FAQs for Seminar Toolbox

Frequently Asked Questions

pH, Conductivity, DO, and Ion Measurements
General Topics

In the following our experts give the answers to the most commonly asked questions about pH-,
conductivity-, dissolved oxygen (DO)- and ion (ISE)- measurement, with special regard of
METTLER TOLEDO equipment for electrochemical analyses.

1. FAQ's: pH Applications

1. How to measure pH in textiles

We do not have application notes on this. From customers feedbacks we understand that
the process is similar in most companies: A small amount of water is used to moisture the
textile and the pH is then measured with a flat surface membrane (e.g. InLab Surface).
The main problem with this application is the following: textile itself is a solid and does not
have a pH value. What is measured with the electrode is the pH value of the liquid (water
to wet the textile plus outflowing reference electrolyte) which is increased or decreased by
the textile due to its ability to dissolve or absorb protons.

As a consequence, the pH is different if the amount of water changes or the pH value of the
reference electrolyte (which is definitively not constant but normally between 6 and 7). And
the result of the measurement cannot be interpreted as an absolute value but must be used
to compare with any theoretical values and limits. The pH value would be different if the pH
was not measured on the surface but in a solution where a piece of textile was mixed
before. Following exactly a certain SOP is crucial for useful and comparable results.

2. How to understand the selectivity coefficient (Kpot) for interfering ions in ISE
measurement

Ion Selective Electrodes measure the particular ion that needs to be determined while
simultaneously sensing other ions. The ion that is to be determined is referred to as the
"determinant" and other ions to which an electrode responds are known as "interferents" or
interfering ions. It is possible to calculate the preference of an electrode for the determinant
over the interferent. This is called the selectivity of the electrode. The preference, expressed
as a ratio, is called the selectivity coefficient (KPot). Each electrode has its own set of
selectivity coefficients (one for each interfering ion).

For example (K+-ISE sensor):

KPot (K+, Na+) = 2.6 x 10-3

Where K+ is the determinant and Na+ the interferent

 In this particular case, the preference for K+ (potassium) over Na+ (Sodium) for this
electrode is 1:3.2 x 10-5 or 31'623:1. This means that the electrode is 31'623 times
more selective to K+ than to Na+.

3. What is the dissolved oxygen amount in water at ambient pressure in mg/L?

It can be explained by understanding the principle of air calibration. Water absorbs gases -
oxygen, nitrogen, air etc. - the amount of gas that can be absorbed depends on the
pressure of the gas in contact with the water as well as of the solubility of the gas in the
water. When the pressure of dissolved oxygen in the water equals the pressure of oxygen in
the air we say the water is 100% saturated. For a certain pressure, the solubility of a gas
in water depends on the temperature of the water.

4. How to measure pH in strong acidic of alkaline solutions

The following measures must be taken:

- For acidic samples below pH 1:

 Use a sensor with an HA glass.

 Always calibrate and measure at the same temperature (preferably room temperature).
 Rinse the sensor thoroughly after each measurement
 Only compare pH values of similar samples and measured under the same conditions.
 If absolute pH values are required, take the decreased activity of the acid into consideration
(what you measure is the activity (aH+ ). To get the real H+ concentration (CH+) multiply
the measured activity with the activity coefficient (gH+) of H+ . g must be calculated for
every type of solution. A reasonable approach to calculate g is the Debye and Hückel
theory.
 Use 1 M HCl p.a. to prepare calibration solutions.
 When measuring outside the calibration range, be aware of the fact, that the error increases
the more distant the next calibration point is.

- For alkaline samples above pH 13:

 Use a sensor with an HA glass.

