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CHM 4102



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In potentiometry, the potential of an electrochemical cell

is measured under static conditions because no current
flows while measuring a solutions potential, its
composition remains unchanged.

Information on a composition of the sample is obtained

through the potential appearing between two
The first quantitative potentiometric applications appeared
soon after the formulation of Nernst equation.

In 1889, the Nernst equation relating an electrochemical cells

potential to the concentration of electroactive species in the

Potentiometric methods of analysis are based upon

measurements of the potential of electrochemical cells under
conditions of zero current, where the Nernst equation
governs the operation of potentiometry.
Nernst equation:
Ecell = E0cell - (RT/nF) lnQ

Ecell = cell potential under nonstandard conditions (V)

E0cell = cell potential under standard conditions
R = gas constant, which is 8.31 (volt-coulomb)/(mol-K)
T = temperature (K)
n = number of moles of electrons exchanged in the electrochemical
reaction (mol)
F = Faraday's constant, 96500 coulombs/mol
Q = reaction quotient
Basic Principles
A device for measuring the potential of an electrochemical
cell without drawing a current or altering the cells
The potential of an electrochemical cell is measured under
static conditions.
Because no current, or only a negligible current flows while
measuring a solutions potential, its composition remains
For this reason, potentiometry is a useful quantitative
Potentiometric measurements
Made by using a potentiometer to determine the difference in
potential between a indicator electrode and a reference
Cathode is the sensing electrode. (right half-cell)
Anode is the reference electrode. (left half-cell)

Ecell = Ec Ea

Where : Ec is the reduction potential at the cathode.

: Ea is the reduction potential at the anode.
Potentiometric Electrochemical Cells

To determine difference in potential between sensing

electrode and reference electrode

Separation of the 2 electrodes to prevent the redox from

occurring spontaneously on surface of one of electrodes

Constructed that one of half cells provided a known

reference potential of other half cell indicates the
analyte concentration
Example 1

Schematic diagram of an electrochemical cell of potentiometric measurement

Salt bridge contain inert electrolyte such as KCl connects the
two half-cells.
The ends of the salt bridge are fixed with porous frits (to
allow the ions of electrolyte to move freely between the
half-cells and the salt bridge).
This movement of ions in the salt bridge completes the
electrical circuit.
Reference electrode : left electrode (anode) which
undergoes oxidation.
Sensing electrode : right electrode (cathode) which
undergoes reduction.
When the potential of an electrochemical cell is measured,
the contribution of the liquid junction potential must be
Ecell = Ec Ea Elj
Example 2
Introduction to ion selective electrode (ISE)

The cell consists of both an indicator and reference

Since the potential of the reference electrode is constant,
the potential developed at the indicator electrode that
contains information about the amount of analyte in a
During the measurement, there is little to no current
An electrochemical cell for making a potentiometric
measurement with a membrane electrode also known
as an ion-selective electrode, ISE.
Electrochemical cell for a potentiometric measurement with an ISE.
Ion selectivity

A specific ion electrode will only respond to the presence

of one species.
In reality, ion-selective electrodes can experience
interferences by responding to the presence of other
We can account for the lack of 100% specificity by
incorporating the activity of j and a selectivity coefficient
(kij) into this equation:
This new equation is called the Nikolskii-Eisenman

The selectivity coefficient is a numerical measure of how

well the membrane can discriminate against the
interfering ion.
To put this in perspective, if an electrode has equivalent
responses to the two ions, then kij = 1.0.
From the equation, the smaller the kij values, the less
impact the interfering ion will have on the measured
When kij values are less than 1, the ISE is more
responsive to the analyte ion
When kij values are greater than 1, the ISE is more
responsive to the interfering ion. For example, a kij value
of 0.01 means that the electrode is 100 times more
responsive to ion i over j.
The selectivity of the ISE is determined by the
composition of the membrane.
Ideally the membrane allows the uptake of only one
specific ion into it.
The three main components of making a
measurement at an ISE are
an inner reference, or standard solution
an outer analyte, or sample,
solution separated by a thin membrane.
The potential developed at the membrane is the
result of either an ion exchange process or an ion
transport process occurring at each interface
between the membrane and solution.
Ion Exchange Process

Lithium cation displaces a potassium cation from the

organic anion, R-:
KR + Li+ LiR + K+
We can imbed the lipophilic R- in a membrane and place it
in a solution of Li+
KR(mem) + Li+(aq) LiR(mem) + K+(aq)
To construct an ion-selective electrode an inner
reference solution added to the other side of the
This solution would contain a fixed concentration of the
ion of interest, Li+ in this example.
This is typically accomplished by placing a thin
membrane at the end of the plastic tube and filling the
tube with a standard (known concentration) solution of
the analyte.
A reference electrode is placed in the inner solution and
a second reference electrode is in contact with the
analyte (outer) solution.
Ion transport

A membrane, containing an ionophore, between an

unknown analyte solution and a known reference
solution .
The ionophore is a neutral carrier molecule
represented by the blue oval.
The ionophore cannot diffuse out of the membrane and
but can trap the analyte ion (A+) at the interface
between the solution and membrane.
Without the ionophore, the analyte would be unable to
partition into the organic membrane.
As with the ion-exchange process, equilibrium is
established at both solution-membrane interfaces. The
resulting charge separation at each interface leads to a
phase-boundary potential.
Now potential develop across the membrane.
Reference electrode

It has a standard potential on its own and its potential

does not change to whichever solution it is dipped.
Always treated as the left-hand electrode (anode)
Example of reference electrode :
Standard hydrogen electrode (SHE)
Saturated calomel electrode
Silver-silver chloride electrode
Standard hydrogen electrode (SHE)
Defined as the potential that is developed between H2
gas adsorbed on the Pt metal and H+ of the solution .
It is used for
determination of electrode potential of metal
electrode system
determination of pH of the solution

Pt,H2 (g, 1atm) | H+ (aq, a = 1.00) ||2 H+ (aq) + 2 e H2 (g)

Saturated calomel (Hg2Cl2) Electrode (SCE)
Contains of an inner jacket and outer sleeve.
Inner jacket has wire contact with Hg and plugged with a mixture of
calomel Hg2Cl2 & KCl.
Outer sleeve has crystals of KCl & porous plug of asbestos
Application: pH measurement, cyclic voltammetry and general
aqueous electrochemistry.
Advantages: ease of construction and stability of potential.

