Module 5:

Electrochemical sensors

By,
Prof Manisha Bhendale
pH measurement:(Potential of hydrogen):
“pH can be measured by measuring the voltage produced between two special electrodes
immersed in the liquid solution. One electrode, made of a special glass, is called the
measurement electrode. It's a job is to generate a small voltage proportional to pH (ideally 59.16
mV per pH unit).”
A very important measurement in many liquid chemical processes (industrial, pharmaceutical,
manufacturing, food production, etc.) is that of pH: the measurement of hydrogen ion concentration in
a liquid solution.
A solution with a low pH value is called an “acid,” while one with a high pH is called a
“caustic.” The common pH scale extends from 0 (strong acid) to 14 (strong caustic), with 7
in the middle representing pure water (neutral):
What is pH?
pH is defined as follows: the lower-case letter “p” in pH stands for the negative
common (base ten) logarithm, while the upper-case letter “H” stands for the element
hydrogen. Thus, pH is a logarithmic measurement of the number of moles of
hydrogen ions (H+) per liter of solution.
The logarithmic pH scale works like this: a solution with 10-12 moles of H+ ions per
liter has a pH of 12; a solution with 10-3 moles of H+ ions per liter has a pH of 3. While
very uncommon, there is such a thing as an acid with a pH measurement below 0 and
a caustic with a pH above 14. Such solutions, understandably, are quite concentrated
and extremely reactive.

pH measurement:
Principle of pH measurement is based upon the property of H+ ions which reacts
with the special gas electrode and produces a potential between the solution and
electrode.
This potential difference is measured with a suitable circuit.
❖ pH Measurement specifies the degree of relative acidity or alkalinity of an aqueous
solution at a given temperature.
❖ It is generally measured using a pH Meter.
❖ All living beings depend on a proper pH level to sustain life and hence pH
Measurement becomes an important aspect of our lives.
❖ pH Measurement specifies the degree of relative acidity or alkalinity of an aqueous
solution at a given temperature.
❖ pH is represented in the form of an equation as the negative logarithm of the
Hydrogen ion concentration.
❖ In an aqueous solution, a pH of 7 describes a neutral solution because the
activities of Hydrogen (H+) and Hydroxide ions (OH-) are equal.
❖ The solution is described as acidic when the pH is below 7,as the activity of
Hydrogen ion is dominant when compared to Hydroxide ion. Hence a solution is
termed more acidic when the Hydrogen ion activity increases and the pH value
decreases.
❖ The solution is described as basic (or alkaline) when the pH is above 7, as the
activity of Hydroxide ion is dominant when compared to Hydrogen ion.
The pH Scale of Common Products:
pH Electrodes:
➢ While pH can be measured by color changes in certain chemical powders (the “litmus
strip” is a familiar example from high school chemistry classes), continuous process
monitoring and control of pH requires a more sophisticated approach.
➢ The most common approach is the use of a specially-prepared electrode designed to
allow hydrogen ions in the solution to migrate through a selective barrier, producing a
measurable potential (voltage) difference proportional to the solution’s pH:
➢ The design and operational theory of pH electrodes is a very complex subject,
explored only briefly here. What is important to understand is that these two
electrodes generate a voltage directly proportional to the pH of the solution.
➢ At a pH of 7 (neutral), the electrodes will produce 0 volts between them. At a low pH
(acid) a voltage will be developed of one polarity, and at a high pH (caustic) a voltage
will be developed of the opposite polarity.
https://www.allaboutcircuits.com/textbook/direct-current/chpt-9/ph-measurement
➢ Two electrodes are used for the pH measurement. One is reference
electrode and other is measurement electrode.
➢ Measurement electrode must be constructed of special glass. Almost
all pH measurement are best suited with glass electrode.It consists
of thin ion selective membrane of soda lime glass sealed at the end
of the glass tube that has no ion selective properties.
➢ Reference electrode is made from a chemical solution of neutral (7)
pH buffer solution (usually potassium chloride) .
➢
State & explain the types of pH measurement electrodes?

