POTENTIOMETRY

INTRODUCTION
Potentiometry /potentiometric titration is one of the methods of electro-analytical chemistry. It
can be defined as,
A method to determine the concentration of analyte/solute in a given solution by measuring
the potential between two electrodes.
The first potentiometric titration was carried out by Robert Behrend in 1893.
Potentiometric titration is preferred over manual titrations as it gives more accurate and precise
results than other titrations in which different reagents are used as indicators.
Principle of Potentiometric Titration

The principle of potentiometric titration is based upon the ability of certain membrane materials
to generate an electrical potential (electromotive force, EMF) that can be used to measure the
concentration of ions in the solution.
Components of potentiometric titration

Potentiometric titration is a technique similar to direct titration, but in this, no indicator reagent
is used; instead, an electrode is used as an indicator. Following are the components used in
potentiometric titrations,

 Analyte –general electrolyte solutions

 Electrodes- Reference and indicator electrode
 Voltmeter/Ph meter

REFERENCE ELECTRODE
A reference electrode is an electrode that has a stable and well-known electrode potential.

 Its potential remains the same regardless of the solution to which it is dipped
 It is always treated as an anode

Types of Reference Electrode

Following are the three most commonly used Reference electrodes
Standard hydrogen electrode (SHE)
In this electrode, Pt wire is dipped into 1M H+ ions solution and H2 gas is bubbled at 1 atm. It’s a
primary reference electrode. The assembly is enclosed in a glass covering.Its potential is
considered to be zero.
Electrode reaction:
half cell: Pt,H2 (g, 1atm) | H+ (aq, a = 1.00) ||2 H+ (aq) + 2 e ─ ↔ H2 (g)
Eo = 0.00V
Applications

 determination of electrode potential of the metal electrode system .

 determination of pH of the solution.
Advantages

 It can be used over the entire pH.

 It can be used as a reference electrode when dipped with standard acid solution and as a
indicator electrode when dipped into a sample solution.
 It is the primary reference standard against which the potentials of other electrodes are
measured

Limitations

 It is difficult to be used and to keep H2- gas at one atmosphere during all determinations.
 It needs periodical replating of Pt. Sheet with Pt. Black

Saturated calomel electrode

It consists of an inner jacket and an outer sleeve. Inner jacket has wire contact with Hg and plugged
with a mixture of calomel (Hg2Cl2 and KCl ). The outer sleeve has crystals of KCl & porous plug of
asbestos. The space between the inner jacket the and outer sleeve is filled with saturated KCL/1N
KCL/0.1 The potential of the electrode depends on the concentration of the KCL solution and
temperature.
Electrode Reaction
Hg(l) | Hg2Cl2 (sat’d), KCl (aq, sat’d) || Hg2Cl2(s) +2e– ↔2Hg(l ) + 2Cl-(aq)
E0 = 0.242V
Application

 Used in pH Measurement
 Used cyclic voltammetry and general aqueous electrochemistry.

Advantages
 Easy of construction and Stability of Potential.

Limitations
 Sensitive to temperature change.
Silver-silver chloride electrode
The silver/silver chloride reference electrode is composed of a silver wire (Ag) that has been
coated with a layer of solid silver chloride (AgCl), immersed in a solution that is saturated with
KCl and AgCl.
Electrode Reaction

AgCl (s) + e - ↔Ag (s) + Cl-

E=0.199V
Application
 Mainly used with saturated potassium chloride (KCl) electrolyte.

Advantages

 Widely used because simple, inexpensive, very stable.

 Less toxicity and environmental problems with consequent cleanup and disposal
difficulties.

Disadvantages/Limitations
 It is more difficult to prepare than SCE.
 AgCI in the electrode has large solubility in saturated KCl.
INDICATOR ELECTRODE
It is an electrode that responds to variation in the potential of analytic solution
It is denoted by IE.

Mechanism
This electrode contains a membrane that is sensitive to the activity of the analyte. Therefore, the
potential of IE depends on the concentration of the analyte. The analyte enters the electrode
membrane, which causes a change in membrane potential.

TYPES OF INDICATOR ELECTRODE

Metal Indicator Electrode
The potential of a metallic electrode is determined by the position of a redox reaction at the
electrode–solution interface. Three types of metallic electrodes are
commonly used in potentiometry.
i. First-Order Electrode
ii. Second-Order Electrode
iii. Third-Order Electrode
iv. Redox Electrode

i.First Order Electrode

An indicator electrode in which a metal is in direct contact with a solution containing its ion is
called an electrode of the first kind.

