POTENTIOMETRY

The Potentiometry or Potentioetric Titrations are based exclusively upon the monitoring of
a potential at an appropriate sensing-electrode (reference electrode) as a determinant critical
function of the volume of a titrant.
In potentiometry, the curves are usually plotted in two manners,

 millivolts (mV) vs Volume of titrant added (mL)

 pH vs Titrant volume

The electroanalytical techniques are exclusively based upon a specific electrical

characteristic feature as stated under:
Measurement of potential : Potentiometry
Measurement of conductance : Conductometry
Measurement of diffusion current : Polarography (Voltammetry)
Evaluation of material produced : Coulometry at the electrode

Thus, all these evaluations and measurements are directly associated with the critical analytical
concentration of the specific analyte under investigation.

Introduction:
 In potentiometric titration reference and indicator electrodes are immersed in the
solution of analyte and potential on indicator electrode is measured with relation to
reference electrode.
 Titrant is added to the analyte solution and change in
potential is measured. At the end point there is a sharp
change in potential on indicator electrode.
 Graph is plotted between indicator electrode potential
and volume of titrant added, and the end point is determined.
 Reference electrode has its own standard potential and
remains unchanged, while indicator electrode responds to
change in electromotive force (EMF) of solution.
 EMF is calculated as, Ecell = Ereference+ Eindicator+ Ejunction

Electrochemical cells:
There are two types of electrochemical cells, for instance

a) Electrolytic cell using electricity

b) Galvanic cell producing electrical energy
Electrolytic cell:
An electrolytic cell is an electrochemical cell that drives a non-spontaneous redox reaction
through the application of electrical energy. They are often used to decompose chemical
compounds, in a process called electrolysis—the Greek word lysis means to break up.
Important examples of electrolysis are the decomposition of water into hydrogen and oxygen,
and bauxite into aluminium and other chemicals. Electroplating (e.g. of copper, silver, nickel
or chromium) is done using an electrolytic cell. Electrolysis is a technique that uses a direct
electric current (DC).
An electrolytic cell has three component parts:
an electrolyte and two electrodes (a cathode and
an anode).
The electrolyte is usually a solution of water or
other solvents in which ions are dissolved. Molten
salts such as sodium chloride are also electrolytes.
When driven by an external voltage applied to the
electrodes, the ions in the electrolyte are attracted to
an electrode with the opposite charge, where
charge-transferring (also called faradaic or redox)
reactions can take place. Only with an
external electrical potential (i.e. voltage) an
electrolytic cell decompose a normally stable,
or inert chemical compound in the solution. The electrical energy provided can produce a
chemical reaction which would not occur spontaneously otherwise.

Galvanic cell:
A galvanic cell, or voltaic cell, is an electrochemical cell that derives electrical energy from
spontaneous redox reactions taking place within the cell. It generally consists of two different
metals connected by a salt bridge, or individual half-cells separated by a porous membrane.
In its simplest form, a half-cell consists
of a solid metal (called an electrode) that
is submerged in a solution; the solution
contains cations (+) of the electrode
metal and anions (-) to balance the
charge of the cations. The full cell
consists of two half-cells, usually
separated by a semi-permeable
membrane or by a salt bridge.
A specific example is the Daniell cell,
where a salt bridge, which is a tube filled
with saturated salt solution like KCl,
NaCl etc., is used as separator (see
figure). Through the salt bridge
movement of the ions between the
solutions takes place.
The zinc (Zn) half-cell has a solution of ZnSO4 (zinc sulfate) and the copper (Cu) half-cell has
a solution of CuSO4 (copper sulfate).
Let an external electrical conductor connect the Cu and Zn electrodes. In the Zn half-cell, Zn
from the Zn electrode dissolves into the solution as Zn2+ ions (oxidation), releasing electrons
that enter the external conductor.
In the Cu half-cell, the Cu ions plate onto the Cu electrode (reduction), taking up electrons that
leave the external conductor. Since the Cu(2+) ions (cations) plate onto the Cu electrode, the
latter is called the cathode. Correspondingly the Zn electrode is the anode. The electrochemical
reaction is:
Zn + Cu2+→ Zn2++ Cu
In addition, electrons flow through the external conductor, which is the primary application of
the galvanic cell.

Nernst equation:
When a metal M is duly placed in a solution containing its own very ions Mn+, it generates
critically a definite ‘electrode potential’ across the two electrodes. Thus, is actual value is
provided genuinely by the Nernst Equation as expressed below:
𝑹𝑻
E = E0 + 𝒍𝒏 𝒂 𝑴n+
𝒏𝑭
Where,
E = Electrode potential
E0 = Standard electrode potential
a = Thermodynamic activity of ion to which the ‘electrode’ is sensitive
R= Gas constant (8.3143 JK-1mol-1)
T= Absolute temperature (Kelvin ‘K’)
F= Faraday constant (96500 C mole-1 of electrons)
n= No. of electrons involved in the ‘electrode reaction’

Electrodes used in Potentiometry:

In potentiometry, the instrument consists of two electrodes,
Reference electrode:
o The reference electrode is the electrode which has a standard potential of its own
potential value and it is stable when dipped into sample solution. The salt bridge is used
to prevent the interference of the analyte solution with that of reference solution.
o Here analyte solution is the solution whose potential is to be measured.
o Always treated as the left-hand electrode (anode)
o Example of reference electrode:
 Standard hydrogen electrode (SHE) → Primary electrode
 Saturated calomel electrode
Secondary electrodes
 Silver-silver chloride electrode

Indicator electrode:
It is used to measure the potential of the analyte solution comparing with that of reference
electrode. Its potential is directly proportional to ion concentration of the analyte.
Ex: Hydrogen electrode.
Glass electrode.
Antimony –antimony oxide electrode
There are two classes of indicator electrodes:
 Metal indicator electrodes
 Ion-selective electrodes

Standard Hydrogen Electrode:

 Defined as the potential that is developed between H2 gas adsorbed on the Pt metal and
H+ of the solution.
 It is used for
i. Determination of electrode potential of metal electrode system
ii. Determination of pH of the solution
 SHE is a primary reference electrode.
 It can be used as both reference and indicator electrodes.
o Hydrogen electrode when dipped in standard acid solution → Reference electrode.
o Hydrogen electrode when dipped in analyte solution → Indicator electrode.

Apparatus:
֎ It consists of glass tube having
holes at bottom.
֎ This tube consists of one more
tube having platinum wire with
platinum foil, where platinum foil is
coated with platinum black.
֎ The Hydrogen (H2) gas is passed
through the tube which can come
out from hole at the bottom of the
tube.
֎ The whole tube is dipped in 1M
HCl at 25°C.

Working:
1. The potential of SHE is zero at all temperature.
2. When hydrogen electrode is connected to other electrode (indicator electrode) through
salt bridge, potential of indicator electrode can be measured.
Eg: Zinc electrode is connected to hydrogen electrode by KCl salt bridge.
Pt, H2/H+//Zn++/Zn
The cell reaction is:
H2 + Zn+2 → 2H+ + Zn
Half-cell reaction is:
H2 → 2H+ + 2e-
Zn+2 + 2e- → Zn
The electrode potential of indicator electrode is determined by the following formula:
0.0591 1
E = E0 - 𝑛 log[ 𝐻 +]
3. When pure and dry H2 gas is passed through the inlet tube, a part of the gas gets
adsorbed and the excess bubbles out through the perforations. Between the H2 gas
absorbed on the surface of the metal and H+ of the solution, an equilibrium is
established and an electrical double layer of opposite charges is formed. The potential
developed is called H2 electrode potential.
 4. In the above system, when the H2 gas at a pressure of 1atm is bubbled through 1M HCl,
the electrode (constructed) or formed is called STANDARD HYDROGEN
ELECTRODE (SHE) or Normal H2 electrode (NHE). This is represented as Pt, H2 /
H+(760 mm of Hg) (IM).
5. The standard H2 electrode potential is defined as the potential that is developed between
the H2 gas adsorbed on the Pt metal and H+ of the solution when the H2 gas at a pressure
of 760 mm of Hg is in equilibrium with H+ of unit concentration.

Limitations:
1. It is rather difficult to regulate the pressure of the H2 gas to be at exactly 1atm
throughout the experiment.
2. Excess of H2 bubbling out carries little HCl with it and hence the H+ concentration
decreases. In such a system, it is difficult to maintain the concentration of HCl at 1M.
3. Platinum foil gets easily poisoned by the impurities present in the gas and HCl. In fact,
the attainment of equilibrium is ensured by trial and error.
4. If the solution contains any oxidizing agent, the H2 electrode cannot be used.