 Take the sodium and lithium concentration into consideration (e. g.: when preparing the
calibration buffer use a solution with the same alkali ion content like your sample)
 Avoid stirring and prolonged contact of the sample with air (CO2 uptake).
 Reduce exposure time of the sensor to alkaline solutions to a minimum
 Rinse the sensor thoroughly after each measurement
 Always calibrate and measure at the same temperature (preferably room temperature).
 Only compare pH values of similar samples measured under the same conditions.
 Use 1 M NaOH p.a. to prepare calibration solutions.
 When measuring outside the calibration range, be aware of the fact, that the error increases
from the more distant the next calibration point is.
5. What are the reason for a pH electrode not to be TRIS buffer compatible

TRIS and free silver ion (Ag+) tend to react and form very stable complexes that precipitate and can
clog ceramic junctions of pH sensors (just like Ag+-protein complexes)

That's why TRIS-containing solutions require sensors with open or sleeve diaphragm or with the
ARGENTHAL system together with a silver ion trap.

Cleaning of sensors contaminated by Ag+-TRIS precipitations is difficult.

Whereas the Ag+-protein complexes can be resolved using the proteinase pepsin in 0.1 M HCl,
there is no specific treatment to remove the Ag+-TRIS precipitates.
If placing the sensor in a 50-60°C water bath for several minutes or immersing it in 0.1 M HCl for
12 h doesn't help improve its performance, the sensor has to be replaced by a new one, preferably
one with open or sleeve junction. Or, even better, use a sensor with ARGENTHAL reference system
and silver ion trap from now on.

6. How to measure pH in fluoride

The main problem is that fluoride attacks glass. With InLab Hydrofluoric the pH value in samples
with up to 1 g/L hydrofluoric acid (HF) can be measured in the standard way.

For higher HF concentrations glass-free electrodes are needed. Thus far, the only useful solution is
the combination of the two titration sensors Sb850-S7/120 and DX202-SC. It is not possible to
calibrate them with our pH meters because the offset is far from 0 mV. But a manual calibration
can be made by measuring the mV value in different pH buffers and calculating the slope and offset
(e.g. with Excel); mV readings of future pH measurements can then be matched with this curve to
get the pH value of the HF solution.
All in all, a titration using the same electrode would certainly be much more accurate than a direct
measurement.

7. Should a sample be stirred during pH measurement?

Before starting a pH measurement, always stir the sample to render it homogeneous. This ensures
that the measured value is valid for the whole sample and not just for the part where the electrode is
situated.

Stirring during pH measurement in clear solutions is not necessarily needed.

The following guidelines regarding stirring have to be taken into consideration:

 Stirring during calibration requires stirring during measurement and vice versa
 For the sake of comparability of measurement all samples should be stirred at the same
speed
 For highly reproducible measurements the sensor should always be placed at the same
position, depth and at the same angle in the measuring beaker
 Heterogeneous solutions should be stirred, but carefully, so as to not harm the pH
membrane with the swirling particles
  Stirring speeds up the pH measurement by enhancing achievement of equilibriums of both
pH and temperature
 Too many air bubbles in the stirring vortex might interfere with the pH measurement
 Avoid contact of the pH sensor tip with the rotating stirrer

8. Is there a relationship between the pH and conductivity of a sample?

Yes, pH and conductivity are related but not linearly or in an absolute manner.
A pH sensor responds solely to H+ in the solution whereas in conductivity the sensors measures
the activity of all charged ions (anions and cations) present in the solution. The higher the
concentration of ions, the higher the conductivity.

Furthermore, the mobility of an ion has an enhancing impact on conductivity. Among the common
ions in solution, the most mobile cation is the Hydrogen ion [H+] with a value of 350 units, and
the most mobile anion is the Hydroxyl ion [OH-], 199 units. The other common ions have values
ranging between 40 and 80 units. This means strongly acidic (or strongly basic) solutions will
have high conductivities. Since pH is a measure of the concentration of Hydrogen ions, the
following rules apply:

 In acidic solutions (< pH 7): the lower the pH (i.e. the higher the H+ concentration) the
higher the conductivity.
 In alkaline solutions (> pH 7): the conductivity increases with increase of pH (increase of
OH- ion) .
Neutral pH (pH 7) is due to equal concentration of H+ and OH- ions. But it does not mean the
solution does not contain any other ions which would contribute to the conductivity of the solution.
Let's consider an example: pH of deionized water is theoretically 7.0 and conductivity is 0.055
µS/cm. If you add NaCl salt to it, the resulting NaCl solution will still be of neutral pH but the
conductivity of the solution could greatly increase depending on the amount of NaCl added.

