Titration
Titration
Titration
Principles
An analyte is chemically reacted with a standard solution of a reagent
of precisely known concentration or with a concentration that can be
precisely determined. The amount of a standard solution required to
completely react with all of the sample is used to estimate the purity
of the sample.
The process of determining the quantity of a substance A by
adding measured increments of substance B, with which it reacts
(almost always as a standardized solution called the titrant, but also
by electrolytic generation, as in coulometric titration) with
provision for some means of recognizing (indicating) the endpoint
at which essentially all of A has reacted.
If the endpoint coincides with the addition of the exact chemical
equivalence, it is called the equivalence point or stoichiometric or
theoretical endpoint, thus allowing the amount of A to be found
from known amounts of B added up to this point, the reacting
weight ratio of A to B being known from stoichiometry or
otherwise.
Terms for varieties of titration can reflect the nature of the
reaction between A and B.
Thus, there are acid– base, complexometric, chelatometric,
oxidation–reduction, and precipitation titrations.
Additionally, the term can reflect the nature of the titrant, such
as acidimetric, alkalimetric, and iodometric titrations as well as
coulometric titrations, in which the titrant is generated
electrolytically rather than being added as a standard solution
Titration curve
A plot of a variable related to a relevant concentration
(activity) as the ordinate vs. some measure of the amount of
titrant, usually titration volume (titre) as the abscissa.
If the variable is linearly related to concentrations, such as the
electrical conductance or the photometric absorbance, the term
linear titration curve is used.
When a logarithmic expression of the concentration or activity
is used, such as the or the electrical potential in , the curve is
referred to as a logarithmic titration curve.
Titrimetric methods are still widely used in pharmaceutical
analysis because of their robustness, cheapness and capability for
high precision.
The only requirement of an analytical method that they lack is
specificity.
Primary standards and standard solutions
Primary standards are stable chemical compounds that are
available in high purity and which can be used to standardise the
standard solutions used in titrations.
Titrants such as sodium hydroxide or hydrochloric acid cannot
be considered as primary standards since their purity is quite
variable.
So, for instance, sodium hydroxide standard solution may be
standardised against potassium hydrogen phthalate, which is
available in high purity.
The standardised sodium hydroxide solution (secondary
standard) may then be used to standardise a standard
solution of hydrochloric acid.
Direct acid/base titrations in the aqueous phase
Strong acid/strong base titrations
Figure shows the titration curve obtained from the titration of a
strong acid with a strong base.
The pH remains low until just before the equivalence point, when
it rises rapidly to a high value.
In many titrations a coloured indicator is used, although
electrochemical methods of end-point detection are also used.
An indicator is a weak acid or base that changes colour between
its ionised and un-ionised forms; the useful range for an indicator is
1 pH either side of its pKa value.
For example, phenolphthalein (PP) pKa 9.4 (colour changes
between pH 8.4 and pH 10.4) undergoes a structural rearrangement
as a proton is removed from one of its phenol groups when the pH
rises, and this causes the colour change (Fig. ).
Methyl orange (MO) pKa 3.7 (colour changes between pH 2.7 and
pH 4.7) undergoes a similar pH-dependent structural change. Both
these indicators fall within the range of the inflection of the strong
acid/strong base titration curve.
There are only a few direct strong acid/strong base titrations
carried out in pharmacopoeial assays. Strong acid/strong base
titrations are used in pharmacopoeial assays of: perchloric acid,
hydrochloric acid, sulphuric acid and thiamine hydrochloride.
Weak acid/strong base and weak base/strong acid titrations
On addition of a small volume of the strong acid or strong base to
a solution of the weak base or weak acid, the pH rises or falls rapidly
to about 1 pH unit below or above the pKa value of the acid or base.
Often a water-miscible organic solvent such as ethanol is used to
dissolve the analyte prior to the addition of the aqueous titrant.
Figure shows a plot of pH when 1 M NaOH is added to 25 ml of a
1 M solution of the weak acid aspirin.
In the case of aspirin, the choice of indicator is restricted by where
the inflection in its titration curve lies; PP is suitable as an indicator
whereas MO is not.
In the example of the titration of quinine with hydrochloric acid
(Fig, MO is a suitable indicator because it falls within the
inflection of the titration curve whereas PP is not suitable
Some acids or bases can donate or accept more than one
proton, i.e. 1 mole of analyte is equivalent to more than 1
mole of titrant.
If the pKa values of any acidic or basic groups differ by
more than ca 4, then the compound will have more than one
inflection in its titration curve.
Sodium carbonate is a salt of carbonic acid and it can
accept two protons. The pKa values of carbonate and
bicarbonate are sufficiently different (pKa 10.32 and 6.38)
for there to be two inflections in the titration curve. The two
stages in the titration are:
In a titration of sodium carbonate, the first inflection is
indicated by PP and the whole titration by MO (Fig).
Taking values from Table 3.2, the reaction potential is given by:
1.36 – 1.065 =0.29 V
Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.
Alternative Proxies: