Chapter 3- Volumetric analysis

Volumetric analysis is a quantitative technique that involves reactions in

solutions generally to determine their concentration.
The accurate concentration of a solution is usually determined by reacting
it with another solution whose concentration is known accurately, a
standard solution.
There are two methods by which a solution may have its concentration
determined accurately
-By reacting it with another solution whose concentration is known
accurately
- By taking a substance called a primary standard and dissolving it in a
known volume of water.
To qualify as a primary standard a substance must have a number of the
following properties
- It must have a high state of purity
- It must have an accurately known formula
- It must be stable. In other words, it composition or formula must not
change over time
- It should be cheap and readily available
- It should have a relatively high molar mass so that weighing errors are
minimised
A secondary standard can be prepared by measuring its concentration
against a primary standard
Both hydrated sodium carbonate and sodium hydroxide are unsuitable for
use as primary standards because they react with the atmosphere
Volumetric flasks are used to prepare primary standards
The process of volumetric analysis generally follows these steps:
- Prepare primary standard
- Fill burette with required solution
- Pipette required solution into conical flask
- Add a few drops of indicator
- Titrate until indicator changes colour
The end point of the titration occurs when experimental evidence (often a
change in colour of an indicator) tells you to stop the titration
In some redox titrations no indicator is needed as substances involved n
the analysis may have conjugate forms that display distinctly different
colours, however due to the colourless solutions used in many acid-base
reactions, indicators are necessary to know when to stop an acid base
titration
Calculations require that a titration be stopped when one substance has
just finished reacting with the other, the equivalence point. Therefore it is
important to choose an indicator that changes colour closest to the
equivalence point
Indicator Colour at lower pH Colour at higher pH pH range for colour change
Methyl Orange Red Yellow 3.1 4.4
Methyl Red Red Yellow 4.2 6.2
Litmus Red Blue 5.0 9.0
Bromothymol Blue Yellow Blue 6.0 7.6
phenolphthalein Colourless Crimson 8.3 10.0

The equivalence point for a strong acid and strong base is around pH 7
The equivalence point for a weak acid and strong base is around pH 9
The equivalence point for a strong acid and weak base is around pH 5
The calculations involved in volumetric analysis generally include
- Converting the known information into moles
- Predicting the number of moles of the substance
- Changing from moles of this substance to the type of information that
you require
- Note: dilution may have occurred at some stage and calculations need
to allow for this
Back titrations are an indirect method of volumetric analysis
They are used when the substance being used is:
- Insoluble
- A weak acid or a weak base where it is not possible to get a sharp end
point
- Volatile
Back Titrations involve the following steps:
- Add an acid to the particular substance in excess. Make sure you know
the exact concentration and volume of the acid
- Titrate the substance wit ha base. By doing this you are titrating with
the excess acid
- After doing the titration work out the volume of the excess acid
- Then find the volume needed to react with the solid substance (v
(used)- v (excess)= v(needed))
- Then use mole ratio to work out the mol of the solid substance
It is important to understand the steps in a procedure and predict the
effect on the final calculated result if the steps are not performed correctly
Some common errors in volumetric analysis are:

Effect if substance under analysis is

Situation in the Comments

Burette Titration Flask

Rinsing water left in Underestimated Overestimated The burette solution is diluted

burette with water, so more is used

Rinsing water left in Overestimated Underestimated The solution aliquot in the

pipette titration flask is diluted

Indication chosen Overestimated Underestimated The choice of indicator can be

changes colour too soon critical

Water in titration flask No effect No effect All necessary measurement

are made before the chemicals
are mixed with this water

Indicator changes Not applicable Overestimated The excess left after the
colour to soon during a chemical being analysed has
back titration reacted is being titrated here.
This is always in the flask