In summary: pH and conductivity of a sample have to be determined separately for each of the
sample and cannot be theoretically correlated.

2. FAQ's: pH Instruments
1) How often should I clean my pH electrode?

Your pH electrode should be cleaned regularly. Fats, oils, and grease should be cleaned with a
non-ionic surfactant solution or methanol. Proteins should be cleaned with an acidic pepsin
cleaning solution. After cleaning, rinse the electrode with deionized water, then store in the correct
solution.

2) What is reference electrolyte?

The main function of the reference electrolyte is to, via the reference element and the reference
junction, electrically connect the measured media to the pH meter.
3) How do I know if my pH reading is accurate?

The first step to ensuring you are getting an accurate pH reading is to use your calibration points as
a bracket for the pH range of your sample. It is recommended to use at least two points. Use best
practices such as keeping the glass bulb hydrated and opening the fill hole.

4) What is my calibration slope and offset, and what does that mean?

The calibration slope is a conversion from an electrode signal in mV to a pH reading. The offset is
the mV reading of the electrode when it is submerged in pH 7 buffer. Your offset should not exceed
plus or minus 30 mV.

5) What calibration points should I use?

Calibration should cover the range of the desired measurement values. The most common pH
electrode calibration method is two-point calibration. During a two-point calibration, the pH meter
will determine the slope and offset of the pH electrode.

6) What is ATC?

ATC (Automatic Temperature Compensation) allows the pH meter to compensate for temperature
variations that may affect the accuracy of your pH measurements.

7) How is the temperature compensated when measuring pH?

pH measurements depend on the sample’s temperature. Two points are important:

A) Temperature influence on the slope of the electrode:

The pH electrode provides a potential (mV) between the measuring and the reference half-cell.
The instrument calculates the pH value from this potential using the temperature dependent
factor -2.3 * R * T / F where R is the universal gas constant, T the temperature in Kelvin and F
the Faraday constant. At 298 K (25 °C), the factor is -59.16 mV/pH. This is called the
theoretical slope of the electrode at the reference temperature (25 °C). At different temperatures
the slope values can be calculated accordingly. E.g.: -56.18 mV/pH at 10 °C, -58.17 mV/pH
at 20 °C, -60.15 mV/pH at 30 °C and so on. This influence of the temperature on the pH
measurement is corrected by automatic (ATC) or manual temperature compensation (MTC).
Hence, it is important to know the temperature of the sample or to use a temperature probe. A
wrongly set temperature results in an error of 0.12 pH units per 5 °C difference.

B) Temperature influence on the pH value of the sample

The pH value of the sample changes with the temperature. This is a chemical effect and
therefore individual for each type of sample. This influence CANNOT be compensated; only the
 real pH value at the actual temperature is displayed. Hence, it is important to compare only pH
values measured at the same temperature.
Exception: the temperature dependence of pH of many commercial buffer solutions is stored in
the instrument. As result the electrode can be calibrated at different temperatures because the
measured potentials are automatically referred to 25 °C or 20 °C. To benefit from this feature it
is important to select the correct buffer group and to measure the temperature during
calibration.

8) How can I get support for LabX software?

If your LabX software is registered, you can become a member of the LabX products knowledge
base and get access to LabX product information for end-user:

Release notes, frequently asked questions and details on open issues from our R&D, technical
support and user community. Go to: http://activation.mt.com and login with your user credentials to
see the link to the knowledge base.