Reference electrode Measuring electrode glass electrode

Reference electrodes :
Ag/AgCl Electrode: This consist of silver wire or plate coated with a silver chloride (AgCl) in
contact with salt bridge of potassium chloride(KCl) saturated with AgCl.
Hg/HgCl Calomel electrode: Inner tube contains Hg/HgCl in which platinum wire is immersed.The inner
tube also consists of a glass wool at bottom where small hole is provided for bridging. Salt bridge of KCl is
used at outer tube.
Measuring glass electrode: The electrode consist of thin ion selective membrane of soda lime
glass,sealed at end of glass tube that has no ion selective properties. The tube contains internal
reference solution & internal reference electrode immersed in it.The ref. Electrode is Ag/AgCl
Combined electrode: The design involves reference electrode & measuring glass electrode
combined in one design.This is much easier to handle than two separate electrodes so much
popular.
pH measurement: refer the link
https://electricalfundablog.com/ph-measurement-working-principle-applications
Actual arrangement:
➢ pH Measurement is obtained precisely using a pH Meter.
➢ It has few key components namely Measuring Electrode, Reference Electrode, Temperature Sensor and the Sample
Solution being measured.
➢ The pH Meter measures the voltage of an electrochemical cell and based on the Temperature Sensor determines
the pH of a solution.
➢ Off late, in most of the pH Meters the electrodes and the Temperature Sensor are fabricated into a single body and
are called as Combination Electrodes. Fig. 3 shows pH Measurement using Measuring Electrode made of glass,
Reference Electrode, Temperature Sensor and Liquid junction.
➢ The overall potential or the voltage is the algebraic sum of the potentials of the Measuring Electrode, Reference
Electrode and the Liquid Junction.
➢ The Reference Electrode provides a stable voltage as it has a fixed concentration of Potassium Chloride solution
which is a neutral solution.
➢ On the contrary, the potential of the Measuring Electrode depends only on the pH of the solution.
➢ The potential difference (voltage) between a glass membrane of Measuring Electrode and a Reference Electrode
which is dipped in the Sample Solution to be tested is measured.
➢ When the two Electrodes are dipped in the Sample Solution, ion-exchange process occurs where in some of the
Hydrogen ions move towards the outer surface of the Measuring Electrode and replace some of the metal ions
inside it.
➢ Similarly, some of the metal ions move from the Glass Electrode into the Sample Solution.
➢ The sensitivity of the Reference Electrode potential to changes in pH is negligible or it is unaffected by changes in
pH and hence provides a stable voltage.Ion-exchange process also takes place on the inner surface of the Glass
Electrode from the sample solution.
➢ This creates a potential difference (Hydrogen- ion activity) between them. The Liquid Junction potential is usually
small and relatively constant which mainly depends on the concentration of the ions in the sample solution. All
three potentials are summed up and measured by High Impedance Voltmeter.
The output of the Impedance Voltmeter is Voltage readings and it has to be calibrated to get precise pH
Measurement. Calibration is done by dipping the Measuring Electrode into Buffer Solution of known pH
which helps in interpreting millivolt reading as pH measurement of the Sample Solution at the given
temperature.
Applications of pH Measurement:

● pH Measurement is very crucial in Agriculture industry for soil evaluation. Major crops require
alkaline environment and hence pH Measurement becomes necessary.

● It is also used in Food industry especially for dairy products like cheese, curds, yogurts, etc.
● It becomes mandatory for chemical and pharmaceutical industries.
● It becomes a significant factor in the production of detergents.
● pH level monitoring is essential in water treatment plants and RO water purifiers.

Advantages of pH Measurement:
● pH Measurement is inexpensive and robust.
● Pocket size pH Meters are user friendly.
● Readings are accurate and precise.

The disadvantages are: Temperature impacts the output readings.

