Working Principle of pH meter and

construction of pH electrodes
 Ph Meter:
A pH meter is an instrument used to measure hydrogen ion activity in solutions - in other words,
this instrument measures acidity/alkalinity of a solution. The degree of hydrogen ion activity is
ultimately expressed as pH level, which generally ranges from 1 to 14.

This pH measurement is directly related to the ratio of hydrogen ion concentration and hydroxyl
ion concentration ([H+] and [OH-], respectively). The general breakdown of pH levels is listed
below:

 Neutral solution: pH = 7
 Acidic solution: pH < 7
 Basic solution: pH > 7

A neutral solution will show a pH of 7 due to the equal activities of hydrogen and hydroxide
ions. Acidic solutions exhibit pH readings below 7 (higher hydrogen ion activity compared to
hydroxide ion activity), and basic (or alkaline) solutions exhibit pH levels above 7 (hydroxide
ion activity is greater than that of hydrogen ion).

How does a pH meter work?

A pH meter is consisted of three different parts:
 an internal electrode
 a reference electrode
 a high input impedance meter.
Glass probe often contains the two electrodes
 Internal electrode
 Reference electrode.
The internal electrode is a Silver wire covered with Silver Chloride (Ag/AgCl wire), and
reference electrode is often made up of the same materials. Inside the probe is a buffer solution at
pH of 7. Measured pH is the difference in [H +] between the reference buffer inside the probe and
the sample solution.
The pH measurements are made by comparing the pH reading of a sample solution to that of a
reference solution with defined pH, such as buffers. Therefore, it is important to calibrate the
instrument with appropriate buffer solutions before making any measurements.
The figure below is a simple depiction of a glass electrode used with pH meters.

Principle of pH Meter:
Working of pH meter is wholly based on the ion exchange between the sample and the glass
electrode’s inner solution, which generates electrical voltage. The result of the principle of pH
meters is based on the hydrogen ion concentration and the relation between electric voltage and
the pH reading.

Electrodes are typically made of glass because part of pH meter maintenance is keeping the
probe hydrated so that it does not degrade. A pH electrode consists of

 A reference junction
 A glass membrane
 An electrode body
 A reference electrode
 A reference electrolyte

The glass membrane in a pH probe has a buffer solution that allows hydrogen ions to enter the
membrane, and the noted differences create voltage potential. The electrodes inside the probe
measure this voltage potential that is calculated to be the pH of the solution.
 Working Principle of pH Meter:

Ph meter is 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 containing a potassium chloride solution 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.

Design of pH Probe:

pH probe is a combination electrode, which combines both the glass and reference electrodes into
one body. The combination electrode consists of the following parts :

 A sensing part of electrode, a bulb made from a specific glass

 Internal electrode, usually silver chloride electrode or calomel electrode
 Internal solution, usually a pH=7 buffered solution of 0.1 mol/L KCl for pH electrodes
 Reference electrode, usually the same type as 2
 Reference internal solution, usually 0.1 mol/L KCl
 Junction with studied solution, usually made from ceramics or capillary with asbestos or quartz
fiber.
 Body of electrode, made from non-conductive glass or plastics.

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.

SILVER CHLORIDE ELECTRODE:

 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:

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
 pH METER WORKING:

 pH meter measures the potential difference and its changes across the glass membrane. The
potential difference must be obtained between two points; one is the electrode contacting the
internal solution. A second point is obtained by connecting to a reference electrode, immersed in
the studied solution. Often, this reference electrode is built in the glass electrode (a combination
electrode), in a concentric double barrel body of the device.

The potential difference relevant to pH measurement builds up across the outside glass/solution
interface marked.

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 (2)

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 H3O+
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

Eglass electrode = E ‘ + RT/2.303F log a(H3O+)

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.

Parts of Glass Electrode

Resources:

https://microbeonline.com/ph-meter-parts-principle-and-applications/

https://www.azolifesciences.com/article/What-is-a-pH-Meter-and-How-Does-it-Work