Analytical Chemistry

NT10402

Titrimetric methods of analysis

Jahurul Haque, PhD
Faculty of Food Science and Nutrition
Universiti Malaysia Sabah
 Titrimetric Methods
• Titrimetric methods (Titration methods) include a large and
powerful group of quantitative procedures based on
measuring the amount of a reagent of known concentration
that is consumed by an analyte in a chemical or
electrochemical reaction.
• Volumetric titrimetry involves measuring the volume of a
solution of known concentration that is needed to react
essentially completely with the analyte.
• Gravimetric titrimetry differs only in that the mass of the
reagent is measured instead of its volume.
• In coulometric titrimetry, the ‘reagent’ is a constant
direct electrical current of known magnitude that consumes
the analyte.
Principles of volumetric analysis
Volumetry : the volume of standard reagent needed to react with analyte is
measured
Titrimetry : increments of the titrant are added to the analyte until their reaction
is complete.
Titrant vs Analyte
N V = N’V’
nMV = n’M’V’

N= known
V= measure

N’= unknown
V’= known
Titration :
A procedure for determining the amount of some unknown substance (the
analyte) by quantitative reaction with a measured volume of a solution of
precisely known concentration (the titrant ).

Titrant :
The substance that quantitatively reacts with the analyte in a titration . The
titrant is usually a standard solution added carefully to the analyte until the
reaction is complete. The amount of analyte is calculated from the volume of
titrant required for complete reaction.

Indicator :
A substance that undergoes an sharp, easily observable physical change when
conditions in its solutions change. For example, acid-base indicator and redox
indicator .
Equivalence point :
point in a titration at which equivalent amounts of titrant is the exact
amount necessary for stoichiometric reaction with the analyte.

N= known
V= measure

N’= unknown
V’= known
End point : the point in a titration when a physical change occurs that is
associated with the condition of chemical equivalence.
The experimental estimate of the equivalence point in a titration
titration error : eT = Vep – Veq
Vep = actual volume at end point,
Veq = theoretical volume of equivalence point
Blank titration
Direct titration : titrant is added to the analyte until the reaction is complete.
Back titration : Adding a known excess of reagent to the analyte, then, a
second reagent is used to titrate the excess of the first reagent.

A Excess T1
T1 T2

Ex. PO43– + 3Ag+  Ag3PO4 (s)

Ag+ + SCN –  AgSCN (s)
 Evolution of the buret

Buret,
buret stand,
clamp,
white porcelain base,
wide-mouth Erlenmeyer flask
Normally, the buret is filled titrant solution to within 1 or 2
mL of the zero position at the top. The initial volume of
the buret is read to the nearest 0.01 mL.
Standard solution : 
A solution of precisely known concentration.

Primary standard :
An ultra-pure (99.9% purity) compound that serves as the reference
material for a titrimetric method of analysis.

Secondary standard :
A compound whose purity has been established by chemical analysis and
that serves as the reference material for a titrimetric method of analysis
Standardization :
a process in which the concentration of a solution is determined by using the
solution to titrate a known amount of another reagent.
Steps in a titrimetry 

Weighing 99.9% 2ndary standard

pure primary
standard reagent Titration other Find N’
xx.xxxx g sample solution normality
Dissolve in a V’ ?
volumetric flask
Transfer pipet
N’ ?
Preparation of primary Erlenmeyer Flask V ml
standard solution Find V’ ml
indicator Beaker
Calculation Normality
NV Titration unknown
sample solution
Preparation of unknown
sample solution
N’V’ Buret
 Equivalence Points and End Points

• The equivalence point of a titration cannot 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 the titration.
• Every effort is made to ensure that any volume or mass
difference between the equivalence point and the end point
is small.
• Such differences do exist, however, as a result of
inadequacies in the physical changes and in our ability to
observe them.
• The difference in volume or mass between the equivalence
point and the end point is the titration error.
• Indicators are often added to the analyte solution
to give an observable physical change (the end
point) at or near the equivalence point.
• Large changes in the relative concentration of
analyte or titrant occur in the equivalence-point
region.
• These concentration changes cause the indicator to
change in appearance.
• Typical indicator changes include the appearance
or disappearance of a color, a change in color, or
the appearance or disappearance of turbidity.
 Primary Standards
A primary standard is a highly purified compound that
serves as a reference material in all volumetric and mass
titrimetric methods. The accuracy of a method is critically
dependent on the properties of this compound. Important
requirements for a primary standard are
1. High purity
2. Atmospheric stability
3. Absence of hydrate water so that the composition of the
solid does not change with variation in relative humidity
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.
 Desirable Properties of standard Solutions
The ideal standard solution for a titrimetric method
will
1. Be 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.
 Establishing the Concentration of Standard
solutions
• The accuracy of a titrimetric method can be no better than
the accuracy of the concentration of the standard solution
used in the titration.
• Two basic methods are used to establish the concentration
of such solutions. The first is the direct method 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.
• The second is by standardization in which the titrant to be
standardized is use to titrate (1) a weighed quantity of a
primary standard, (2) a weighed quantity of a secondary
standard, or (3) a measured volume of another standard
solution.
 Expressing the Concentration of Standard
Solutions

The concentrations of standard solutions are

generally expressed in units of either molarity c or
normality cN. The first gives the number of moles
of reagent contained in one liter of solution, and
the second gives the number of equivalents of
reagent in the same volume.

M = moles/L
N = equivalents/L
 Some Useful algebraic Relationships
Most volumetric calculations are based on two pairs of
fundamental equations that are derived from definitions of
millimole, mole, and molar concentration. For the chemical
species A, we may write
mass A (g)
amount A (mol) =
molar mass A (g / mol)
mass A (g)
amount A (mmol) =
millimolar mass A (g / mmol)
We may derive a second pair from the definition of molar
concentration. That is,
 mol 
amount A (mol) = volume (L)  concentration A  
 L 
 mmol 
amount A (mmol) = volume (mL)  concentration A  
 mL 
 TITRATION CURVES

• An end point is an observable physical change that occurs near

the equivalence point of a titration.
• The two most widely used end points involve (1) changes in color
due to the reagent, the analyte, or an indicator and (2) a change in
potential of an electrode that responds to the concentration of the
reagent or the anlyte.
• To understand the detection of end points and the sources of
titration errors, we will construct titration curves for the system
under consideration.
• Titration curves consist of a plot of reagent volume on the
horizontal axis and some function of the analyte or reagent
concentration on the vertical axis.

Titration curves are plots of a concentration-related variable

versus titrant volume.
 Types of Titration Curves
• Two types of titration curves (and thus two general
types of end points) occur in titrimetric methods.
• sigmoidal curve
• Linear segment curve

• The sigmoidal type offers the advantages of speed and

convenience.

• The linear segment type is advantageous for reactions

that are complete only in the presence of a considerable
excess of the reagent or analyte.
The vertical axis in a sigmoidal
titration curve is either the p-
function of the analyte or titrant
or the potential of an analyte- or
titrant-sensitive electrode.

The vertical axis of a linear-

segment titration curve is an
instrument signal that is
proportional to the concentration
of the analyte or titrant.
 Concentration Changes During
Titrations

• The equivalence point in a titration is characterized by major

changes in the relative concentrations of reagent and analyte.

• The data in the second column of the table show the changes in
the hydronium ion concentration as a 50.00-mL aliquot of a
0.1000 M solution of hydrochloric acid is titrated with 0.1000
M sodium hydroxide.
Figure 13-3: Titration curves of pH and pOH versus volume of base
for the titration of 0.1000 M HCl with 0.1000 M NaOH.