Hg(l) | Hg2Cl2 (satd), KCl (aq, satd) || Hg2Cl2(s) +2e 2Hg(l ) + 2Cl-(aq)
Silver-silver chloride electrode

Widely used because simple, inexpensive, very stable

and non-toxic.
Mainly used with saturated potassium chloride (KCl)
Advantages : easy to use
Disadvantage : difficult to prepare

Ag(s) | AgCl (satd), KCl (x M) ||AgCl(s) + e Ag(s) + Cl- (aq)

Sensing Electrodes
The potential of the sensing electrode in a potentiometric
electrochemical cell is proportional to the concentration of
Two classes of indicator electrodes are used in potentiometry:
metallic electrodes
Electrodes of the first kind
Electrode of the second kind
Redox electrode
membrane electrodes (ion-selective electrodes)
glass pH electrode
Metallic electrodes

Electrodes of the first kind

A metal in contact with a solution containing its cation.
The potential is a function of concentration of Mn+ in a
Mn+ / M. The most common ones:
Silver electrode (dipping in a solution of AgNO3)
Ag+ + e Ag
Copper electrode
Cu+2 + 2e Cu
Zn electrode
Zn+2 + 2e Zn
Electrode of the second kind
A metal wire that coated with one of its salts precipitate.
Respond to changes in ion activity through formation of
A common example is silver electrode and AgCl as its salt
This kind of electrode can be used to measure the
activity of chloride ion in a solution.
Redox electrode
An inert metal is in contact with a solution containing the
soluble oxidized and reduced forms of the redox half-
The inert metal is usually is platinum (Pt).
The potential of such an inert electrode is determined
by the ratio of the reduced and oxidized species in the
A very important example of this type is the hydrogen
Membrane electrodes

Glass pH electrode
Advantages over other electrodes for pH measurements:
Its potential is essentially not affected by the presence
of oxidizing or reducing agents.
It operates over a wide pH range.
It responds fast and functions well in physiological
Glass pH electrode
For measurement, only the bulb needs to be submerged.
There is an internal reference electrode and electrolyte
(Ag| AgCl| Cl) for making electrical contact with the glass
membrane, its potential is necessarily constant and is set by
the concentration of HCl.
A complete cell, then, can be represented by:
Theory of the glass membrane potential

Both the inside and outside surfaces of the glass membrane in

the GE bulb have SiOH groups.
The interior surface of the glass membrane is in contact with a
constant concentration of HCl, and so the number of SiO
groups on the interior surface remains constant.
By contrast, the number of SiO groups on the exterior of the
glass membrane will change when the pH of the solution the
glass membrane is immersed in changes.
The difference in charge on the inside and outside of the glass
membrane results in a membrane potential.
If we can set up an experiment to measure the membrane
potential, then this corresponds to measuring the pH of the
solution in which the glass electrode is immersed.
Alkaline Error

Systematic error occurs when using glass pH electrode to

measure pH of extremely alkaline solution

Glass pH electrode responds very selectively to H+ ions,

but, sensitive to alkali metal ions too

Caused by interference of high concentration of alkaline

metal ions, e.g: Li+, Na+, K+
Alkaline Error cont.

At high pH where [H+] <<< [Na+], electrode begins to

respond to [Na+].
Ion exchange reaction occurs at membrane surface

Alkaline ions will replace H+ ions completely/partially in

outer gel layer of glass membrane.
Result: pH value measured < actual pH
Usually noticeable: - pH> 12
- [Li+ /Na+] 0.1 mol/litre
Figure 2: Cross-section of glass pH membrane.
Alkaline metal cations will compete with H+for free spaces
in solvated layer.
Alkaline Error cont.

Figure 1: Deviation from linear pH

dependence due to alkaline error

Alkaline error pH value alkaline concentration

Application of Potentiometric Measurement
Clinical Chemistry
Ion-selective electrodes are important sensors for clinical samples
because of their selectivity for analytes in complex matricies.
The most common analytes are electrolytes, such as Na+, K+, Ca2+,H+,
and Cl-, and dissolved gases such as CO2.

Environmental Chemistry
For the analysis of of CN-, F-, NH3, and NO3- in water and
One potential advantage of an ion-selective electrode is the
ability to incorporate it into a flow cell for the continuous
monitoring of wastewater streams.

Potentiometric Titrations
Use a pH electrode to monitor the change in pH during the
For determining the equivalence point of an acidbase titration.
Possible for acidbase, complexation, redox, and precipitation
titrations, as well as for titrations in aqueous and nonaqueous
NO3, NH4, Cl, K, Ca, I, CN in soils, plant material, fertilizers and

Detergent Manufacture
Ca, Ba, F for studying effects on water quality

Food Processing
NO3, NO2 in meat preservatives
Salt content of meat, fish, dairy products, fruit juices, brewing
F in drinking water and other drinks.
Ca in dairy products and beer.
K in fruit juices and wine making.
Corrosive effect of NO3 in canned foods
Thank you