Advantages:
1. Used as both indicator and reference electrode.
2. Gives reproducible results
Disadvantages:
1. Not used if strong oxidising and reducing agents are present.

Saturated calomel electrode:

The Saturated calomel electrode (SCE) is a reference electrode based on the reaction
between elemental mercury and mercury(I) chloride. It has been widely replaced by the silver
chloride electrode, however the calomel electrode has a reputation of being more robust. The
aqueous phase in contact with the mercury and the mercury(I) chloride (Hg2Cl2, "calomel") is
a saturated solution of potassium chloride in water. The electrode is normally linked via a
porous frit to the solution in which the other electrode is immersed. This porous frit is a salt
bridge.
Apparatus:
 It consists of glass tube having side arm tube.
 Pure mercury is placed at the bottom and is covered with
a paste of calomel (Mercury - Mercurous chloride) and KCl.
 The platinum wire is placed at the centre of glass tube,
which makes electrical connections with mercury.

Working:
Calomel electrode when connected with indicator electrode
by salt bridge, EMF (electromotive force) of the indicator
electrode is calculated.
Calomel electrode when connected to hydrogen electrode it is used for measuring pH of the
solution.
Hg/Hg2Cl2.KCl//H+/H2.Pt
Advantages:
1. It can be used over wide pH range.
2. It can be used in various solvents.
Disadvantages:
1. Unstable at temperature above 80°C.
2. The calomel electrode contains mercury, which poses much greater health hazards than
the silver metal used in the Ag/AgCl electrode.

Silver-Silver Chloride (Ag-AgCl) electrode:

A silver-silver chloride electrode is a type of reference
electrode, commonly used in electrochemical
measurements. For environmental reasons it has widely
replaced the saturated calomel electrode. For example, it
is usually the internal reference electrode in pH
meters and it is often used as reference in reduction
potential measurements.
Construction:
The electrode assembly consists of a silver metal
electrode in contact with solid silver chloride (usually as
a coating on the silver metal) immersed in an aqueous
chloride salt solution saturated with silver chloride. All
these are contained in a small vessel, typically made of
glass tubing. The internal electrolyte of the reference
electrode assembly and the external electrolyte into
which the whole assembly is immersed are in ionic
contact through a separator. A typical separator is a
small porous ceramic plug sealed into the end of the
glass tubing.
Working:
The standard potential of this electrode is determined by combining with hydrogen electrode.
Ag/AgCl.KCl//H2/H+.Pt
Advantages:
The electrode has many features making it suitable for use:

1. Simple construction
2. Inexpensive to manufacture
3. Stable potential
4. Non-toxic components
Disadvantages:

1. Light: UV light decomposes AgCl to give silver(0) which gives the electrode a black
appearance.
2. Base: Ag2O or AgOH will form if the [OH-] is on the order of 0.1 M and the electrode
potential will be a mixed Ag/AgCl/Ag2O potential and will depend on the pH. Ag2O
will also form in the pores of the frit used.
3. NH3 Buffers: NH3 will complex silver and will dissolve AgCl.
4. Sulfide: Silver sulfide is quite insoluble.

Glass electrode:

A glass electrode is a type of ion-selective electrode made of a doped glass membrane that is
sensitive to a specific ion. The most common application of ion-selective glass electrodes is
for the measurement of pH. The pH electrode is an example of a glass electrode that is sensitive
to hydrogen ions. Glass electrodes play an important part in the instrumentation for chemical
analysis and physico-chemical studies. The voltage of the glass electrode, relative to some
reference value, is sensitive to changes in the activity of certain type of ions.

Construction:

A typical modern pH probe is a combination electrode, which combines both the glass and
reference electrodes into one body. The combination electrode consists of the following parts
(see the drawing):

