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Measurement Hints
Tips for Care
Calibration
System Check
Editorial
Dear Reader,
The determination of pH value, conductivity and related parameters such as ion
concentration, resistivity, and salinity, are frequent and ordinary tasks in many labs.
Samples may originate from many different areas. Sample composition, i.e. solvent and
major components, can differ considerably and cover a wide concentration range. The most
common solvent of pH and conductivity samples is water. However, other solvents are used
as well. In addition, user needs in the lab reach from simple, manual determination to fully
automated analysis systems including data gathering via software and other features.
To meet this array of requirements, a big number of methods exist and a wide variety of
instrument solutions have been developed by meter and sensor manufacturers. Standard
methods are in use for numerous applications. For special needs many dedicated solutions
exist as well. However, the vast number of possibilities can make selecting the right
instrument and/or sensor cumbersome.
This guide provides some insights into meter and sensor characteristics and performance,
enabling users to make better decisions and find the right instrument and electrode. Tips and
hints for sensor maintenance and care help to exhaust their usable life and achieve reliable
results. This wealth of information helps finding the most suitable instrument solution but as
well measuring successfully each time.
METTLER TOLEDO
Disclaimer
This guide represents selected, possible application examples. Examples have been tested with all possible care
in our lab with the analytical instrument mentioned in the applications. The experiments were conducted and the
resulting data evaluated based on our current state of knowledge.
However, this guide does not absolve you from personally testing its suitability for your intended methods,
instruments and purposes. As the use and transfer of an application example are beyond our control, we cannot
accept responsibility.
When chemicals and solvents are used, the general safety rules and the directions of the producer must be observed.
Content
Content
1
Calibration
10
pH Electrode Troubleshooting
12
More Information
16
METTLERTOLEDO
[1]
[2]
This InLab storage solution can be ordered from METTLER TOLEDO (30111142)
This thiourea solution can be ordered from METTLER TOLEDO (51340070)
METTLERTOLEDO
Any Pro type InLab sensor InLab Micro Pro, Science Pro, Expert Pro has
integrated temperature probes, eliminating worries over wrong temperature
settings or not capturing temperature.
For sensors without an integrated temperature probe, using a separate temperature probe is recommended.
[1] [3] This regeneration solution can be ordered from METTLER TOLEDO (51350104)
[2]
This pepsin solution can be ordered from METTLER TOLEDO (51340068)
METTLERTOLEDO
METTLERTOLEDO
Clean with RNase and DNase cleansers and autoclave to eliminate biohazard
The pH electrode models InLab Power, Power Pro, Viscous and Viscous Pro can be sterilized by autoclaving.
By cleaning the sensors with RNase and DNase decontamination solutions first, the potential for biological
contamination is s ignificantly reduced.
METTLERTOLEDO
A pH electrode needs to be calibrated regularly. It is recommended that you do this at least once a day before
you start measuring. In a calibration the slope and offset of an electrode are determined. The theoretical slope
and offset are given by the Nernst equation:
E = E0 + 2.3RT / nF * log [H3O+] = E0 + 2.3RT / nF * pH
Slope = 2.3RT / nF
Offset = Should be 0 mV at pH 7.00
The calibration is necessary to adjust the slope and offset of an electrode to their true values for the measuring
system in question. The calibration curve is then used to correlate the measured mV values of the electrode to
the pH value of the solution measured.
mV
Theoretical behaviour
(Slope 59.16 mV /pH, offset: 0 mV)
Offset correction
Slope and offset correction +
pH
Calibration
2. Calibration
Figure 5: Correlation between mV value measured by pH electrode and pH value in sample. Curves shown are for the theoretical behavior,
for offset compensated behavior and slope & offset compensated behavior.
Since an electrode is characterized by both its zero point and its slope, it is advisable to do a minimum of a
two point calibration for reliable measurements and better precision. When measurements are performed over a
large range of pH values it is recommended that one takes at least 3 calibration points. Most pH meters can do
35 point calibrations.
It is important to note that one should only measure samples within the chosen region of calibration.
When calibrating an electrode, most pH meters request that you input the type of buffers which will be used.
