The Theory of pH Measurement

What is the exact meaning of the term pH?

pH as a term was coined by Sorensen in 1909. He described the concentration of
hydrogen ion as a logarithmic scale which he called “Pondus Hydrogeni” or the exponent
of hydrogen. pH is a quantitative unit of measure which describes the degree of acidity or
alkalinity of a substance. It is measured on a scale of 0 to 14. The term pH is derived
from “p” the mathematical symbol of the negative logarithm, and “H” the chemical
symbol of Hydrogen.

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.

How are pH values measured?

pH is a potentiometric measurement where the electrode used produces an electrical
signal which the pH meter converts to a pH reading The signal produced and measured is
a voltage and since voltage is a potential difference, two potentials are needed to make a
measurement:

1. The sensing electrode provides a potential proportional to the logarithm of the

hydrogen ion activity in the sample.

2. The reference electrode ideally provides a stable and consistent potential

independent of the activity of the sample.

The potential difference between the reference and sensing electrode is measured by the
meter and converted into a pH value.

How does a pH meter measure the response of a pH electrode?

The potential difference developed between the reference electrode and sensing electrode
is dependant on the activity of the hydrogen ions in solution. For an ideal electrode the
response is defined by the Nernst equation:

E = Eo – 2.3 (RT/nF) log aH+

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

Figure 1. Slope of an ideal electrode @ 25°C

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 does the term asymmetry potential mean?

For an ideal electrode the potential difference between the reference and measuring
electrode is 0mV at pH 7. As the ideal electrode doesn’t exist the deviation of a few mV
at pH 7 that is found with real electrodes is called the asymmetry potential, Eo. In
practical terms it is a measure of the performance of the reference electrode - if the result
is outside of +/- 15mV this is indicative of problems with the reference electrode such as
contaminated electrolyte or reference element poisoning.

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.

What is a combination electrode?

All pH sensors consist of a measuring glass electrode and reference electrode. A
combination electrode is an electrode which contains both the reference and measuring
electrode in the one body.

What is the function of the reference electrode?

The reference electrode provides a constant potential regardless of the composition of the
solution it is placed in. The voltage difference between the reference and measuring

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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.

What exactly is the function of the diaphragm on a pH electrode, and why is it

important?
The diaphragm on a pH electrode allows a flow of electrolyte from the reference solution
into the solution being measured. This completes the electrical circuit between the
reference and sensing electrode and gives the potential difference which is measured by
the pH meter. The type of diaphragm used will influence the outflow of electrolyte into
the sample, which will in turn effect the response speed of the electrode. The common
diaphragm types are listed below along with their inherent properties. For most common
applications a platinum diaphragm is the one of choice.

Diaphragm Resistance Outflow rate sat. Application

Type (approx.) KCl @ 25°C
Platinum 0.5 kΩ 0.1ml/hr Normal applications or
extremes of conductivity
Ceramic 1 kΩ 0.05ml/hr For general measurements in
aqueous solutions where
conductivity is greater than
500µs/cm. Unsuitable for high
salt content.
Ground Joint or 0.2 kΩ 0.5 – 2ml/hr Non-aqueous, high salt, poorly
Sleeve conducting solutions that
require easy cleaning
(pastes/emulsions) etc; low
ionic strength.
Annular Gap 0.1 kΩ N/A Low maintenance gel filled
electrodes

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:

Membrane type Shape Property Application

Sphere Low resistance Common applications

Dome High resistance, shock Automatic cleaning

proof, applications
easy clean
Flat High resistance, shock pH measurement on
proof, surfaces (e.g. skin,
easy clean paper)
Cylinder Medium resistance, Fermenter electrodes
shock proof

Spear High resistance, shock Suitable for sticking in

proof semi-solid media (e.g.
cheese, meat)
Cone Low resistance, robust, Universally applicable
easy clean

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:

Membrane glass type Properties

L Suitable for wide application area, has low impedance and thus
gives rapid response time over wide temperature range
H Optimised for use in alkaline range and high temperature
applications up to 135°C. Also has very low alkaline error (Na+
error).
S This type will bear rapid temperature changes. In hot alkaline

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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.

