Dr. M.

Saqlain Tahir
Potentiometry Head of Quality Assurance
Highnoon Laboratories Limited
Electrochemistry
The relationship between chemical reactions and electricity.
• Certain chemical reactions can create electricity.
• Electricity can make certain chemical reactions happen that wouldn’t
happen otherwise.
Electrochemical Cell
It is a device for the conversion of electrical energy into chemical
energy and vice versa. It consists of two electrodes dipping into an ionic
solution and connected by an external metallic conductor.
Types
• Voltaic or Galvanic Cell
• Electrolytic Cell
Electrochemical Cells
A galvanic cell is a device where the chemical energy is converted into
electrical energy, such as dry cell or lead storage battery. In an
electrolytic cell, the electrical energy from an external source is used to
bring about a physical or a chemical change. Charging of a lead storage
battery or electrolytic purification of metals are examples where
electrical energy brings about chemical changes.
Electrode Potential
The potential difference that exists across the metal-solution interface is
known as electrode potential. If the ions in the solution are at unit
activity, the electrode potential is termed as the standard electrode
potential.

Concentration is the amount of solute dissolved per unit volume of the

solution. The effective concentration is known as activity. Both these
terms are related as
a = fc
where f is activity coefficient
EMF
It is an abbreviation for electromotive force, and is defined as the
difference of potential between the electrodes which causes the
current to flow from one electrode to the other.
Theory (Potentiometry)
When a metal M is dipped into a solution containing its own ions Mn+,
an electrode potential is established, the value of which is given by the
Nernst equation:
E = E0 – RT/nF.(lnaMn+)
Where E0 is the standard electrode potential of the metal. E is
measured by combining the electrode with the reference electrode.
The Nernst equation gives a simple relationship between the relative
potential of an electrode and concentration of corresponding ionic
species in the solution.
Principle (Potentiometer)
A potentiometer is a device which is used to measure the emf of a cell.
It operates on the Poggendorff compensation principle. The principle of
this method is to balance the unknown emf or potential difference
against a known emf, which can easily be varied. When these two emf’s
are exactly equal, no current will flow through a galvanometer placed in
the circuit. The galvanometer is therefore employed as a null
instrument.
Principle (pH meter)
A pH meter is a special type of millivolt potentiometer designed to
measure the emf of a cell in which the electrolyte contains H+ ions. The
emf (E) of a galvanic cell can be related by means of the Nernst
equation to the activity of H+ ions in the solution. The voltage produced
by the cell is converted by the potentiometer (pH meter) to a current
which is proportional to the pH of the sample. The current is translated
into a pH reading on a dial. A glass electrode is employed as a
measuring electrode and a calomel electrode is needed as a reference
electrode.
Electrochemical Cell
Potentiometry is one type of
electrochemical analysis methods.
Electrochemistry is a part of chemistry,
which determines electrochemical
properties of substances. An electrical
circuit is required for measuring
current (unit: ampere, A) and potential
(also voltage, unit: volt (V)) created by
movement of charged particles.
Galvanic cell (electrochemical cell, Fig.
1) serves as an example of such
system.
Electrochemical Cell
Electrochemical cell consists of two solutions
connected by a salt bridge and electrodes to
form electrical circuit. Sample cell on figure 1
consists of solutions of ZnSO4 and CuSO4.
Metallic Zn and Cu electrodes are immersed
in respective solutions. Electrodes have
contacts firstly through wires connected to
the voltmeter and secondly through
solutions and a salt bridge, forming an
electric circuit. Salt bridge consists of a tube
filled with saturated salt solution (e.g. KCl
solution). The ends of the tube are capped
with porous frits that prevent solutions from
mixing, but permit movement of ions.
Electrochemical Cell
Three distinct charge transfer processes are described for the system in Fig 1:
1. Electrons move in electrodes and wires from zinc electrode to copper electrode.
2. 2. Ions move in solutions:
a. In solution on the left, zinc ions move away from the electrode and sulfate ions move towards it.
b. b. In solution on the right, copper ions move towards the electrode and negatively charged ions
(sulfate) away from it.
c. c. In salt bridge positive ions move right and negative ions left. 3.
3. On the surfaces of electrodes electrons are transferred to ions or vice versa:
a. Zinc electrode dissolves: Zn → Zn2+ + 2e-
b. Metallic copper is deposited on the electrode surface: Cu2+ + 2e-→ Cu ↓
Electrochemical Cell
Three processes mentioned above are important parts of a closed electrical circuit making the flow of electrical current possible.
Potential on an electrode depends on the ions present in the solution and their concentration. This way electrochemical cells can
be used to determine ions and their concentration in solution. The dependence of potential between electrodes from
concentration of ions is expressed by Nernst equation.
E = E0 – RT/nF.(lna)
E – electrode potential,
E0 – standard potential of the electrode,
R – universal gas constant (8.314 J/(K.mol)),
F – Faraday constant (96485 C/mol),
T – temperature in kelvins,
n – charge of the ion or number of electrons participating in the reaction,
a – activity of the ions.

