pH Measurement

BITS Pilani
Note to students

These slides should only be considered as supporting material. To have a

thorough understanding of the topic, these must be accompanied by
textbook, reference materials and lecture notes.

2 BITS Pilani, Deemed to be University under Section 3, UGC Act

pH Measurement

• pH measurement is the quantification of hydrogen ion activity in a liquid solution.

• It is one of the most common forms of analytical measurement in industry, because pH has a
great effect on the outcome of many chemical processes.
• pH measurement and control plays a crucial role in may industries, such as,
o Food processing,
o water treatment,
o pharmaceutical production,
o steam generation (thermal power plants),
o and alcohol manufacturing.
• pH is also a significant factor in the corrosion of metal pipes and vessels carrying aqueous
(water-based) solutions, and hence pH monitoring and control can save a lot of capital
investment as well.

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A typical continuously stirred tank type
bioreactor

By GYassineMrabetTalk - Own work, CC BY-SA 3.0,

https://commons.wikimedia.org/w/index.php?curid=8301774
BITS Pilani, Deemed to be University under Section 3, UGC Act
pH Measurement: Colorimetric pH
measurement…
• Simplest measurement technique
• Some chemical compounds dissolved in an aqueous solution will change color if the pH
value of that solution falls within a certain range.
• Litmus paper is a common laboratory application of this principle, where a color changing
chemical substance infused on a paper strip changes color when dipped in the solution.
• Comparing the final color of the litmus paper to a reference chart yields an approximate pH
value for the solution.

Hydrangea plant: An organic pH indicator

BITS Pilani, Deemed to be University under Section 3, UGC Act
pH measurement: Potentiometric
methods…
• Color change is not suited for continuous pH
measurement in industrial applications.
• The most common method for pH
measurement in industrial application is
electrochemical.
• Special pH-sensitive electrodes are inserted
into an aqueous solution, which generate a
voltage dependent upon the pH value of that
solution.
• The electrochemical pH measurement is
based on the Nernst equation, which
describes the electrical potential created by
ions migrating through a permeable
membrane.

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH measurement: Potentiometric
methods…

2.303𝑅𝑇 𝐶1
𝑂𝑟 𝑉= log
𝑛𝐹 𝐶2

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH measurement: Potentiometric
methods…
• In case of pH measurement, the Nernst
equation describes the amount of
electrical voltage developed across a
special glass membrane due to
hydrogen ion exchange between the
process liquid solution and a buffer
solution inside the bulb formulated to
maintain a constant pH value of 7.0
Selectively
pH.
permeable glass !!
• Special pH-measurement electrodes are
manufactured with a closed end made
of this glass, a small quantity of buffer
solution contained within the glass
bulb.
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pH measurement: Potentiometric
methods…

pH electrode

• The Nernst voltage developed by glass pH electrode

is an indication of pH of the solution.
BITS Pilani, Deemed to be University under Section 3, UGC Act
pH measurement: Potentiometric
methods…
Reference electrode

• In order to establish a complete circuit from the

glass membrane to the voltmeter, we must create
a zero-potential electrical junction with the
process solution.
• To do this, we use another special electrode
called a reference electrode immersed in the
same liquid solution as the pH measurement
electrode.

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH measurement: Potentiometric
methods…

Typical industrial pH measurement unit

Typical industrial pH measurement units use

combination electrode, which combines both the
glass measurement electrode and the porous
reference electrode in a single unit.

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pH Measurement: Typical installation

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH Measurement: Potentiometric
methods
• The voltage produced by the pH measurement assembly is quite modest.
• Suppose, a solution whose pH is 6.0 is to measured using a pH measurement assembly, then,
•
∵ 𝑝𝐻 = − log10 𝐻 +

∴ 𝐻 + = 1 × 10−6 M
Using this concentration, we can find the output voltage, which will be.

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH Measurement: Potentiometric
methods
• Astounding rangeability: Due to the logarithmic nature of the Nernst equation.
• However, the disadvantage of high rangeability is the potential for large pH measurement errors
if the voltage detection within the pH instrument is even just a little bit inaccurate.
• The problem is made even worse by the fact that the voltage generation circuit (pH
measurement assembly) has an extremely high impedance due to the presence of the glass
membrane.
• The pH instrument measuring the voltage produced by a pH probe assembly must have an input
impedance that is orders of magnitude greater yet, or else the probe’s voltage signal will
become “loaded down” by the voltmeter and not register accurately.

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH Measurement: Potentiometric
methods
• Very high impedance of
voltage generation assembly.
• To reduce any loading effect
the voltage measurement or
circuit must have even higher
input resistance.

• The problem can become

severe because of capacitance
effects present in the
connecting cable.

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH Measurement: Potentiometric
methods

• Use of voltage buffer can reduce the time constant value significantly.

BITS Pilani, Deemed to be University under Section 3, UGC Act

pH Measurement: Potentiometric
methods

• Inclusion of RTD and pre-amplifier

can further enhance the performance
of pH probe assembly.

BITS Pilani, Deemed to be University under Section 3, UGC Act