1. A sensing part of electrode, a bulb made from a specific glass

2. Internal electrode, usually silver chloride electrode or calomel
electrode
3. Internal solution, usually a ph=7 buffered solution of
0.1 mol/l kcl for ph electrodes or 0.1 mol/l mcl for pm electrodes
4. When using the silver chloride electrode, a small amount of agcl
can precipitate inside the glass electrode
5. Reference electrode, usually the same type as 2
6. Reference internal solution, usually 0.1 mol/l kcl
7. Junction with studied solution, usually made from ceramics or
capillary with asbestos or quartz fiber.
8. Body of electrode, made from non-conductive glass or plastics.
The bottom of a pH electrode balloons out into a round thin glass
bulb. The pH electrode is best thought of as a tube within a tube. The
inner tube contains an unchanging 1×10−7 mol/L HCl solution. Also
inside the inner tube is the cathode terminus of the reference probe.
The anodic terminus wraps itself around the outside of the inner tube
and ends with the same sort of reference probe as was on the inside of the inner tube. It is filled
with a reference solution of KCl and has contact with the solution on the outside of the pH
probe by way of a porous plug that serves as a salt bridge.
Working:
The glass bulb should be placed in small quantity of water for the electrical conductivity of the
glass bulb. If the glass bulb undergoes dehydration then there will not be any electrical
conductivity, which in turn affects the determination of pH of any sample. The glass bulb is
composed of Ag/AgCl as internal reference electrode and standard calomel electrode as the
external reference electrode.

Ag/AgCl SCE
Internal External
Test Glass
Reference Reference
Solution Electrode
Electrode Electrode

Each vertical line indicates potential developed during reaction. Glass bulb is composed of
sodalime glass and the test solution consists of H+ ions.
Si-O-Na + H+ → Si-O-H + Na+
During the course of reaction, all the cations from the glass bulb undergo exchange with H+
ions of the test solution. The glass membrane acts as highly semipermeable membrane for
exchange and absorption of H+ ions, therefore helps in determination of pH.
Potential of the glass electrode depends on the following factors:
 Composition of the glass bulb
 Thickness of the glass bulb
 Surface area of glass bulb
Applications:
Glass electrodes are commonly used for pH measurements. There are also specialized ion
sensitive glass electrodes used for determination of concentration of lithium, sodium,
ammonium, and other ions. Glass electrodes have been utilized in a wide range of applications
— from pure research, control of industrial processes, to analyze foods, cosmetics and
comparison of indicators of the environment and environmental regulations: a microelectrode
measurements of membrane electrical potential of a biological cell, analysis of soil acidity, etc.
Advantages:
 It can be used over entire pH range.
 Simple to operate.
 It can be used in viscous, coloured solutions.
 Not affected by oxidising and reducing agents, tannins.
 It obeys Nernst equation.
 Physiological solution can be determined.
Disadvantages:
 Glass is fragile, should be handled carefully.
 Minute scratches on glass membrane, makes it useless.
 The glass bulb must be hydrated all time.
 There may be chance for development of internal resistance because of electrical
conductivity.
Metal indicator electrodes:
These develop electric potential in response to redox reaction on the metal surface. These are
mainly classified into three types of electrodes used in the potentiometry.
They are as follows.
1. First kind electrodes: They are composed of the metal rod immersed in its metal
solution. These electrodes respond to the ionic activity of the electrode.
Ex: Silver electrode dipped in the silver nitrate solution.
Ag+ + e ↔ Ag
Copper electrode dipped in the copper sulphate solution.
Cu+2 + 2e ↔ Cu
Zinc electrode dipped in the Zinc sulphate solution.
Zn+2 + 2e ↔ Zn
2. Second kind electrode: These are composed of the metal wires coated with the salt
precipitates. These electrodes respond to the changes in the ionic activity through the
formation of the complex. This kind of electrode can be used to measure the activity of
chloride ion in a solution.
Ex: Silver electrode and silver chloride as its salt precipitate.
Ag/ AgCl/ KCl
Mercury electrode and mercury chloride as its salt precipitate.
Hg/ Hg2Cl2/ KCl
3. Third kind electrodes: These electrodes are also known as inert electrodes and redox
electrodes. They are composed of inert metal electrode immersed in the redox solution.
The potential of such an inert electrode is determined by the ratio of the reduced and
oxidized species in the half-reaction. The usually used inert material is Platinum (Pt).
Ex: Pt-H2 electrode

Types of potentiometric titrations:

Acid-base reactions: Glass / calomel electrode for determination of pH.
Ex: Titration of HCl with NaOH
Titration of CH3COOH with NaOH
Precipitation reactions: Membrane electrodes for the determination of the halogens using
silver nitrate reagent.
Ex: Titration of mixture of Cl- & Br- & I- with AgNO3
Redox titration: Platinum electrode.
Ex: Reaction of Fe3+/ Fe2+ with Ce4+/Ce3+
Complex formation titration: Metal and membrane electrodes for determination of many
cations (mixture of Bi3+, Cd2+ and Ca2+ using EDTA)