For particular questions you may also contact Software Factory Support at labxsupport@mt.com

9) What does IP67 mean?

IP stands for 'Ingress Protection.' An IP number is used to specify the environmental protection of
enclosures around electronic equipment. These ratings are determined by specific tests. The IP
number is composed of two numbers, the first referring to the protection against solid objects and
the second against liquids. The higher the number, the better the protection.

3. FAQ's: pH Electrodes

1. How to find the right sensor for you application

There are several ways to find the appropriate sensor

 Under www.mt.com/electrode-guide
 In the sensor brochure, pages 34/35
 Contact your local Mettler-Toledo representative or dealer

2. What is the measuring error of a pH electrode?

The measuring error cannot be determined by looking at the electrode alone, it must be
considered as a function of the whole measuring system including the pH meter. There are
a number of factors that affect the accuracy of a pH measurement, such as the condition
 and age of the electrode, the electronics of the instrument, the temperature probe and the
accuracy of the calibration, amongst other factors: Here is a list of some of them:

 Temperature sensor: accuracy: ± 1 °C

 pH sensor, zero point accuracy: 7.0 ± 0.25 pH
 Buffer solutions accuracy: ± 0.02 pH
 pH meter accuracy: ± 0.002 pH and ± 0.1 °C
 3 point calibration accuracy: ± 0.02 pH).

Across the system we can expect the measuring error of a customary sample (e.g. clear
aqueous solutions or buffers in the range of pH 2 - 9) under standardized conditions
(temperature, stirring, endpoint criterium), to be approximately 0.05 pH units.

It is only possible to determine the accuracy of the measuring system more precisely by
empirical determination. This can be done by measuring the pH value with the same
electrode several times, rinsing regularly in-between measurements. The readings must
then be statistically evaluated to disclose the accuracy.

3. How to store sensors correctly?

All user manuals come with the necessary information about the short and long time
storage of the respective probe.

General tips for long time storage:

 pH and ORP electrodes: with wetting cap filled with reference electrolyte (often 3
mol/L KCl); it is also possible to store the electrode in pH buffer 4 or in 0.1 mol/L
HCl
 Ion selective electrodes: dry
 Conductivity sensors: dry
 Polarographic DO sensors: with measuring module filled with electrolyte and with
green protective cap mounted (dry) to protect from mechanical damage
 Galvanic DO sensors: with storage vial filled with 10% NaCl
 Optical DO sensors: in the calibration tube ensuring first that the sponge has been
dampened with distilled water or keep the sensor in a beaker filled with distilled
water

4. What is the normal lifetime of a pH electrode?

When using and storing a pH electrode the recommended way, the expected lifetime is 1 to
3 years. Some customers use their electrodes for up to 8 years! There are, however, a
number of factors that can contribute to shorten the lifetime of an electrode. One of them is
 the use of hot or very alkaline samples. Other factors may be mechanical damages, drying
out or storage of the membrane in water of low ionic strength.

Nevertheless, even electrodes that have been well maintained and properly stored may start
performing poorly after some time. In such cases, it may be possible to regenerate the pH-
sensitive glass membrane using an ammonium bifluoride regeneration solution (ME-
51340073) and restore the electrode to its previous level of performance. This regeneration
solution is based on a highly diluted solution of hydrofluoric acid which etches away a very
thin layer of the glass membrane, exposing a fresh surface area.

Blockage of ceramic diaphragms can also lead to a significant reduction of the pH sensor's
performance (see also "How to clean pH and ORP electrodes").

The lifetime of electrodes with the SteadyForce reference system such as InLabÒ Power or
InLabÒ Viscous is mainly limited by the residual overpressure of the electrolyte. Depending
on the usage requirements, it can be used for 6 to 12 months.

