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The formal definition of pH is the negative logarithm of the hydrogen ion concentration
i.e. pH = -log10[H]+
In practice it is the hydrogen ion activity which is measured rather than its concentration.
The potential difference between the reference and sensing electrode is measured by the
meter and converted into a pH value.
where: E = total potential (in mV) developed between the sensing and reference
electrode
Eo = standard potential of the electrode at aH+ = 1 mol/l
R = Gas constant
T = temperature °K
n = valency of ion
F = Faraday constant
aH+ = activity of the hydrogen ion in solution
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The term 2.3RT/nF is referred to as the Nernst slope. For an ideal electrode the slope at
25°C is 59.16 mV per decade change in hydrogen ion activity (see Figure 1).
450
350
S lo p e = 5 9 .1 6 m V /p H
250
Electrode potential (mV)
150
A s ym m e tr y P o in t (E o )
50
-5 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
-1 5 0
-2 5 0
-3 5 0
-4 5 0
pH
In practice the response of a real electrode does not exactly follow that predicted by the
Nernst equation and must be compensated for. During calibration the meter determines
the actual slope and asymmetry potential for the electrode in use and then matches the pH
meter to the correct characteristics of the electrode in use.
What are the acceptable ranges for the slope and asymmetry potential of a pH
electrode?
For an ideal electrode the theoretical slope is -59.16 mV/pH and the asymmetry potential
at pH 7 is 0 mV. In practice, a range of -55 mV/pH to -60 mV/pH (or 95 – 102%) and an
asymmetry potential of +/- 15 mV is acceptable.
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electrodes is a function of the pH value of a solution. Common reference systems in use
are Silver/Silver chloride/ (Ag/AgCl) and Mercury/Calomel (Hg2Cl2). The Silver/Silver
Chloride reference is far the most frequently employed because it has universal
applicability, a wide operating temperature range and is relatively non-toxic.
What does the term resistance mean in relation to pH electrodes, and why is it
important?
This is a measure of the electrical resistance of the measuring electrode of a pH electrode.
It is influenced by the chemical composition of the glass, its thickness and shape. The
resistance of pH membrane glass is important as it increases with decreasing temperature.
A change in resistance leads to a change in electrode response, in particular the higher the
resistance of the membrane the slower the electrode response is. This can result in an
electrode not being useable at a particular temperature. For example, electrodes designed
for low alkaline error at high temperatures are generally of higher than normal resistance
and should not be used at all at low temperatures. For this reason manufacturers specify
temperature ranges in which their electrodes can be used with confidence.
Why does the glass bulb at the bottom of electrodes come in a variety of shapes?
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The glass membrane on pH electrodes comes in a variety of different shapes based on the
fitness for purpose of the electrode. The most common membrane shapes in use today are
outlined below:
In practice there is a trade-off between the speed of response of the electrode and its
ruggedness, thus the application the electrode is being selected for will govern the choice
of membrane design. The classical sphere shaped membrane offers low electrical
resistance due to its large surface area but is relatively fragile. The cone shaped
membrane is seen as a universal design as it is robust, of medium resistance and is easy to
clean.
What is the difference between the various types of membrane glass for pH
electrodes?
As pH is measured in a wide variety of solutions at varying temperatures it is not possible
to formulate a single pH membrane glass which can give accurate and reliable pH
measurements in all conditions. For this reason different types of membrane glass have
been developed to give good performance in a variety of measurement conditions. The
most common membrane glass types found in Schott electrodes are as outlined below:
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solutions it has very constant measuring values and fast
response time
A Offers fast response time in drinking water, service water and
sewage, and also suitable for general applications
If the wrong membrane type is selected for a particular application it may be rendered
unusable without any obvious signs of change.
The subject of the above questions is comprehensively covered in the technical paper
entitled “The Effects of Temperature on pH Measurement” published by J. J. Barron, C.
Ashton. & L. Geary of the Reagecon Technical Services team. It includes details of
practical remedial actions which can be taken to reduce or eliminate these effects.
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Reagecon manufacture a large number of different types of pH buffers. What is the
difference between these types of buffer and what are they used for?
Reagecon manufactures the most comprehensive range of pH buffers in the world which
are designed to suit all end user requirements. The most popular pH buffer types
manufactured are outlined below:
All of these buffers are manufactured to exacting specifications and are supplied with
detailed Certificates of Analysis which shows traceability to a N.I.S.T. SRM.
