weak base is in equilibrium with itself. Thus,
the beginning pH is lower than that of a strong base.

More moles of the weak base are required to completely react with
the amount of strong acid present, because the base is not entirely
dissociated.

For every mole of acid, there is less than one mole of base able to
react: there is an excess of acid.

Strong acid-weak base titrations reach their equivalence point at a

pH less than 7.
 Titration of
Weak Acid with Weak Base

• Weak acid-weak base

titrations are difficult
because each solution is in
equilibrium.
• The pH of the equivalence
point is around 7.