Introduction to

Titrations
Taking Advantage of Stoichiometric Reactions
 Definitions
Titrimetry – group of analytical methods based on determining
the quantity of a standard reagent (of known concentration) that
is required to react completely with the analyte

Volumetric titrimetry – type of titrimetry in which the standard

reagent is measured volumetrically

Gravimetric titrimetry – type of titrimetry in which the mass of

the standard reagent is measured

Coulometric titrimetry – type of titrimetry in which the quantity

of charge (in coulombs) required to complete a reaction with the
analyte is measured
 Definitions
VOLUMETRIC TITRIMETRY – type of titrimetry in which the
standard reagent is measured volumetrically

Neutralization Titrations – used for the determination of

natural and synthetic acids (alkalimetry) and bases
(acidimetry)

Compleximetric Titrations – based on complex formation

between metal ions and ligands

Precipitimetric Titrations – based on formation of

precipitates

Redox Titrations – the analyte is consumed by an

oxidizing or a reducing reagent of known concentration
 VOLUMETRIC TITRIMETRY - More Definitions

Standard Solution – a reagent of known concentration that is

used to carry out a titrimetric analysis

Titration – process in which a standard reagent is added to a

solution of an analyte until the reaction between the analyte and
reagent is judged to be complete

Back-Titration – process in which the excess of a standard

reagent used to consume an analyte is determined by titration
with a second standard solution. Resorted to when the rate of
reaction between the analyte and reagent is slow.
Titration Process
 VOLUMETRIC TITRIMETRY - More Definitions
Equivalence Point – point in a titration when the amount of
added standard reagent (Veq) is stoichiometrically equivalent to
the amount of the analyte in the sample

End Point – the point in a titration (Vep) when a physical change

occurs that is associated with the condition of equivalence

Chemical Indicators – substances added to the analyte in small

amounts in order to give an observable physical change (the End
Point) at or near the Equivalence Point

appearance or disappearance of a color

change in color
appearance or disappearance of turbidity
 VOLUMETRIC TITRIMETRY – Some More Definitions
End Point Detection Methods: Visual judgment OR
Instrumental (colorimeters, turbidimeters, voltmeters, current
meters, conductivity meters)

Titration Error – the difference in volume data between the

Equivalence Point (theoretical) and the End Point (experimental)

Et = Vep - Veq
VOLUMETRIC TITRIMETRY – still Some More Definitions
Primary Standard – an ultrapure compound that serves as the
reference material for a titrimetric method of analysis

PROPERTIES OF A PRIMARY STANDARD:

1. High purity
2. Atmospheric stability
3. Absence of hydrate water
4. Ready availability at modest cost
5. Reasonable solubility in the titration medium
6. Reasonably large molar mass so that the relative error
associated with weighing the standard is minimized

Secondary Standard – a compound whose purity has been

established by prior chemical analysis and that serves as the
reference material for a titrimetric method of analysis
 VOLUMETRIC TITRIMETRY –Definitions pa din
Standard Solution – solution of the primary or secondary
standard reagent

PROPERTIES OF A STANDARD SOLUTION:

1. Sufficiently stable so that it is only necessary to determine its

concentration once
2. React rapidly with the analyte so that the time required
between additions of reagent is minimized
3. React completely with the analyte so that satisfactory end
points are realized
4. Undergo a selective reaction with the analyte that can be
described by a balanced equation
 VOLUMETRIC TITRIMETRY –Definitions last na
METHODS FOR ESTABLISHING THE
CONCENTRATION OF STANDARD SOLUTIONS:

1. Direct Method – process in which a carefully weighed quantity

of a primary standard is dissolved in a suitable solvent and
diluted to a known volume in a volumetric flask

2. Standardization – process wherein the concentration of a

volumetric solution (TITRANT) is determined by titrating it
against (1) a carefully weighed quantity of a primary or (2) a
secondary standard or (3) an accurately known volume of
another standard solution

CONCENTRATION of the Standard Solution is expressed in MOLARITY

CALCULATIONS – Direct Method of establishing concentration

Example 1
Describe the preparation of 0.500 L of 0.1000 M
Na2CO3 (105.99 g/mol) from the primary standard
solid.

Example 2
A standard 0.0100 M solution of Na+ is required for
calibrating a flame photometric method for
determining Na in samples. Describe how 500.0 mL of
this solution can be prepared from the primary standard
Na2CO3.
Example 3
How would you prepare 50.0 mL portions of standard
solutions that are 0.005000 M, 0.00200 M, and
0.00100 M in Na+ from a standard solution of Na+ with
a concentration of 0.0100 M?
CALCULATIONS – Standardization against a primary standard or
another standard solution

Example 4
A 50.00 mL volume of HCl solution required 29.71 mL
of 0.01963 M Ba(OH)2 to reach an end point with
bromocresol green indicator. Calculate the molarity of
the HCl solution.
Example 5
Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol)
required 43.31 mL of KMnO4. What is the molarity of
the KMnO4 solution?

MnO4- + C2O42- → Mn2+ + CO2 + H2O

CALCULATIONS – Determining Amount of Analyte from Titration Data

Example 6 [REDOX TITRATION]

A 0.8040 g sample of an iron ore is dissolved in acid.
The iron is then reduced to Fe2+ and titrated with 47.22
mL of 0.02242 M KMnO4 solution. Calculate the
results of this analysis in terms of (a) % Fe (55.847
g/mol) and (b) % Fe3O4 (231.54 g/mol)
 Example 6

• The mass of Fe²⁺is then given by

4-15
 Example 6
• The percent Fe²⁺ is

• (b) To determine the correct stoichiometric ratio,

we note that

4-16
 Example 6
• Therefore,

• and

4-17
• As in part (a),

4-18
Example 7 [COMPLEXIMETRIC TITRATION]
The organic matter in a 3.776 g sample of a mercuric
ointment is decomposed with HNO3. After dilution,
the Hg2+ is titrated with 21.30 mL of a 0.1144 M
solution of NH4SCN. Calculate the % Hg (200.59
g/mol) in the ointment.

Hg2+ + 2SCN- → Hg(SCN)2 (aq)

CALCULATIONS – Determining Amount of Analyte from Titration Data

Example 8 [ACID-BASE with BACK-TITRATION]

A 0.4755 g sample containing (NH4)2C2O4 and inert materials
was dissolved in H2O and made strongly alkaline with KOH,
which converted NH4+ to NH3. The liberated NH3 was distilled
into 50.00 mL of 0.05035 M H2SO4. The excess H2SO4 was
back-titrated with 11.13 mL of 0.1214 M NaOH. Calculate (a)
the % N (14.007 g/mol) and (b) the % (NH4)2C2O4 (124.10
g/mol) in the sample.
CALCULATIONS – Determining Amount of Analyte from Titration Data

Example 9 [REDOX with BACK-TITRATION]

The CO in a 20.3 L sample of gas was converted to CO2 by
passing the gas over iodine pentoxide heated to 150°C:
I2O5(s) + 5CO(g)  5CO2(g) + I2(g)
The iodine was distilled at this temperature and was collected in
an absorber containing 8.25 mL of 0.01101 M Na2S2O3:
I2(aq) + 2S2O32-(aq)  2I-(aq) + S4O62-(aq)
The excess Na2S2O3 was back-titrated with 2.16 mL of 0.00947
M I2 solution. Calculate the mass in milligrams of CO (28.01
g/mol) per liter of sample.
Instrumental methods of water analysis