Does temperature have any effect on pH measurement?

What practical steps can I take to reduce the effects of temperature on pH

measurement?

Does Automatic Temperature Compensation (ATC) compensates for sample

measurements taken at different temperatures?

What does ATC actually do?

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.

What does the term junction potential mean?

This is the portion of the total observed potential difference between the measuring and
reference electrode that is formed at the liquid / liquid junction between the reference
electrode filling solution and the test sample. The contribution of the liquid junction
potential to the measured potential should be kept as small and as constant as possible.
This can be achieved by careful selection of electrode, and good probe maintenance.

What affect does junction potential have on pH readings?

The flow rate of electrolyte from the reference electrode into the sample is affected by the
design of the electrode diaphragm. Low or irregular flow rates may cause variation in the
liquid junction potential which will result in erroneous readings. This is why it is
important to select the correct electrode for the application of interest.

What is meant by the response time of an electrode, and why is it important?

The response time of an electrode is the length of time necessary to get a stable reading
when the electrode is moved from one solution to another of different pH or temperature.
Response time is dependent on the electrode type, the measuring sample, temperature, the
magnitude and direction of concentration change and the presence of interfering
substances. A slow response time can be indicative of the incorrect selection of electrode
for the intended application.

Good Measurement Practice

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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:

Buffer type Description

pH buffer @ 20°C Value assigned at 20°C to ±0.01pH units
pH buffer @ 25°C Value assigned at 25°C to ±0.01pH units
Technical Buffers Manufactured in accordance with DIN
19266 and tested at 25°C to ±0.02pH units
Professional Range Value assigned at 20°C as per N.I.S.T and
at 25°C as per DIN 19266
Buffer capsules Value assigned at 25°C to ±0.02pH units

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:

Pack option Uses/Advantages

500ml, 1L & 5L Suitable for wide range of uses
Colour Coded Buffers Ease of identification
Twin Neck Bottle Ideal for field work as there is no need for a
separate measuring container. Also avoids
possibility of contaminating bulk solution
“Bag In Box” Available in 5L or 10L size, ideal for large
volume users
Buffer Capsules Ideal for users who perform calibration
infrequently or where storage is an issue

Does it make any difference which pH buffer I use to calibrate my pH meter?

Most modern pH meters are supplied with the facility for automatic buffer recognition.
The manufacturer will have programmed in a pH versus temperature profile into memory
for a specific type of buffer such as DIN or NIST (see table below)

DIN 19266 buffers @25°C NIST buffers @ 20°C

1.679 ± 0.010 1.677 ± 0.010
3.776 ± 0.010 3.788 ± 0.010
4.005 ± 0.010 4.001 ± 0.010
6.865 ± .0.010 6.879 ± 0.010
7.413 ± 0.010 7.429 ± 0.010
9.180 ± 0.010 9.225 ± 0.010
10.012 ± 0.010 10.062 ± 0.010
12.454 ± 0.050 12.627 ± 0.050

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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.

Should I stir my sample when taking a pH measurement?

It is not strictly necessary to stir samples for pH measurement. Although stirring the
solution ensures a quicker response, if the buffer solutions are stirred, then the sample
should also be stirred. It is important that the stirring is carried out at the same speed for
both samples and buffers. By stirring at a uniform rate this ensures a representative
sample measurement is obtained (this is particularly important for colloidal or particulate
samples) and also improves electrode response time. Electrodes with ceramic diaphragms
suffer from interference under stirring. The platinum diaphragm on the other hand does
not suffer from this interference and is thus the diaphragm of choice for most common
applications.

What value pH buffers should I use to calibrate my pH meter?

For proper calibration, buffer solutions of carefully selected accuracy and pH range are
required. The calibration should be performed using two buffers whose values bracket the
expected value of the samples being measured. In practice many pH meters are equipped
with auto buffer recognition - this requires the use of the buffer values specified by the
meter manufacturer. It is essential that the difference between the two calibration buffers
should be no more than 2 – 3 pH units apart. This represents 2 – 3 decades of difference
in pH value (i.e. a 100 to 1,000 times increase in H+ ion concentration).

What practical steps should be performed when calibrating a pH meter?

