Determine the pH of the solution by pH meter

General description:
pH:
Negative log of H+ ion concentration
Methods to measure pH:
 pH strip
 pH kit (a dye solution is added in a test solution and then colour change
is compared with known strip)
 pH meter
pH meter is a scientific instrument that measures the concentration or the
activity of hydrogen ions in water based solutions including its acidity or
alkalinity expressed as pH. It measures the difference in electrode potential
between a pH electrode and reference electrode, and so the pH meter is
sometimes referred to as ‘potentiometric pH meter’. pH meters are usually
used to measure the pH of liquids, though special probes are sometimes used
to measure the pH of semis-solid substances.
Principle:
pH measurement is based on the use of a pH sensitive electrode (usually glass),
a reference electrode, and a temperature element to provide a temperature
signal to the pH analyzer. The pH electrode uses a specially formulated, pH
sensitive glass in contact with the solution, which develops a potential (voltage)
proportional to the pH of the solution. The reference electrode is designed to
maintain a constant potential at any given temperature, and serves to
complete the pH measuring circuit within the solution. It provides a known
reference potential for the pH electrode. The difference in the potentials of the
pH and reference electrodes provides a millivolt signal proportional to pH. The
potential difference that develops between the two electrodes is measured as
voltage, as defined by Nernst equation:
2.303 RT
>> V =E constant +
F
pH

where
V = voltage of the completed circuit
E constant = potential of reference electrode
R = the gas constant
T = the absolute temperature
F = the Faraday constant
Components of pH meter:
Indicator electrode:
Consist of silver (Ag) wire coated with silver chloride (AgCl) immersed into an
internal solution of 0.1 mmol/K HCL and placed into a tube containing special
glass membrane tip.
The membrane is only sensitive to H+ ions.
When the pH electrode is placed into a test solution movement of H+ ions near
glass tip produces a potential difference between internal and test solution
which is measured as pH.
It is connected to positive (+ve) terminal of voltmeter.
Reference electrode:
Commonly used is calomel which is a paste of mercurous chloride (HgCl 2) in
contact with mercury (Hg) in an electrolyte solution of KCl.
At constant electrolyte concentration and temperature a stable voltage is
produced. A cable is connected to negative (-ve) terminal of voltmeter.
Two types of reference electrodes are used:
Ag/AgCl
Hg/HgCl2
 Voltmeter:
Electromotive force (e.m.f) produced is in millivolts (mV).
Zero potential suggest that each half-cell is generating same voltage.

Combination Electrode:
Has both indicator and reference electrodes.
Consist of Ag/AgCl internal reference electrode sealed in a narrow glass tip. The
reference electrode is an Ag/AgCl wire wrapped around indicator electrode.
Outer glass is filled with KCl. The solution to be measured must cover glass tip
completely.

Working:
Calibration:
It is a method to standardize a pH meter.
  Turn the temperature control, if available, to the temperature of the standard calibration
buffers and the test solutions.
 Clean the electrode tip by pressing with tissue paper.
 Immerse the electrode in a standard buffer. Common standard buffers are with pH 4,7, and
10 with an accuracy of ±0.02 pH unit. The standard buffer should have a pH within two
pH units of the expected pH of the test solution. The bulb of the electrode must be
completely covered with solution.
 Turn the pH meter to “on” or “read” and adjust the meter with the “ calibration dial”
(sometimes called “intercept”) until the proper pH of the standard buffer is indicated
on the dial.
 Turn the pH meter to the standby position.
 Remove the electrode and again rinse with distilled water and carefully blot dry with
the tissue.
 Immerse the electrode in a standard buffer of different pH and turn the pH meter to
“read”. The dial should read within ±0.05 pH unit of the known value.
 If it does not adjust to the proper pH then again check the first standard pH buffer.
 If there is an increase in pH, stabilize it with adding 0.1N HCl which lowers the pH.
 If there is a decrease in pH, stabilize it with adding 0.1N NaOH which increases the
pH.
 Add acid or alkali drop by drop and always stir the solution with glass rod after each
addition.
 Clean the electrode and immerse it in the test solution.
 Record the pH of the test solution.
 Calibration should be done daily because glass electrode dose not produce
electromotive force (e.m.f) over longer periods of time.