● pH Measurement using glass electrodes must be clean as deposition on the electrodes affects the
readings.
pH mater..This is how it looks like…..
 What is conductivity and why should it be measured?
➢ Electrical conductivity is an inherent property of most materials and ranges from extremely
conductive materials, such as metals, to non-conductive materials, like plastic or glass. In
between the two extremes are aqueous solutions, such as sea water and plating baths.
➢ In metals, the electrical current is carried by electrons while in water it is carried by charged ions.
➢ In both cases, the conductivity is determined by the number of charge carriers, how fast they
move, and the capacity of the carrier.
➢ Thus for most water solutions, the higher the ion concentration from dissolved salts, generally
the higher the conductivity. Conductivity will increase with an increase in ion concentration until
the solution becomes too crowded, thus restricting the freedom of the ions to move.
➢ Conductance is defined as the reciprocal of resistance and is measured in Siemens (S), which was
formerly referred to as mho (ohm spelled backwards).
➢ Conductivity is an inherent property of any given solution.A measurement results in the
conductance of the sample and it is converted to conductivity. This is done by determining the cell
constant (K) for each setup using a known conductivity standard solution.
Conductivity = (Cell conductance X Cell constant)
Reference:
https://www.thermofisher.com/in/en/home/life-science/lab-equipment/ph-electrochemistry/conductivity-measurement-testin
g.html
Conductivity Measurement:
➢ The electrical conductivity of a solution of an electrolyte is
measured by determining the resistance of the solution
between two flat or cylindrical electrodes separated by a
fixed distance.[3]
➢ An alternating voltage is generally used in order to minimize
water electrolysis.[citation needed] The resistance is measured
by a conductivity meter. Typical frequencies used are in the
range 1–3 kHz.
➢ The dependence on the frequency is usually small,[4] but
may become appreciable at very high frequencies, an effect
known as the Debye–Falkenhagen effect.
➢ A wide variety of instrumentation is commercially
available.[5] Most commonly, two types of electrode sensors
are used, electrode-based sensors and inductive sensors.
➢ Electrode sensors with a static design are suitable for low
and moderate conductivities, and exist in various types,
having either two or four electrodes, where electrodes can
be arrange oppositely, flat or in a cylinder.
➢ Conductivity sensors are typically calibrated with KCl
solutions of known conductivity.
Resistance, R, is proportional to the distance, l, between the electrodes and is inversely proportional to the cross-sectional area of the
sample, A (noted S on the Figure above). Writing ρ (rho) for the specific resistance, or resistivity.

In practice the conductivity cell is calibrated by using solutions of known specific resistance, ρ*, so the individual quantities l and A need
*
not be known precisely, but only their ratio.[10] If the resistance of the calibration solution is R , a cell-constant, C = l⁄A, is derived.

The specific conductance (conductivity), κ (kappa) is the reciprocal of the specific resistance.

Conductivity is also temperature-dependent. Sometimes the ratio of l and A is called as the cell constant,
denoted as G*, and conductance is denoted as G. Then the specific conductance κ (kappa), can be more
conveniently written as
The specific conductance of a solution containing one electrolyte depends on the concentration
of the electrolyte. Therefore, it is convenient to divide the specific conductance by concentration.
This quotient, termed molar conductivity, is denoted by Λ
m,

Which is alos called as cell constant,

Cell constant is measured by ..

1) Measuring resistance when cell is completely dipped in solution,whose
conductivity is accurately known.
2) Comparing the resistance measured with that obtained in cell of known constant
by dipping both the cells in the same solution at the same temperature.

Three types of cells used are:

1) Two electrode
2) Four electrode
3) Electrodeless, where only first one is used practically.
Conductivity Applications: Many industries and applications rely on
measuring conductivity, these include:
● Water treatment and industrial applications (drinking water and
wastewater)
● Hospital equipment
● Boiler water
● Brewing beverages such as beer and wine
● Natural waters
● Aquaculture applications
● Environmental applications
● Agricultural applications
● Hydroponics applications
● Oceanographers measuring seawater
Thank you…..