When carrying out the calibration the following points should all be borne in mind

• 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.

Why should control standards be used when measuring pH?

For confidence in pH measurement control standard should be run regularly as a check on
the functioning of the measurement system. If a control sample is run after calibration
and the expected result obtained this will give the user a 99% confidence level in the
calibration of the meter, and any results obtained for subsequent sample measurements.
In a situation where multiple users are performing pH measurements the use of a control
sample will provide confidence in the results being obtained from the different operators.
The control buffer selected for use should be within the calibration range of the meter.

What do I need to do to check that my pH meter is functioning correctly?

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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 does annual calibration involve?

To fully demonstrate that all components of the pH measuring system are functioning
correctly, the following steps should be performed:
• Certified, traceable electrical simulators and standards should be used to verify that
the pH meter is processing input signals correctly.
• The performance of the temperature probes should be compared to a certified
reference thermometer
• The pH meter and electrode should be calibrated using certified, traceable pH buffers.
• The correct performance of the pH electrode should be verified using certified,
traceable control standards.
For most pH users it is not practical to purchase and maintain a certified traceable pH
simulator, as it is expensive. Reagecon’s Technical Services Department can provide a
calibration service to customers that meets all their requirements, be it Instrument
Calibration or Validation.

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.

Reagecon’s Technical Services Department has developed calibration and validation

protocols for a wide range of pH instruments. This service can be performed at the
customers’ premises, or alternatively the instrument can be sent to Reagecon for
calibration in our purpose-built Metrology Laboratory.

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.

What applications should gel filled electrodes be used for?

Gel filled electrodes are generally supplied with plastic bodies. They are thus more
rugged than liquid filled glass electrodes, hence they are commonly used with portable
meters.

Measuring the pH of water from a water purification system can be problematic.

Why is this?
The objective of a water purification system is to produce a finished product of low ionic
strength. This also means that there is low hydrogen ion concentration present, which can
result in slow response times and inaccurate pH results if using a general-purpose pH
electrode. The problem can be overcome by selecting an electrode that has the following
characteristics:
• A diaphragm with a high outflow rate of electrolyte.
• An A glass membrane (gives a short response time in low ionic strength media).

The Schott Blueline 13 electrode combines both of these features in a laboratory

electrode and is thus ideal for this application.

What is the alkaline error in pH measurement?

In strongly alkaline solutions measurement errors can appear due to a contribution to the
potential from alkali ions - Lithium (Li+) and Sodium (Na+) ions in addition to that of the
hydrogen ions. Na+ and Li+ ions interact with the glass membrane and can partially or
completely replace the H+ ions present. The resulting low hydrogen ion activity results in
the observed pH reading being more basic than the true value. This effect occurs in
solutions with a pH value > 11 and increases with increasing temperature. The magnitude
of the alkali error depends on the concentration of the interfering ion with respect to the
H+ ion concentration. Membrane glasses with large alkali errors have only a short service
life in the presence of high concentrations of alkali metal ions

How can the pH of a strong alkaline solution be measured accurately?

If you need to perform measurements in solutions containing high concentrations of
alkali metal ions it is advisable to use a special membrane glass type (e.g. Schott
membrane type H used in the H62 electrode) when the pH value exceeds pH 11.

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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.

What working life can I expect from a pH electrode?

The working life of a pH electrode is heavily dependant on the application, and how it is
maintained. A well-maintained pH electrode will function for 6 to 24 months in most
typical applications. However, the life span of an electrode will be greatly reduced by
exposure to high temperatures, high process pressure, or by exposure to aggressive media
(such as HF or very caustic applications) which can result in damage to the membrane or
reference system. As the membrane on a pH electrode ages the speed of response reduces
decreases until it becomes unacceptably slow.

Care & Maintenance

How should I store my pH electrodes when not in use?

Why should I store electrodes in Electrode Storage Solution?

How should I clean my pH electrode?

How should I clean my electrode between pH measurements?

How can pH electrodes be rejuvenated?

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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.

What is the minimum level of filling solution to use in a refillable pH electrode?

The filling solution level must be higher than the sample level to maintain a uniform flow
of filling solution. A level of at least 2cm above sample height is recommended.

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