The Nernst temperature compensation corrects only for the electrode millivolt output change with temperature, not the actual
pH change of the buffer solution with temperature which is unique for each buffer.]
Potentiometry
Potentiometry is based on the measurement of the potential of an electrode
system (e.g. electrochemical cell). Potentiometric measurement system consists of
two electrodes called reference and indicator electrode, potentiometer and a
solution of analyte (figure 2).

Reference electrode is an electrode with potential which is

a) independent of concentration of analyte (or other) ions in solution;
b) independent of temperature.
Potential of an indicator electrode depends mainly on the concentration of the
analyte ions (in this case hydrogen ions).
Potentiometry
Potentiometric measurements enable
selective detection of ions in presence
of multitude of other substances.

In case of figure 2, the potential of the

indicator electrode is sensitive to
hydrogen ions. In a system like this,
the potential is measured in reference
to a calomel electrode, e.g. calomel
electrode functions as the reference
electrode.
How does it work?
Suppose you dip the probe in a
solution, for example, a solution
of hydrochloric acid. Hydrochloric
acid (HCl) solution contains small
hydrogen ions (H+) and big
chloride ions (Cl-) as shown in the
following diagram:
How does it work?
When the probe is immersed in
the solution, the smaller hydrogen
ions are able to penetrate the
boundary area of the glass
membrane and the larger chloride
ions remain in the solution itself.
Thus, the result is a separation of
charge as shown in following
diagram:
How does it work?
The same process happens inside
the probe which contains a
neutral potassium chloride
solution, that is, it has pH = 7 and
has a constant concentration of
hydrogen ions.
How does it work?
Now, if the hydrogen ion
concentration, or pH, in the outer
solution differs from that of the
inside solution, then a measurable
potential difference is detected and
pH is simultaneously calculated.
In our case, since HCl is acidic; it will
contain more hydrogen ion
concentration than the inside
solution. Hence, the potential
difference measured will give a pH<7
How does it work?
In case of a neutral solution, the inside and outside concentrations of
hydrogen ions will be the same and no potential difference is formed
and pH = 7 will be measured. In the case of an alkaline solution, the
hydrogen ion concentration outside will be less than the solution
inside. Hence, the potential difference measured will give a pH>7
Apparent pH
Where a pH measurement system is calibrated by use of an aqueous
buffer and then used to measure the “pH” of nonaqueous systems, the
ionization constant of the acid or base, the dielectric constant of the
medium, the liquid-junction potential (which may give rise to errors of
approximately 1 pH unit), and the hydrogen-ion response of the glass
electrode are all changed. For these reasons, the values so obtained
with solutions that are only partially aqueous in character can be
regarded only as apparent pH values.
Ideal Reference Electrode
Ideal Reference Electrode
– Has a potential that is accurately known, constant and completely
insensitive to the composition of the analyte solution

--Different types of reference electrodes are present:

Standard Hydrogen Electrode
Calomel Reference Electrode
Silver/Silver Chloride Reference Electrode
Silver/Silver Chloride Reference Electrode
A silver chloride electrode is a type of reference electrode, commonly used in
electrochemical measurements. For example, it is usually the internal reference
electrode in pH meters. The reaction is between the silver metal (Ag) and its salt —
silver chloride (AgCl, also called silver(I) chloride). The corresponding equations can
be presented as follows:
Ag+ + e- ⇆ Ag(s)
AgCl(s) + e- ⇆ Ag(s) + Cl-
This reaction is characterized by fast electrode kinetics, meaning that a sufficiently
high current can be passed through the electrode with the 100% efficiency of the
redox reaction (dissolution of the metal or cathodic deposition of the silver-ions). The
reaction has been proved to obey these equations in solutions of pH values between 0
and 13.5.
Indicator electrode
– Which is immersed in a solution of the analyte, develops a potential,
E, which depends on the activity of the analyte.
– Is selective in its response
Ideal Indicator electrode
– Responds rapidly and reproducibly to changes in the concentration of an analyte ion (or groups
of analyte ions).
--Different types of indicator electrodes are present:
Metallic Electrodes
o Metal Electrodes of the 1st Kind
o Metal Electrodes of the 2nd Kind
o Metal Electrodes of the 3rd Kind
o Redox Electrodes
Membrane Electrodes
o Ion Sensitive Electrodes (ISE)
o Molecular selective electrodes (MSE)
Salt bridge, Diaphragm
The salt bridge or diaphragm or liquid junction is an integral part of the
reference electrode. It provides the electrical connection between the reference
electrode and the sample being measured. Salt bridges have a variety of forms.
Some are highly porous, where the pores are filled with ions from the filling
solution and from the sample. Depending on the mechanical design of the
diaphragms, the movement of material from inside the reference half cell into
the porous material, and from the sample into the porous material is different.
For example using a gel-filled salt bridge only ions are permitted to flow across
the porous material and the liquid level of the reference compartment remains
constant. Other materials allow liquid to flow out of the reference compartment,
requiring periodic refilling. These types of diaphragms minimize contamination
of the reference half cell, since ions do not flow back from the sample.
Salt bridge, Diaphragm
The liquid junction is the most problematic part of the probe. If it clogs due to
sample particles going into the porous area or because crystals of the filling
solution forming inside the junction, the final reading is false or takes much
too long to stabilize. If the electrolyte level inside the reference compartment
is low, then another problem can arise where sample solution enters the
reference compartment. This dilutes the electrolyte with sample solution and
the reference potential is no longer constant. In certain cases there is
blockage due to precipitates forming inside the junction. This can occur if Ag+
ions come together with S2- ions to form Ag2S precipitate. In samples with S2-
ion, or with biological or medical samples, it is recommended to use a
reference probe with double junction, where the outer electrolyte is
absolutely free of Ag+ ions.
Salt bridge, Diaphragm
– Preventing components of the analyte solution from mixing with
those of the reference electrode
– A potential develops across the liquid junctions at each end of the salt
bridge.
– Potassium chloride is an ideal electrolyte for the salt bridge because
the mobilities of the K+ ion and the Cl- ion are nearly equal.
BASIC PRINCIPLE OF A pH METER
GLASS BULB
• A pH meter will be made up of a probe, which itself is made up of two electrodes. This probe passes
electrical signals to a meter which displays the reading in pH units. The glass probe has two electrodes
because one is a glass sensor electrode and the other is a reference electrode. Some pH meters do have
two separate probes in which case one would be the sensor electrode and the other the reference
point.
• Both electrodes are hollow bulbs with a silver chloride wire suspended into it. The glass sensing
electrode has a bulb made up of a very special glass coated with silica and metal salts. This glass sensing
electrode measures the pH as the concentration of hydrogen ions surrounding the tip of the thin walled
glass bulb. The reference electrode has a bulb made up of a non-conductive glass or plastic.
• When one metal is brought in contact with another, a voltage difference occurs due to their
differences in electron mobility. Similar is the case with two liquids. A pH meter measures essentially
the electro-chemical potential between a known liquid inside the glass electrode (membrane) and an
unknown liquid outside. Because the thin glass bulb allows mainly the agile and small hydrogen ions to
interact with the glass, the glass electrode measures the electro-chemical potential of hydrogen ions or
the potential of hydrogen. To complete the electrical circuit, also a reference electrode is needed.
HOW IS THE pH PROBE DESIGNED??
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
innermost 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 0.1 mol/L 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 OF A pH METER
• The bulb is sealed to a thicker glass or plastic tube, and filled, for example, with a solution of HCl (0.1
mol/dm3). In this solution is immersed a silver/silver chloride electrode with a lead to the outside through a
permanent hermetic seal. The filling solution has constant Cl- concentration, which keeps the Ag/AgCl inner
electrode at fixed potential.
• The pH sensing ability of the glass electrode stems from the ion exchange property of its glass membrane.
• Glass is mostly amorphous silicon dioxide, with embedded oxides of alkali metals. When the surface of glass is
exposed to water, some Si-O- groups become protonated
• Si-O- + H3O + ≡ Si-O-H + + H2O
• The exchange of hydronium (or written as proton, H +) between the solid membrane and the surrounding
solution, and the equilibrium nature of this exchange, is the key principle of H 3O+ sensing. As with any interface
separating two phases between which ionic exchange equilibrium is established, the glass membrane/solution
interface becomes the site of a potential difference
• E glass electrode = E‘ + RT/2.303F log a(H 3O+) Where E’ represents the sum of the constant offset potentials of
the inner glass surface/solution and the two Ag/AgCl electrodes. At 30°C the potential of the glass membrane
changes by about 60 mV for each one unit of pH
Electrode storage
Objective
Ensure that the pH sensitive gel layer which forms on the pH glass
membrane remains hydrated and ion rich
Always store
 In inner electrolyte (e.g. 3 mol/L KCI)
 In buffer solutions (e.g. pH 4 or 7)
 In HCl diluted (approx. 0.1 mol/L)
Never store
Dry, in distilled water or non-aqueous solutions
Reduces lifetime
 Needs conditioning before use (costs time)
Electrode cleaning
Aqueous sample
Rinse with distilled water after every measurement (contamination of next sample)
Dip it dry with paper towel
! Never wipe it with paper towel (electrostatics)

