BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY

CHEM 115
Chemistry-I

Assignment No: 1
Name of the Assignment: Working principle,
Construction, Calibration, Advantages, Disadvantages of
pH Electrodes

Date of Submission: 23.01.2023

Submitted by:
Name: MD. Shihab Uddin
Student ID:2116024
Level/Term: 1/1
Department of Water Resources Engineering

Submitted to:
Dr. Chanchal Kumar Roy
Assistant Professor
Department of Chemistry
 pH ELECTRODES
Working Principle Of pH Electrodes:

pH Measurement specifies the degree of relative acidity or alkalinity of an

aqueous solution at a given temperature. Theoretically, pH is derived from the
word “Pondus Hydrogenii” which means “Potential Hydrogen” or Power of
Hydrogen.
Generally, 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 electro chemical 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.

The working of pH meter is based on Nernst equation. Nernst equation derives

the relation between the electric voltage and ion concentration. The Nernst
equation derived for H+ ion concentration is the basis of pH meter. The working
principle of pH meter is the potentiometry. The pH meter consists of glass (also
called as indicator electrode) and reference electrode. The glass electrode
consists of glass membrane, which is sensitive to hydrogen ion concentration
of test sample solution. And the glass electrode potential varies from sample to
sample[𝐸𝑥 ]. The reference electrode is standard and has constant potential[𝐸𝑠𝑡𝑑 ].
The reference electrode does not respond to test sample solution. The pH
meter measures and compares the potential difference between both glass and
reference electrodes.

∆𝑬 = 𝑬𝒙 − 𝑬𝒔𝒕𝒅
Here,

∆𝐸 = potential difference between both glass and reference electrodes.

𝐸𝑥 = glass electrode potential
𝐸𝑠𝑡𝑑 = reference electrode potential

Using the Nernst equation, the potential difference is used to measure the
hydrogen ion concentration indicating the pH of given solution. Due to the
potential difference between two electrodes, the electron flows and generates
current. This generated current is measured by voltmeter. The relationship
between the potential difference, generated current and pH has been derived.
The potential difference of 1 pH is 59.16mV at 25° C and hence when there is
difference of one pH unit, there will be change in voltage by 59.16mV. This
relationship is employed in measuring the pH.

𝑬𝒄𝒆𝒍𝒍 −𝑬𝒐
pH = ……..…at 𝟐𝟓𝒐 𝑪
𝟎.𝟎𝟓𝟗
Here,

𝐸𝑐𝑒𝑙𝑙 = ∆𝐸
𝐸° = it′ s a constant and is different for the pH meter cells

The acidic solution is rich in H+ ion concentration. When pH probe is dipped in

an acidic solution, the H+ ion moves close to the glass membrane of the
sensitive glass bulb (external side of the bulb). Similar reaction occurs inside
the bulb, which is filled with buffer solution of neutral pH. This neutral buffer
solution has constant number of Hydrogen ions. The H+ ions present inside the
bulb also moves close to glass membrane (internal side of the bulb). Hence, this
causes the difference in the concentration of hydrogen ion or degree of
hydrogen ion activity across the membrane causing difference in the potential
(voltage). When the hydrogen ion concentration inside the glass bulb is less
than the outside solution (test solution), then the given solution is acidic and
hence the pH is lower than 7.

When the Hydrogen ions concentration across the membrane is same then it is
called as neutral pH and the pH is equal to 7. If the concentration of hydrogen
ion of inside the bulb than outside solution then the given solution is alkaline
and the pH is more than 7. The pH meter measure the potential difference at
both the electrodes and calculate the pH as per the Nernst equation.

Construction Of pH Electrodes:

Modern pH meter is a combined type, in which glass and reference electrode

are placed into a rod like structure. The combined electrode consist of
following parts-
 Figure: Combined Electrode of pH meter

Glass Electrode:
This is the simplest and most common electrode. It consists of a sturdy glass
tube with a thin glass bulb(i) welded to it. Inside there is a known solution of
potassium chloride (KCl) buffered to a pH of 7.0. The silver electrode(ii) with a
silver chloride tip makes contact with the internal solution(iii). To minimize
electronic interference, the probe is protected by a blade protector, which is
often located inside the glass electrode.

Reference Electrode:

It consists of a cavity containing mercury and calomel (Hg2Cl2) that are in

contact with each other. The contact between the mercury and the calomel is
carried out by means of a platinum wire, while the small inner chamber is
surrounded by a solution of saturated KCl.

The contact between the saturated KCl and the measured solution, the liquid
connection, is made through a porous ceramic pin. The potential produced at
this point is constant and is determined by the solubility product of the
calomel and the concentration of the KCl solution.