5. When is the regeneration solution needed for pH sensors?

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 in the process. The pH-sensitive glass membrane can
be reactivated using a regeneration solution. This solution is a mixture of hydrochloric
(HCl) and hydrofluoric (HF) acids. 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! Keep the volume of the solution to a
minimum by using a small acid-resistant vessel. Dip the tip of the electrode into the
regeneration solution for 5 to 15 minutes. The maximum immersion point is at the level
with the upper shoulder of the pH-sensitive glass. Never dip the sensor shaft into the
solution because the hydrofluoric acid will damage it.

Then rinse the electrode thoroughly with water and condition it for approximately an hour in
a buffer solution of pH7. Finally, place the sensor overnight in the specific reference
electrolyte.

6. What are the tolerance limits for slope and offset of pH sensors?

We didn't find any international standard that defines which slope is allowed and which
not. DIN 19268 says, that for an accuracy of 0.03 pH unit of the measurement a slope of
at least 58 mV/pH at 25 °C (equals 98%) must be achieved during calibration (there are
many more pre-conditions about the selection of buffers, temperature measurement,
response time and so on).
 Every user or company has to define which slope is acceptable based on their own
regulations. As a general rule a 95% slope is still OK for accurate results and 90% is still
OK for general results.
How to control it? Simply perform calibrations on a regular base, e.g. every morning.
Ideally, these values should be registered somewhere (at least the last five results) to
recognize if the electrode suddenly fails one day or if the slope slowly decreases over time.
The latter is normal because of ageing, the former indicates an incident, e.g. a clogged
diaphragm.
With ISM pH electrodes the last five calibration results are stored on the chip. This is helpful
and replaces the manual reporting mentioned above.
With some instruments it is also possible to perform electrode tests which check the slope
without changing the calibration data. Beside slope and offset the drift value is also often
determined.

7. What is the expected outflow of reference electrolyte in pH sensors?

1 mL per 24 hours for electrodes with ceramic diaphragm (e.g. InLab Routine)
3 mL per 24 hours for electrodes with sleeve diaphragm (e.g. InLab Science)
Electrodes with solid state electrolyte and open junction (e.g. InLab Expert) have no outflow
but only "exchange" ions via diffusion

8. What does ISM mean?

ISM stands for Intelligent Sensor Management. Every ISM marked sensor encloses a chip
that saves relevant data and exchanges them with the meter.

The saved information comprises the following data:

 Values, name, serial number, date and time of the certification made at the end of
the production at the factory
 Values date and time of the last five calibrations
 The maximum temperature that the sensor has ever been exposed to

This allows for better data security, monitoring of the sensor history and eases handling of
the sensor when used with different meters capable of reading ISM sensors.

9. What are the differences between analog, ISM and digital sensors?

An analog sensor provides exclusively analog measuring signal to the meter (e.g. mV for
pH and mA for NTC temperature measurement. The signals are converted to digital values
only in the meter. No exchange of other data with the meter takes place.
 A digital sensor transforms all analog data into digital signals before sending them to the
instrument. Calculations of calibration results and temperature compensated pH values are
also processed on the sensor prior to transmission to the meter. Therefore, digital sensors
are only compatible with designated meters featuring suitable connectors and firmware.

An ISM sensor is a hybrid. Whilst providing exclusively analog measuring signals (e.g. mV
for pH) to the instrument, digitalized data such as calibration history, certification infos,
sensor name and serial number stored in a chip placed in the electrode head can be
exchanged with the meter. For former generations of pH meter, which are not able to read
ISM data, it makes no difference whether an ISM sensor or a non-ISM sensor is connected.

4. FAQ's: Buffers and Solutions

1. Where can a certificate or a material safety data sheet for solutions be obtained?

The certificates of all calibration solutions and many electrolytes can be downloaded at
www.mt.com/buffer.
The respective material safety datasheets are available at www.mt.com/msds.