Usage and care:

 Read the pH when voltage appears.

 Always keep the electrode dipped in 3 mol/KCl solution, never leave the
electrode dry.
 Be cautious about the electrode level displayed on the screen. It
symbolizes the fitness of electrode. Any kind of unusual appearance can
cause pH fluctuation.
 Buffer solutions should always be clear without any turbidity or mycelia
growth. Same is the case if the buffer is used to protect electrode.
 Always prepare buffer solutions every month for calibration.
 Always prepare buffer solutions in sterile water.
 Never mishandle the electrode like using it for stirring the solutions.
 Always use sterile water to clean the electrode after dipping it in
solutions.
 Never place the electrode in solutions which are in extreme temperature
conditions.
 No hurry should be there for reading the pH.
 Do not forget to make entry with appropriate comments in the log book.
 The equipment and its premises should be clean if there is any spill.
 As with all delicate equipment, the pH meter and electrode must receive
proper care and maintenance.
 All electrodes should be kept clean and stored in solutions suggested by
manufacturers.
 Glass electrodes are fragile and expensive, so they must be handled with
care.
 If pH measurements of protein solutions are often taken, a protein film
may develop on the electrode, it can be removed by soaking in 5%
pepsin in 0.1M HCl for 2 hours and rinsing well with water.
 The pH instrument should always be set on “ standby “ when the
electrode is not in a solution.
Advantages:
 It is an accurate and sensitive method.
 pH of highly coloured and turbid solutions can be measured by this
method.
 pH of semisolids like cheese can be measured.
 pH meter can be used again and again.
 It is not affected by factors like slight change in temperature or presence
of any oxidizing or reducing agent.
Disadvantages:
 .Deposits on the electrode membrane can interrupt the processes
 The pH meter is often needed to calibrate.
 A special buffer solution is required to calibrate it.
 The pH calibration may be influenced by temperature and carbon dioxide
absorption.
 There is a possibility of breaking due to fragile glass electrodes.

Viva and practical questions

Q1. What is zero calibration (asymmetry potential adjustment)?
Ans. The interior of a glass electrode is filled with a pH 7 solution. If the glass
electrode is immersed in a pH 7 solution, the potential difference should be
0mV because identical buffer solutions are present on both sides of the
membrane of the glass electrode.
In practice, a potential develops due to the strain caused during glass
production, shape, glass compositions, or other factors. This is called the
“asymmetry potential”. The asymmetry potential also occurs due to
contamination of the internal solution of the reference electrodes, dryness of
or clogging in the liquid junction, etc. in addition to the glass electrode.
To eliminate this asymmetry potential, a pH sensor is zero calibrated using the
pH 7 standard solution.
Q2. What tips can you give for pH buffer use?
Ans. These solutions of known pH value allow the user to calibrate the pH
meter to make accurate measurements.
For the highest accuracy:
 Standardisation should be performed with fresh buffer solutions.
 Buffers used should bracket the range of pH for the sample being tested.
 Buffers should be at the same temperatures the samples. (For example;
if all your samples are at 50°C using a beaker in a water bath).
Q3. What is temperature compensation?
Ans. The pH value of a solution is temperature dependent as temperature
affects the ion activity in a solution. As a result, pH readings should be
compensated for temperature to standardize the readings. pH meters will have
either manual temperature compensation (MTC) or automatic temperature
compensation (ATC). The meter with MTC need to enter a temperature reading
in manually and the ATC meters will take a temperature reading and adjust the
pH reading automatically.
Q4. Why is pH measurement important?
Ans. pH measurement is important for various industrial and scientific
applications such as water treatment, food and beverage processing and
chemical manufacturing.