Methods for determining the end point in potentiometric titrations:

1. Normal titration curve: It is obtained by plotting the successive values of the cell emf on
ordinate and corresponding values of volume of
titrant added on the abscissa. This gives an S-
shaped curve. The central portion of this curve
which shows the steeply rising portion
Equivalence corresponds to the volume for the end point of
Point
the titration. When there is a small potential
change at the end point like in the titration of
weak acid with strong base, titration of very
dilute solution etc, it is difficult to locate end
point by this method.

Volume of titrant (ml)

2. Analytical or Derivative Method: The end point can be more precisely located from the
first or second derivative curves.
a) First derivative curve: The first derivative
Equivalence point
curve involves the plot of slope of the titration curve
(ΔE/ΔV-ration of change in emf and change in
volume added) against the volume of the titrant
added. At the end point there is maximum change in
EMF or pH. The end point is calculated by drawing
perpendicular from peak of graph on volume axis.

b) Second derivative curve: In second derivative

curve we plot the slope of first derivative curve
(Δ2E/ΔV) against volume. The point on volume
axis where the curve cuts through zero on the
ordinate gives the end point. This point
corresponds to the largest steepest point on
titration curve and maximum slope of the ΔE/ΔV
curve.

3. Gran Plot: This is a new method of end point location in potentiometric titration developed
by G. Gran in 1952 and modified by others. This
method does the numerical manipulation of
titration curves into linear straight lines
intersecting at the equivalence point. The end
point from Gran Plot can be obtained either
taking the points before the end point or taking
the points after the end point. It is obvious that
the results obtained from linear curves would be
more accurate than from the non-linear ones. The
linear straight lines can be extrapolated to the
volume axis to locate the end point. By the
development of calculator, later on computer and using ion selective electrode, use of Gran
Plot is increasing.
Advantages of using Gran's method of locating end point are:
1. Simplicity of measurement
2. Simplicity of Calculation
3. Versatility and Precision
Disadvantages of using Gran's method of locating end point are:
1. Requires skilled person to interpret results
2. Requires special graph paper to plot the value
3. Difficult to plot
4. Time consuming
Potentiometric instrumentation:
A typical modern pH probe is a combination electrode, which combines both glass electrode
and reference electrode into one body.

The combination electrode consists of the following parts:

 A sensing part of electrode, a bulb made from specific glass. Internal electrode is usually
silver chloride electrode.
 Internal solution is usually a pH = 7 buffered solution of 0.1 mol/L HCl for pH electrodes.
When using silver chloride electrode, a small amount of AgCl can precipitate inside the
glass electrode.
 Usually calomel electrode is used as reference electrode and reference internal solution is
0.1 mol/L KCl. Junction is usually made from ceramics or capillary with asbestos or
quartz fiber. Construction of electrode body is made from non-conductive glass or
plastics.
 The bottom of a pH electrode balloons out into a round thin glass bulb. The pH electrode
is a tube within a tube. The inner tube contains an unchanging 1 X 10-7 mol/L HCl
solution. Also inside the inner tube is the cathode terminus of the reference probe. The
anodic terminus wraps itself around the outside of the inner tube and ends with the same
sort of reference probe as it was on the inside of the inner tube. It is filled with a reference
solution of KCl and has contact with the solution on the outside of the pH with a porous
plug that serves as a salt bridge.
Long essay: 10 marks
1. Describe a potentiometric titration assembly with a well-labelled diagram. Briefly
enumerate its working systematically. Discuss in brief the advantages and disadvantages
of potentiometric titration.

Short essay: 5 marks

1. Explain the construction and working of standard hydrogen electrode.
2. Explain the principle in potentiometry and give example of indicator electrodes used in
potentiometry.
3. Discuss the various end point detection methods in potentiometric titrations.
4. Explain the construction and working of standard calomel electrode.
5. Explain the construction and working of silver-silver chloride electrode.
6. Explain electrochemical cells.

Short answer: 2 marks

1. Write a note on electrochemical cell.
2. Give some applications of potentiometric titration.
3. Give the Nernst equation.
4. Define Potentiometry. Enlist different reference and indicator electrode.
5. Draw a neat labelled diagram of Glass electrode.