Titration or Titrimetry
Introduction
-Technique for determining the
concentration of a solution by measuring
the volume of one solution needed to
completely react with another solution.
-Titration process involves addition of
solution of known concentration from
buret to the measured volume of analyte.
Principles of Titration
-it is based on the complete chemical
reaction between the analyte and the
reagent (titrant) of known concentration.
Analyte + Titrant = Product
Terms used in Titration
Analyte- a substance whose chemical
constituents are being identified and
measured.
Titrant- a solution of known concentration
that is added (titrated) to another solution to
determine the concentration of a second
chemical species.
Terms used in Titration
Standard solution- a solution containing an
accurately known concentration.
Standard solutions are generally prepared by
dissolving a solute of known mass into a
solvent to a precise volume, or by diluting a
solution of known concentration with more
solvent.
Terms used in Titration
Equivalence point- point in titration at which the
amount of titrant added is just enough to
completely neutralize the analyte solution.
At the equivalence point in an acid-base titration,
moles of base = moles of acid and the solution only
contains salt and water.
Terms used in Titration
End point-the point at which the color of the
solution changes completely due to the formation
of product due to the addition of indicator.
It is to be noted that weak acids only show one
endpoint in the titration.
Terms used in Titration
Indicator- is a weak acid or a weak base
that has different colors in its dissociated
and undissociated states.
An indicator reacts with an acid or base
to show an equivalence point in a
titration.
An indicator's color depends on the pH of a
solution.
Types of Standard Solution
1. Primary Standard solution- is a reagent
that is very pure, representative of the
number of moles the substance contains,
and easily weighed.
- Also known as the reference standard
A good primary standard meets the
following criteria:
•-Has a high level of purity
•Has low reactivity (high stability)
•Has a high equivalent weight (to reduce error from
mass measurements)
•Is not likely to absorb moisture from the air
(hygroscopic), to reduce changes in mass in humid
versus dry environments
•Is nontoxic
•Is inexpensive and readily available
Examples:
•Sodium chloride (NaCl)-used as a primary
standard for silver nitrate (AgNO3) reactions
•Zinc powder- used to standardize EDTA
(ethylenediaminetetraacetic acid) solutions after it
has been dissolved in hydrochloric or sulfuric acid
•Potassium hydrogen phthalate, or KHP- used to
standardize perchloric acid and an aqueous base in
an acetic acid solution
2. Secondary standard solution –a
chemical that has been standardized against a
primary standard for use in a specific analysis.
Secondary standards are commonly used to
calibrate analytical methods.
Ex. NaOH, once its concentration has been
validated through the use of a primary standard, is
often used as a secondary standard.
Titrimetric Calculation
-based on the following law of
equivalence:
N1V1=N2V2
where:
N1= concentration of analyte in M or N
V1= volume of analyte
N2= concentration of standard solution
V2= volume of standard solution used
Examples:
1. If 25.2 ml of 0.2703 N acid reacts with 35.1
ml of base , what is the normality of the
base ?
Solution:
N1V1(Acid ) = N2V2 (Base)
25.2 x 0.2703 = N2× 35. 1
N2 = 0.1941
✓ The normality of the base 0.1941 N
2. What volume of 0.05 N H2SO4 will be
required to completely neutralize 15 ml of
0.2 N NaOH solution?
3. What will be the normality of HCl in 100ml
of the solution when mixed with NaOH with a
normality of 2N and volume of 50 ml.
Titration Apparatus
Types of Titration
1. Acid-base
1. Complexometric
2. Redox
3. Precipitation
Types of Titration
1. Acid-base
-is a method of quantitative analysis for
determining the concentration of an acid or
base by exactly neutralizing it with a standard
solution of base or acid having known
concentration.
Types of Acid-Base Titration
Types Examples
Hydrochloric acid and
Strong acid-strong base
sodium hydroxide
Ethanoic acid and sodium
Weak acid-strong base
hydroxide
Hydrochloric acid and
Strong acid-weak base
ammonia
Weak acid-weak base Ethanoic and ammonia
Types of titration Indicators
Phenolphthalein is usually preferred
Strong acid-strong base because of its more easily seen
colour change.
Phenolphthalein is used and
Weak acid-strong base changes sharply at the equivalence
point and would be a good choice.
Methyl orange will change sharply
Strong acid-weak base
at the equivalence point.
Neither phenolphthalein, nor
methyl orange is suitable. No
Weak acid-weak base indicator is suitable because it
requires a vertical portion of the
curve over two pH units.
Types of Titration
2. Complexometric
- are used mainly to determine metal ions by
use of complex-forming reactions.
- Although many complexing agents (cyanide,
thiocyanate, fluoride, 1,2-diaminoethane, etc.)
can be used for this purpose, in practice the
titrants are almost always compounds having the
iminodiacetic acid functional groups.
- Ex. EDTA, dihydrate of the sodium salt
Types of Titration
3. Redox
- method of determining the concentration
of a given analyte by causing a redox
reaction between the titrant and the
analyte.
- These types of titrations sometimes require
the use of a potentiometer or a redox
Reduction
A substance can undergo reduction can occur
via:
•The addition of hydrogen.
•The removal of oxygen.
•The acceptance of electrons.
•A reduction in the overall oxidation state.
Oxidation
The following points describe a substance that has
undergone oxidation.
•The addition of oxygen.
•Removal of hydrogen which was attached to the
species.
•The donation/loss of electrons.
•An increase in the oxidation state exhibited by the
substance.
✓Thus, it can be understood that redox titrations
involve a transfer of electrons between the given
analyte and the titrant.
✓An example of redox titration is the treatment of
an iodine solution with a reducing agent. The
endpoint of this titration is detected with the
help of a starch indicator.
Types of Titration
4. Precipitation
- is a type of titration which involves the
formation of precipitate during the
titration technique.
- In precipitation titration, the titrant reacts
with the analyte and forms an insoluble
substance called a precipitate.
Ag+(s) + Cl-(s) AgCl(s)
Types of Precipitation Titration
1. Volhard’s method- this method involves the titration of
bromides, iodides, and chlorides, in an acidic medium. The
chloride in the solution is converted to silver chloride when
reacted with excess silver nitrate solution. The leftover
silver nitrate is estimated against potassium thiocyanate
solution. When all thiocyanate consumes all the silver, the
excess of thiocyanate is made to react with an indicator.
It gives a red color on reacting with ferric ammonium
sulfate indicator and a ferrous thiocyanate complex is
formed
2. Fajan’s method -this method uses the reaction
between the precipitate formed and indicator. The
indicator used is dichlorofluorescein which acts as an
anion in solution. In chloride solution, due to excess
chloride ions, they form the primary layer of the
precipitate. The second layer is formed by the cations of
sodium. The reaction ends with the silver ion in excess.
Therefore, the positively charged silver ion becomes the
primary layer and attracts indicator to form a second
layer.
The color of the indicator signals the end of the reaction.
3. Mohr’s method-this method is used to
determine chlorides in a neutral solution. The
chromate ion in acidic conditions is protonated to
form chromic acid. Therefore, it does not
produce a precipitate. Highly alkaline solutions
result in forming the silver hydroxide.
This formation results in brown color and this
infers the endpoint.