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Paper III
Unit II
Instrumental Methods II
Instruments Based on Electrochemical Properties
of the Analytes
pH Metry
By
Dr. Bhushan Langi
Principle:
• pH meter is an instrument which is used to measure pH of the solution and gives a titration curve.
• During this titration the concentration of H+ ions changed.
• This change in concentration of H+ ions is measured in terms of pH.
pH = - log [H+]
• A graph of pH against volume of titrant added is plotted and the equivalence point is determine from
the curve.
pH
Pocket-sized Handheld
Benchtop Meters
Testers Portable Meter
Economical and Compact Provide reportable pH Provide best accuracy,
for routine, non-critical accuracy for the field, more strong data
measurements manufacturing floor and management
laboratories
Glass Electrode:
Principle:
• The most common electrode used for pH meter is glass electrode.
• Surface of the glass is protonated by both internal and external solution till equilibrium is reached.
• Both the side of the glass is are charged by the absorbed protons, this charge is responsible for
potential difference.
• This potential difference is described by the Nernst equation and is directly proportional to the pH
difference between solutions on both side of the glass.
Diagram: Construction:
Most often used pH electrodes are glass electrodes.
Typical model is made of glass tube ended with small glass bulb.
Inside of the electrode is usually filled with buffered solution of
chlorides in which silver wire covered with silver chloride is
immersed.
pH of internal solution varies - for example it can be 1.0 (0.1M
HCl) or 7.0 (different buffers used by different producers).
The majority of pH electrodes available commercially are
combination electrodes that have both glass H+ ion sensitive
electrode and additional reference electrode conveniently
placed in one housing.
Working:
• Wash the electrode with distilled water and dry it.
• Connect it to pH meter.
• Dipped the bulb of the glass electrode in solution whose pH is to be determine take care the bulb
is completely dipped in the solution, if not the add little amount of distilled water.
• pH of the solution is displayed on the screen of pH meter, record it.
Care of Combined Glass Electrode:
1. The bulb of the glass electrode is very delicate hence it is always enclosed within the outer plastic
jacket.
2. The dry bulb does not function and hence it is always kept in hydrated by dipping the electrode in
distilled water.
3. The combined glass electrode is to be standardised every time before its use by dipping in a buffer
solution of pH 7.0 , 4.2 and 9.2 respectively.
4. As the pH of a solution varies with temperature, hence temperature of the solution must be
maintained constant.
Application in titrimetry: (Strong acid – strong base)
In the strong acid (HCl) against strong base (NaOH), the pH of a known volume of strong acid solution is
measured.
When Strong base (NaOH) is added to the solution of strong acid (HCl), H + ions from the acid combine
with OH- ions from the base producing unionised water.
As a result, H+ ion concentration of the solution steadily decrease and pH gradually increase.
However, near equivalence point, there is rapid decrease in H + ion concentration. Hence the pH is
increases rapidly.
After the equivalence point, NaOH added remains unreacted which completely gives OH - ions. Hence,
pH becomes gradual.
Thus S shaped curve is obtained during the titration of strong acid with strong base.
The graph of pH against volume of NaOH solution added.
Knowing the volume of alkali required for titration, strength of acid can
pH
be calculated.