Example: use of copper electrode to detect Cu2+ in solution

½ reaction: Cu2+ + 2e-  Cu (s)
Advantages
 Involves single reaction
 Detection of cathode is derived from the metal used in the electrode

Limitations
 Metallic indicator electrodes are not very selective and respond not only to their own
cations but also to other more easily reduced cations.
 Many metal electrodes can be used only in neutral or basic solutions because they
dissolve in the presence of acids
 Easily oxidized, can be used only when analyte solutions are deaerated to remove
oxygen
 Certain hard metals (Fe, Cr, Co, Ni) do not provide reproducible potentials

Limited electrodes are

Ag/Ag+ and Hg/Hg2+ in neutral solutions and Cu/Cu2+, Zn/Zn2+, Cd/Cd2+, Bi/Bi3+, Tl/Tl+, and
Pb/Pb2+ in deaerated solutions.

ii.Second-Order Electrode
The metallic electrode that is responsive to the activity of an anion with which its ion forms a
precipitate or stable complex ion.
Example: Detection of Cl- with Ag electrode

½ reaction: AgCl(s) + e -  Ag(s) + Cl- EO = 0.222 V

iii.Third Order Electrode
A metal electrode, under certain circumstances, can be made to respond to a different cation.
Example: Hg electrode to measure Ca
½ reaction: CaY-2  Ca+2 + Y-4
iv.Redox Electrode
Metallic electrodes also can serve simply as a source of, or a sink for, electrons in other redox
reactions. Such electrodes are called redox electrodes. Pt, Au, Pd (inert metals) are responsive to
the activities of the oxidized and reduced forms of the redox couple near the electrode surface.
Example : Detection of Ce3+ with Pt electrode

½ reaction: Ce4+ + e -  Ce3+

Membrane Indicator Electrode
Electrodes are based on the determination of cations or anions by the selective adsorption of
these ions to a membrane surface.It is also known as Ion Selective Electrode.
Mechanism
The mechanism by which an ion-selective potential develops in these devices depends on the
nature of the membrane. In membrane electrodes, in contrast, the observed potential is a kind of
junction potential that develops across a membrane that separates the analyte solution from a
reference solution
Membrane indicator Electrode can be further classified as,

 Crystalline Membrane Electrode

 Non-Crystalline Membrane Electrode

Advantages
 Relatively inexpensive and simple to use.
 Have an extremely wide range of applications and wide concentration range.
 They are invaluable for the continuous monitoring of changes in concentration
  They are particularly useful in biological/medical applications because they measure the
activity of the ion directly, rather than the concentration.
 ISEs are one of the few techniques which can measure both positive and negative ions.
 They are unaffected by sample colour or turbidity.
 ISs can be used in aqueous solutions over a wide temperature range.
Limitations
 Precision is rarely better than 1%.
 Electrodes can be fouled by proteins or other organic solutes.
 Interference by other ions.
 Electrodes are fragile and have limited shelf life.
 Electrodes respond to the activity of uncomplexed ion. So ligands must be absent.
Applications
 Ion-selective electrodes are used in a wide variety of applications for determining the
concentrations of various ions in aqueous solutions.
 To Test drinking water and other drinks.

i.Crystalline/Solid State Membrane Electrode

The membrane is composed of an insoluble inorganic salt. An ion-exchange process leads to the
formation a potential at the membrane.

 Single crystal LaF3 is widely used to determine F-

 Polycrystalline or mixed crystal membranes such as AgCl / Ag2S can be used to determine
Cl-

ii. Non-Crystalline Membrane Electrode

Liquid membrane electrodes

An ion-exchanger or ionophore (neutral macrocyclic ion carrier) is dissolved in a viscous organic
liquid membrane. Without the exchanger or ionophore the ion of interest is unable to penetrate
the membrane.
Example : One of the most famous liquid membrane electrodes has been used for calcium
determination.
Ca2+(aqueous)+2(RO)2PO−2(organic)⇋[(RO)2PO2]2Ca(organic)
Gas-Sensing Electrodes

A number of membrane electrodes respond to the concentration of a dissolved gas. Gas semsing
electrode consist of a thin membrane that separates the sample from an inner solution containing
an ion-selective electrode. The membrane is permeable to the gaseous analyte, but impermeable
to nonvolatile components in the sample’s matrix. The gaseous analyte passes through the
membrane where it reacts with the inner solution, producing a species whose concentration is
monitored by the ion-selective electrode.

Example : In a CO2 electrode, CO2 diffuses across the membrane where it reacts in the inner
solution to produce H3O+.