There are several manufacturers of buffer solutions and the specifications of the most commonly used brands
normally already come programmed as tables in the pH meters. These tables cover groups of buffers for a
range of temperatures. In this way a whole group can be chosen at once allowing the temperature dependence
of the individual buffers used for calibration, to be taken into account. If no internal or external temperature
sensor is used, ensure that you calibrate and measure at the same temperature. In this case remember to
manually input the temperature to allow the meter to perform the buffer temperature correction.
The buffers which are used for the calibration are very accurate solutions with a guaranteed value and precision.
To keep the buffer solutions suitable for calibrations for as long as possible after opening it is advisable that you
follow these guidelines:
Mark the date of first use on the bottle of the buffer solution.
Keep the buffer solution bottles tightly sealed at all times and use the decanted buffer immediately.
Never return used buffer back into the original bottle or mix calibration standards from different manufacturers.
Ensure that no contaminants enter the buffer solution bottle and always keep the bottle sealed.
Store the calibration standard at ambient temperature.
Do not store the bottles of buffer solution in direct sunlight.
Clean the electrodes before calibration and do not calibrate directly in the original buffer solution bottle.
METTLERTOLEDO
Calibration
Never use a calibration standard with an expired use by date or that you suspect is contaminated.
Replace the buffer solution with a new bottle after it has reached its expiry date.
Always repeat the calibration after cleaning your electrode, after electrode maintenance, regeneration or long
term storage of an electrode, as all these factors have an influence on the pH electrode potential.
10
11
12
14
13
pH 6
3 or more P
recommended e.g. pH 4, 7, 10
pH 3
2P
recommended
e.g. pH 4 and 7
pH
1
1P
e.g.
pH 7
METTLERTOLEDO
3.2 Application
Are you using the right electrode for your application? There are different types of
pH electrodes for special applications: non-aqueous, low conductivity, TRIS etc. To
make sure that you are using the right electrode visit the METTLER TOLEDO Sensor
ProductGuide at: www.electrodes.net
3.3 Operator
It is sometimes worthwhile to check the obvious:
Is the unit properly grounded or plugged into the wall outlet?
Are the electrodes plugged into proper terminals and seated firmly?
Is the meter properly calibrated with the correct buffers?
Before taking a measurement, check that the wetting cap has been removed and that
the side filling aperture is open. Remember to rinse the electrodes before measuring
a different buffer or sample.
3.4 pH Meter
Test the pH meter with the shorting clip (standard delivery) or Test Plug Set. If this
plug does not set the potential to 0 mV, the meter may be the problem. In this case
call METTLER TOLEDO Service.
3.5 Buffers
Ensure that you are using the correct buffers in the correct sequence. Always use
fresh buffers. Check expiry date.
METTLERTOLEDO
10
3.7 Electrodes
Visual inspection of the electrode can often provide important clues about the cause
of the problem:
Filling solution
Ensure that the electrolyte level is above the internal elements.
Empty, rinse and refill the electrode reference chamber.
Ensure that you are using the correct electrolyte as written on the electrode shaft or in the operating
instructions, and that the electrolyte fill port is open.
Air bubbles
Check for air bubbles inside the electrode. If some are present remove them by gently shaking the electrode
downward or in the case of electrodes with gel electrolyte placing the electrode upright in warm water.
Blocked junction
see next chapter 4
METTLERTOLEDO
11
White
pH Electrode Troubleshooting
4. pH Electrode Troubleshooting
The electrode
the key toanalysis.
successful
Since
the only
part
The electrode
is the key is
to successful
Since analysis.
the electrode
is thethe
onlyelectrode
part of the is
analytical
instrument
of
the
analytical
instrument
that
is
in
direct
contact
with
the
sample,
its
selection
that is in direct contact with the sample, its selection and maintenance (and therefore sensitivity) has the
and maintenance (and therefore sensitivity) has the strongest influence on precise
strongest
on precise
and accurate
measurements.
However,that
an electrode
thatcorrectly
has beenselected
correctly
andinfluence
accurate
measurements.
However,
an electrode
has been
selectedand
andthat
that has
been
working
properly
may
nevertheless
suddenly
start
performing
badly.
In
this article
has been working properly may nevertheless suddenly start performing
article
wereasons
will help
identify
possible
reasonsforfor
this and
we will badly.
help youInto this
identify
possible
for thisyou
and to
suggest
a number
of procedures
restoring
the
suggest
a number
of procedures for restoring the electrode to its original
electrode
to its original
performance.
performance.