The potential of the reference electrode(iv) system is defined by the reference

electrolyte(v) and the reference element (e.g., silver chloride). Here it is
important that the reference electrolyte has a high concentration of ions, which
results in a low electrical resistance. Filling hole(vii) is used for refilling the
electrolyte. Junction(vi) is made from ceramic junction also called as
diaphragm that allows the contact of sample solution and reference electrolyte.
It does not disturb the electric connection between both the electrodes.
Calibration:

Before calibration, we have to prepare pH meter. The steps are-

1. Turn on pH meter. Before begin to calibrate and use the pH meter, first
need to turn it on and allow adequate time for the meter to warm up.
This should generally take around 30 minutes, but check the pH meter's
operating manual for exact times.
2. Clean electrode. Take the electrode out of its storage solution and rinse
it with distilled water under an empty waste beaker. Once rinsed, blot dry
with Kimwipes or Shurwipes, which are available at most office supply
stores.
 Be sure to rinse electrode in a waste beaker that is different from the
beaker where calibration will happen.
 Avoid rubbing the electrode as it has a sensitive membrane around it.
 If the electrode found particularly dirty, consult operating manual for
recommended cleaning solutions.
3. Prepare buffers. It will be generally needed more than one buffer for
calibrating a pH meter. The first will be a “neutral” buffer with a pH of 7,
and the second should be near the expected sample pH, either a pH of 4
or 9.21. Buffers with a higher pH (9.21) are best for measuring bases,
whereas buffers with a low pH (4) are best for measuring acidic samples.
Once buffers have been chosen, allow them to reach the same
temperature as the pH meter because pH readings are temperature
dependent. Pour buffers into individual beakers for calibration.
 Check with pH meter manufacturer, or current educational or
professional institution, about acquiring pH buffer solutions.
 Buffers should be kept in a beaker for no longer than two hours.
 Discard the buffer after finishing. Do not return it to its original
container.
After preparing pH meter, we can proceed to calibrate pH meter. To calibrate
pH meter we have to-

1. Place electrode in the buffer with a pH value of 7 and begin

reading. Press the “measure” or calibrate button to begin reading the pH
once the electrode is placed in the buffer.
 Allow the pH reading to stabilize before letting it sit for approximately 1-
2 minutes.

2. Set the pH. After having a stable reading, set the pH meter to the value of
the buffer's pH by pressing the measure button a second time. Setting the
pH meter once the reading has stabilized will allow for more accurate
and tuned readings.
  Although not necessary, when you stire your buffer before measuring be
sure to stir all other buffers and samples in the same way.
3. Rinse electrode with distilled water. Rinse and pat dry with a lint-
free tissue, like Kimwipes or Shurwipes, in between buffers.
4. Place electrode in the appropriate buffer for sample and begin
reading. Press the measure button to begin reading the pH once
electrode is placed in the buffer.
5. Set the pH a second time. After reading has stabilized, set the pH meter
to the value of the buffer's pH by pressing the measure button.
6. Rinse the electrode. Distilled water can be used to rinse. Use a lint-
free tissue, like Kimwipes or Shurwipes, in between buffers to dry the
electrode.

Now the pH meter is ready to use. The procedure to use it-

1. Place electrode in sample and begin reading. Once electrode is

placed in the sample, press the measure button and leave the
electrode in sample for approximately 1-2 minutes.
2. Set pH level. Once the reading has stabilized, press the measure button.
This is the pH level of ample.
3. Clean electrode after use. Rinse electrode with distilled water and blot
or dab dry with a lint-free tissue. pH meter may be stored once clean and
dry.
 Consult operation manual for optimal storage practices for specific pH
meter.

Advantages Of pH Electrodes:
 This is a quick and easy process for measuring pH.
 This gives precise results and provides an accurate pH value.
 It is used for various types of applications.
 Covers the acid and alkaline pH range (pH 01 to 14).
 The user can calibrate it with the standard buffer solution (pH 07, pH 04
and pH 09.20).
 An added advantage of the pH meter is that it is portable.
 Compared to reading a color strip or a pH indicator, a pH meter provides
very accurate results.
 A small, battery-powered meter is a great option when using it at a
specific site.
Disadvantages Of pH Electrodes:

 Deposits on the electrode membrane can disrupt processes.

 The pH meter is often necessary to calibrate it.
 A special buffer solution is needed to calibrate it.
 pH calibration can be influenced by temperature and carbon dioxide
uptake.
 There is a risk of breakage due to brittle glass electrodes.