Non-aqueous or dirty sample

First rinse with solvent to get rid of dirt which is not water soluble
Rinse with distilled water, dip it dry
Condition in aqueous solution
Electrode cleaning - diaphragm
Blocked with silver chloride (AgCl)
 With concentrated ammonia
Blocked with silver sulfide (Ag2S)
 With 8 % thiourea in 0.1 molar HCl
Blocked with proteins
 With 5 % pepsin in 0.1 molar HCl
Other junction blockages
 In ultrasonic bath with water or 0.1 molar HCl
Treat one hour, rinse with distilled water, and perform a new electrode
adjustment
Electrode Calibration
Possible errors
 Not done frequently enough
 Done at a different temperature than subsequent measurement
 Wrong or contaminated buffers used

Actions
 Calibrate at least once per day, more if high temperature fluctuations
 Make sure conditions at calibration and measurement (temperature, stirring etc.) are equal
 Always use fresh buffers – if buffers not accurate, pH calibration is not accurate and the
measurement will not be accurate
 Perform at least a two point calibration
 Make sure the calibration points frame the expected sample pH
Electrode Calibration
Significance of pH Measurement
• Large number of qualitative and quantitative analyses are carried out
a definite pH values .
• pH has a great importance in agriculture. Soils are often tested to
determine whether acidic or basic fertilizers are required for a
particular crop.
• Food preservation needs definite pH.
• It has also got a great importance in biochemical reactions such as
digestion of food, working of enzymes etc.
Titration Errors
Potentiometric Titration Curve
Potentiometric Titrator
Electrode calibration – buffer handling
• Buffers have expiry date – don’t order in bulk
• Store well sealed at room temperature
• Take out needed amount and close bottle immediately again
• Never calibrate electrode directly in the bottle
• Never re-use already used buffer solution
• Take single-use buffer sachets
→ Buffers are “testing equipment” !
Electrode calibration – indicating electrode
condition
• “Offset” value (mV) – indicates the age of electrode and provides an estimation
when the electrode need to be changed.
• Calibration Slope (%) – indicates the sensitivity of the glass membrane
 Recommended offset range at pH 7.00 is ± 30mV.
 Recommended calibration slope range is 95% - 105%.
(DIN 19263 requirements: Offset 0 ± 30 mV; Zero Point: pH0 = 7 ± 0.5 pH)
In brief
If electrode is not performing well
Membrane dehydrated, contaminated or damaged
Electrolyte contaminated, has crystallized, hasn’t been filled enough or is missing,
has too low ion concentration
Air bubbles behind the ceramic junction
Diaphragm (junction) contaminated or blocked
Electrode worn out (out of specs), is too old
Simply the wrong way
Filling hole closed during measurement
Storage in deionized water
Wipe to clean glass membrane
Calibration once a week
Temperature has no influence
Never replace electrolyte
Re-use buffers for calibration
Stir extremely fast during measurement and …

pH measurement can’t go wrong !!!! X

Links
https://www.youtube.com/watch?v=aIn4D2QXUy4
https://www.youtube.com/watch?v=PBTn4gTEbkU
https://vulms.vu.edu.pk/Courses/CHE301/Downloads/Analytical%20Chemistry%20
7e%20by%20Gary%20D.%20Christian%20(1).pdf
 EVERY ENDING IS
Thank you REALLY JUST A NEW
BEGINNING