2. Glass membrane
a) Diagnosis
One symptom
may very often have various causes. The following table will
a) Diagnosis
help you to find out what caused your electrode to fail with regard to the pHOne
symptom
may very often have various causes. The following table
sensitive
glass
membrane:
will help you to find out what caused your electrode to fail with regard
to the pH-sensitive glass membrane:
Figure
What can
Fig. 17:What
canbe
befixed?
fixed?
METTLERTOLEDO
12
pH Electrode Troubleshooting
Cause
Ageing of
membrane
glass
Scratches
on
membrane
Broken
membrane
or shaft
Gel layer
destroyed or
dehydrated
Dry storage
of
electrode
Calcium on
glass
membrane
(whitish
lm)
Oil, fat or
tar residues
(visible?)
Deposits of
unknown
substances
(visible?)
Due to
High
temperature,
age of
sensor
Abrasion,
solid
particles,
incorrect
cleaning
Mechanical
or
temperature
shock
Ion decient
media, nonaqueous
applications
Wrong
storage
Measurement media
Measurement media
Measurement media,
no cleaning
Procedures
for restoring
the
electrode
Regeneration
(see next
page)
Sensor
cannot be
repaired
Sensor
cannot be
repaired
Rehydration
with
electrolyte or
tap water
Rehydration
with
electrolyte
or tap water
Dip sensor
in conc.
acetic acid
until
deposits are
dissolved.
Afterwards
regeneration
Clean sensor
with
degreasing
agent, then
rinse with
water. If
necessary,
regeneration.
.
Clean sensor
with suitable
cleaning
agent. If
necessary,
regeneration.
Symptom
Reduced
slope
(>80% <90%)
Very small
slope
(<80%)
Slow
response
Fluctuation
of reading
Zero point
shift
Reading
jumps up
and down
Explanations:
Highly probable
Probable
Possible
b) Regeneration procedure
A reduced calibration slope as a result of changes in the gel-layer on the glass membrane can very often be
observed with older electrodes or electrodes that have been stored dry. Similar effects are noticeable when an
electrode is used for non-aqueous applications because the gel-layer is dehydrated. The pHsensitive glass
membrane is reactivated using a regeneration solution. This solution is a mixture of hydrochloric (HCl) and
hydrofluoric acids (HF).
Since these
acids are extremely aggressive, make sure that you observe all the necessary
7.11.2012
METTLERsafety
TOLEDO
precautions,
e.g.
wear
protective
goggles,
a
laboratory
coat
and
chemical-resistant
gloves!
Page 2 / Version 1
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METTLERTOLEDO
13
pH Electrode Troubleshooting
Since these acids are extremely aggressive, make sure that you observe all the necessary safety
precautions, e.g. wear protective goggles, a laboratory coat and chemical-resistant gloves!
the volume
of solution
to a minimum
by using
a
KeepKeep
the volume
of solution
to a minimum
by using
a small
small
acid-resistant
vessel.
Dip
the
tip
of
the
electrode
into
acid-resistant vessel. Dip the tip of the electrode into the
the regeneration solution for 5 to 15 minutes. The
regeneration
solution for 5 to 15 minutes. The maximum
maximum immersion point is level with the upper shoulder
immersion
point
is level
with(see
the Fig.
upper
thesensor
pHof the pH-sensitive
glass
2).shoulder
Never dipofthe
shaft
into
the
solution
because
the
hydrofluoric
acid
will
sensitive glass (see Fig. 8). Never dip the sensor shaft into
damage
it.
the solution because the hydrofluoric acid will damage it.
Maximum
immersions level
Thencondition
rinse theitelectrode
thoroughly
and solution
for approximately
an with
hourwater
in a buffer
of
pH7.
Finally,
place
the
sensor
overnight
in
reference
condition it for approximately an hour in a bufferthe
solution
electrolyte
specific
to
that
sensor.
of pH7. Finally, place the sensor overnight in the reference
electrolyte specific to that sensor.
3.