CO2(aq)+2H2O(l)⇋HCO−3(aq)+H3O(aq)

Glass Membrane Electrode

Glass electrodes are responsive to univalent cations ( H+, Na+). Glass membrane manufactured
either from SiO2 ,Al2O3,N2) with a negatively charged oxygen atom. It consists of a sturdy glass
tube with a thin glass bulb welded to it. Inside glass tube there is a known solution of potassium
chloride (KCl) buffered to a pH of 7.0. The silver electrode with a silver chloride tip makes
contact with the internal solution. Inside the glass bulb, a dilute HCl solution. To minimize
electronic interference, the probe is protected by a blade protector, which is often located inside
the glass electrode.The electrode is immersed in the solution and pH is measured.
 Glass bulb KCl /Agcl
Silver wire
With HCL

Example: Glass pH electrode

Advantages

 Potential not affected by the presence of oxidizing or reducing agents

 Operates over a wide pH range and Fast response
 Functions well in physiological systems
Limitations
 sensitive to alkali metal ions at pH greater than 12.
 At pH less than 0.5, values obtained with the pH electrode are high.
 Dehydration – must keep membrane moist.
 Errors in low ionic strength – varying junction potentials.

PH METER
A pH meter is an electric device that measures the hydrogen-ion activity in water-based
solutions, indicating its acidity or alkalinity which is expressed as pH.
Principle
The pH meter operates on the principle of measuring the difference in electrical potential
between a pH electrode and a reference electrode, and so the pH meter is also referred to as a
"potentiometric pH meter”.
Construction
Fundamentally, a ph meter comprises a simple electronic amplifier (voltmeter) and a pair of
electrodes, or alternatively a combination electrode, and some form of display calibrated in pH
units.
The Modern probe Ph meter consist of :

 Glass bulb: It is a sensor that senses the H+ ion concentration and it is made from special type
of glass and membrane. The glass bulb consists of 0.1M HCL.
 Glass/indicator electrode : It is the silver chloride electrode.
 Indicator electrode solution: The silver chloride electrode is dipped in buffer solution of 0.1
mol/L KCL of pH 7.
 Reference Electrode: It is also the silver chloride electrode.
 Reference Electrode Solution: The reference electrode is also dipped in buffer solution of 0.1
mol/L KCL of pH 7.
 Junction: It is made a from ceramic junction also called as diaphragm that allows the contact
of sample solution and reference electrolyte. It does not disturb the electric connection
between the electrodes.
Working
Potentiometric pH meters measure the voltage between two electrodes and display the result
converted into the corresponding pH value. It usually has a glass electrode and a reference
electrode, or a combination electrode. When the pH probe is dipped in the solution, the H+ ion
moves close to the glass membrane of the sensitive glass bulb (external side of the bulb). A similar
reaction occurs inside the bulb, which is filled with a buffer solution of neutral pH. This neutral
buffer solution has a constant number of Hydrogen ions. The H+ ions present inside the bulb also
move close to the glass membrane (internal side of the bulb). Hence, this causes the difference in
the concentration of hydrogen ion or degree of hydrogen ion activity across the membrane
causing the difference in the potential (voltage). This is displayed in pH units on the screen of the
pH meter.

 When the hydrogen ion concentration inside the glass bulb is less than the outside
solution (test solution), then the given solution is acidic and hence the pH is lower than 7.
 When the Hydrogen ions concentration across the membrane is same then it is called as
neutral pH and the pH is equal to 7.
 If the concentration of hydrogen ion of inside the bulb than outside solution then the
given solution is alkaline and the pH is more than 7.
 The pH meter measure the potential difference at both the electrodes and calculate the
pH as per the Nernst equation.

Glass electrode
solution AgCl/KCL Glass Bulb filled with HCl

POTENTIOMETRIC TITRATION PROCEDURE

Potentiometric titration involves the measurement of the potential of an indicator electrode with
respect to a reference electrode as a function of titrant volume. In this titration, we measure and
record the cell potential (in millivolts or pH) after adding titrant each time. As we approach the
endpoint, we start adding titrants in very small quantities. The most straightforward and most
used method of endpoint detection in potentiometric titration is plotting a graph between cell
potential and volume of titrant. The midpoint of the steeply rising portion of the graph or curve is
estimated visually and taken as an endpoint.
APPLICATION OF POTENTIOMETRY
 It is used in clinical chemistry for the analysis of metals.
 It is used for the analysis of cyanide, ammonia, etc., in water or wastewater.
 It is used in agriculture for the detection of different elements in soils, fertilizers etc.
 It is used in detergent manufacturing, food processing etc.

REFERENCES
 https://www.vedantu.com/chemistry/potentiometric-titration
 https://www.brainkart.com/article/Glass-Ion-Selective-Electrodes---Potentiometric-
Methods-of-Analysis_29719/
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%20Potentiometry.pdf
 https://chemistry.unt.edu/~tgolden/courses/Lecture%2022%20Potentiometry%20202
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uses
 https://forumautomation.com/t/ph-meter-construction-advantages/5438