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2) Membrane indicator electrodes

1-They are sensitive electrodes to certain ions depending on the
type of membrane material.

2- This sensitivity is produced by a difference in voltage through a

membrane separating two solutions with different concentrations of
the same ion, the first solution with a constant concentration (the
reference solution) and the second solution is the sample solution.

3- The potential developed at this type of electrode results from an

unequal charge buildup at opposing surface of a special
membrane. The charge at each surface is governed by the position
of an equilibrium involving analyte ions, which, in turn, depends on
the concentration of those ions in the solution.

2) Membrane indicator electrodes

4- There are many types of membranes, each of which is sensitive

to a specific type of ions made from different materials depending
on the type of ions to be estimated.

5- Consist of a thin membrane separating two solutions of different

ion concentrations. Most common: pH Glass electrode

6- The concentration of ions using these electrodesis expressed in

the form of the p function (eg. pH, pCa, pLi, ..)

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Glass Membrane Electrode ( pH electrode):

• It is a hydrogen ion sensitive electrode (used to measure pH).

• When a thin glass membrane is placed between two acid solutions of
different conc., a potential difference develops across the glass
membrane and a hydrogen half cell is created.
• The cell contains a glass membrane electrode (indicator
electrode) and the saturated calomel electrode (reference
electrode).

a- separeated:

b- combined:

A complete cell can be represented by

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Glass Membrane Electrode

E = K + 0.059 (pH1 - pH2)
K= constant known by the asymmetry Ex:????
potential.
PH1 = pH of the internal solution 1.
PH2 = pH of the external solution 2.
•Asymmetry potential
The final equation is: •E of the 2 reference electrodes
•pH of the internal solution
E = L - 0.059 pH •Liquid junction potential

Properties of Glass pH electrode

• Potential not affected by the presence of oxidizing or
reducing agents
• Operates over a wide pH range
• Fast response
• Functions well in physiological systems
• Very selective
• Long lifespan

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Alkaline error:

• Due to the electrode ability to respond to other ions such

as Na +, K +, at lower concentration of the hydrogen.
• Such error is due to the capability of the membrane for
responding to other cations such as Na and K besides the
hydrogen ion. As the hydrogen ion activity becomes very
small, these other ions can compete successfully in the
potential-determining mechanism.
• The error is negligible at pH less than about 9; but at pH
values above this, the glass electrode senses other
cations besides H+. this leads to negative errors (pH is
less than the real value)

Acid error:

• At very low pH values (pH < 1), the gel layer of the pH-
sensitive glass membrane absorbs acid molecules. This
absorption decreases the activity of hydrogen ions and
results in a lower potential at the outer membrane phase
boundary.
• The pH measurement therefore shows a higher pH value
than the actual pH value of the sample solution.

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Application of potentiometry
1. Direct potentiometric measurements:
E = L - 0.059 pH
2. potentiometric titration:
• Potentiometric titration is a volumetric method in which
the potential between two electrodes (referent and
indicator electrode) is measured as a function of the
added reagent volume.
• Involves measurement of the potential of a suitable
indicator electrode as a function of titrant volume
• The part of the curve that has the maximum change
marks the equivalence point of the titration.

Potentiometric titration

It is used for all types of volumetric analysis: acid

base, precipitimetry, complexometry and redox

It is used when it is not easy or impossible to detect

the end point by ordinary visual methods i.e:
1. For highly coloured or turbid solutions.
2. For very dilute solutions 10-3, 10-6 M.
3. When there is no available indicator .

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Potentiometric titration

Titration Curves

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End Point Determination

a -Titration curve. b- 1st derivative.

c- 2 nd derivative. d- Gran plot.