Reference diaphragm
Diagnosis
4.3 a)Reference
diaphragm
Faulty electrodes often have a clogged diaphragm. In most cases, the diaphragm is visibly discolored.
a) Diagnosis
Some are black, others are gray or just an off-white color. Sometimes the discoloration is so faint that it is
only
visible when
ceramic
tube is diaphragm.
viewed from In
themost
side through
the diaphragm
glass. A gradual
change
from
Faulty
electrodes
oftenthehave
a clogged
cases, the
is visibly
discolored.
Some
white
on
the
inside
to
off-white
or
gray
on
the
outside
can
be
seen.
Silver
sulfide
makes
the
diaphragm
are black, others are gray or just an off-white color. Sometimes the discoloration is so faint that it is only visible
appear black. Proteins can cause a whitish discoloration that is hardly visible. This form of contamination
whenrarely
the ceramic
tube
from
the side
throughinto
the the
glass.
A gradual
change from
white on the inside
occurs just
onistheviewed
surface.
It usually
penetrates
pores
of the diaphragm.
Lipophilic
to off-white
or gray
onasthe
cancan
becreate
seen. aSilver
sulfide makes the
appear black.
substances,
such
fatsoutside
and oils,
thin, non-permeable
layerdiaphragm
over the diaphragm
that isProteins
often can
invisible.
cause
a whitish discoloration that is hardly visible. This form of contamination rarely occurs just on the surface.
It usually penetrates into the pores of the diaphragm. Lipophilic substances, such as fats and oils, can create a
b)
Cleaning procedures
thin, non-permeable layer over the diaphragm that is often invisible.
The following table gives tips and hints on how to clean ceramic diaphragms. Some of these measures
can be used
on the outside as well as on the inside of the electrode. The same applies of course to Redox
b) Cleaning
procedures
or
separate
reference
whichon
have
contaminated
ceramic
diaphragm.
The following table giveselectrodes
tips and hints
howa to
clean ceramic
diaphragms.
Some of these measures
can be used on the outside as well as on the inside of the electrode. The same applies of course to Redox
or separate reference electrodes which have a contaminated ceramic diaphragm.
7.11.2012
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METTLER TOLEDO
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METTLERTOLEDO
14
White Paper
pH Electrode Troubleshooting
Type of
contamination
Silver sulfide
Cleaning agent
Reaction time
Remarks
Thiourea
5 60 mins.
Approx. 12 hrs.
Chromic-sulfuric acid
mixture
Approx. 30 mins.
> 1 hr.
Approx. 20 mins.
Approx. 30 mins.
Calcium, scale
Acetic acid
Approx. 30 mins.
Soaps, tensides
Approx. 12 hrs.
Proteins
Lipophilic
substances
Despite all the corrective procedures mentioned above, it is not always possible to repair a faulty electrode.
Damage that has occurred to the wiring or casing of an electrode during use, is irreparable. In such cases the
Despite all the corrective procedures mentioned above, it is not always possible to repair a faulty
electrode must be replaced.
electrode. Damage that has occurred to the wiring or casing of an electrode during use, is irreparable. In
such cases the electrode must be replaced.
7.11.2012
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METTLER TOLEDO
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METTLERTOLEDO
15
More Information
5. More Information
5.1 Guides
A Guide to pH Measurement, Mettler-Toledo AG, 51300057, (2013)
Guide pour les mesures de pH, Mettler-Toledo AG, 51300185, (2013)
Anleitung zur Messung von pH, Mettler-Toledo AG, 51300058, (2013)
A Guide to Conductivity Measurement, Mettler-Toledo AG, 30099121, (2013)
Guide des mesures de conductivit, Mettler-Toledo AG, 30099123, (2013)
Ein Leitfaden fr Leitfhigkeitsmessungen, Mettler-Toledo AG, 30099122, (2013)
Gua para la medicin de la conductividad, Mettler-Toledo AG, 30099124, (2013)
A Practical Guide for Life Scientists pH and Conductivity, Mettler-Toledo AG, (2014)
Selected Water Analysis Methods, Application Brochure 37, Mettler-Toledo AG, 51725072 (2007)
5.2 Webinars
We provide web-based seminars (webinars) on different topics. You can participate in on-demand webinars
at any convenient time and place.
Live webinars offer the added benefit of allowing you to ask questions and discuss points of interest with
METTLER TOLEDO specialists and other participants.
www.mt.com/webinars
METTLERTOLEDO
16
www.mt.com
For more information