In addition to the type of buffer, different pack options are available to suit all needs:
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If a different buffer to that specified by the manufacturer is used for calibration this will
result in calibration errors. If you have any doubt on the best buffers to use for your pH
meter then the Reagecon Technical Services team will be happy to advise you.
• Electrodes should never be allowed to run dry because this will create static charges
on the glass membrane resulting in a very sluggish response.
• Cleaning of the electrode between buffers and sample or from sample to sample
should be carried out by a jet of water from a wash bottle, followed by careful rinsing
with the buffer or sample to be measured. For very accurate work it is recommended
to repeat the zero calibration after slope adjustment.
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To have full confidence in your pH measurements it is essential that you can demonstrate
that each component of the measuring system is functioning to specification. If any
component of the measurement system does not meet this requirement, questionable
results will be obtained. For pH measurement, the following must be verified:
• The pH meters ability to correctly process both pH and temperature inputs correctly
• The pH electrodes ability to generate the correct output signal
• The temperature sensors ability to generate the correct output signal
Routine calibration using pH buffers will not demonstrate all of the above, this is why
annual calibration should be performed.
What is the difference between Instrument Calibration and Validation, and which
one do I need?
It is a regulatory requirement for pharmaceutical companies to perform Instrument
Validation on new equipment, and regular Requalification on existing equipment. In
brief, Instrument Validation is a fully documented process that ensures the instrument is
working correctly. It demonstrates that the measuring instrument is working correctly and
hence has no detrimental effect on the quality of the analytical results. For industries
which are not as heavily regulated annual calibration (as previously described) would be
sufficient to demonstrate that the instrument is working correctly.
Electrode Selection
My pH electrode has a hole with a detachable cover at the top of the glass section.
What is the purpose of this hole?
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This hole serves two purposes - to allow replacement of the electrolyte and also to allow
pressure to be equalised during measurement. If the hole is covered during measurement
then the electrolyte will not be able to travel through the electrode's diaphragm into the
sample thus the electrode accuracy and responsiveness will be reduced.
Some electrodes have a hole at the top for replacing the electrolyte, but others don’t.
Why is this?
This electrode contains the electrolyte in a gel format. It is non-refillable, and thus is low
maintenance. Gel filled electrodes are less accurate than liquid filled electrodes due to a
slower response resulting from liquid potentials. In addition, if the electrolyte becomes
poisoned it cannot be changed, and the electrode must be replaced.
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How can the pH of a non-aqueous liquid be measured?
The pH scale is defined in terms of hydrogen ion activity in aqueous solution and is not
therefore strictly applicable to pH measurement in non-aqueous systems. If
measurements are to be performed in non-aqueous liquids, there are several problems
which may be encountered. The low ionic strength and low conductivity of some non-
aqueous solvents may result in high noise or drift. In addition, the glass membrane of the
pH electrode may become dehydrated from immersion in the non-aqueous solvent and
thus lose its ability to respond to H+ ions.
The ideal way to minimize these effects is to use a separate reference and measuring
electrode with an auxiliary salt bridge containing a non-aqueous electrolyte filling
solution .If this is not available a standard pH electrode may be used providing the
following steps are performed:
• Select an electrode with a low resistance membrane and a free flowing diaphragm
such as the Schott Blueline 13.
• Use an electrode containing a non-aqueous filling solution (such as saturated
Lithium Chloride in Ethanol for non-polar solvents or Lithium Chloride in Glacial
Acetic Acid for polar solvents).
• Soak the electrode in the non-aqueous solvent for ten minutes after
standardisation and before use in the sample.
• Between successive measurements, the electrode should be rinsed with the non-
aqueous solvent used to dissolve the sample.
• If the reading begins to drift after considerable time in a non-aqueous solvent, the
pH glass bulb must be rehydrated by immersion in an aqueous buffer.
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What does the term drift mean in relation to pH measurement, and why should I be
concerned about it?
The subject of the above questions is comprehensively covered in the technical paper
entitled “Care, Maintenance and Fault Diagnosis for pH Electrodes” published by J. J.
Barron, C. Ashton. & L. Geary of the Reagecon Technical Services team. It includes
details of practical remedial actions which can be taken to improve the accuracy of pH
measurements and extend the working life of pH electrodes.
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