2. What is the accuracy of pH buffers and conductivity standards?

Tolerances of calibration buffers of pH Lab portfolio:
 DIN/NIST pH buffers ± 0.02 pH units
 DKD buffers ± 0.02 pH units
 Technical buffers ± 0.02 pH units
Tolerances of conductivity standards of pH Lab portfolio:

Standard Sachets (@ 25°C) Bottle (@ 25°C)

1,3 μS/cm - ± 0.05 μS/cm (4%)
5 μS/cm - ± 0.05 μS/cm (1%)
10 μS/cm ± 0.2 μS/cm (2%) ± 0.1 μS/cm (1%)
84 μS/cm ± 1.7 μS/cm (2%) ± 0.8 μS/cm (1%)
1413 μS/cm ± 21 μS/cm (1.5%) ± 21 μS/cm (1.5%)
12.880 mS/cm ± 193 μS/cm (2%) ± 193 μS/cm (1.5%)

3. Should pH buffer 7.0 be included in every calibration?

It is not necessary to include pH 7 for calibration according to the US and European
pharmacopoeia s(USP and EP, respectively). But if the calibration is done in compliance
 with the Japanese Pharmacopoeia (JP), then pH 6.86 buffer (phosphate) is mandatory.
For calibration according to EP, only pH buffer 4.01 (phthalate) is compulsory.

If not working according to any regulation, the principle is easy: For calibration, only those
buffers are needed which bracket the pH range of your samples. For example in a quality
control where every sample should have pH between 3.5 and 3.8, a 2-point calibration
with pH 2.00 and 4.01 is sufficient. There is no need for calibration with pH 7 in such a
case.

4. Does the level of inner pH electrolyte in a bridge electrode need to be greater than the
outer pH electrolyte?

Yes. If the bridge electrolyte has a higher filling level, then it flows into the chamber with the
reference electrolyte (due to the higher pressure at the inner junction). This changes the
composition and it is not pure 3 mol/L KCl anymore. The reference signal of the electrode
depends on the solution's composition, hence, the measured potential between measuring
half-cell and reference half-cell changes due to it.

5. What do I do in the event of KCl leakage and salt buildup on the electrode?

Salt build up is not harmful to the electrode and does not inhibit its performance. It can
easily be removed by rinsing the area with warm water.

6. How long can solutions and standard be used once the bottle has been opened?

The quality of the solution is only guaranteed for a previously unopened bottle (and only
until the expiry date is reached).
For example it is known that acidic buffer solutions can be kept longer than alkaline ones,
since carbon dioxide from air may dissolve in the liquid and change the concentration of
protons towards lower pH values.

We can only provide customers with tips and hints on how to use the solution for as long
as possible whilst getting accurate results. These measures are recommended:

 Mark on the bottle the open date

 Keep the solution tightly sealed at all times and use any poured calibration
standard promptly
 Never pour dispensed solution back into the original bottle, nor mix solutions from
different manufacturers
 Ensure that no contaminants enter the solution bottle
 Store the solutions at normal ambient temperature
  Do not store the solutions in direct sunlight
 Properly clean your electrodes before calibrating and do not calibrate directly in the
original solution bottle
 Never use a solution that has exceeded its expiry date or is suspected of being
contaminated
 Replace your solution with a new bottle once it has reached the expiry date
 When using calibration standard solutions at irregular intervals, the use of solutions
in sachets is recommended.

7. What is the composition of the InLab storage solution?

If InLab pH electrodes are stored in the InLab Storage Solution (Ref. 30111142) then the
ideal storage conditions are met. The solution consists of:

 ~2 mol/L KCl in water

 Potassium hydrogen phthalate (pH 4)

Other solutions suitable for the storage of pH electrodes are:

 FRISCOLYT-B (51340053) for storage of low maintenance pH electrodes with

XEROLYT or XEROLYT EXTRA polymer reference electrolyte and of pH sensors filled
with FRISCOLYT reference electrolyte
 3 M KCl for all types of pH electrodes except InLab Nano

8. What is the composition of the FRISCOLYT reference solution?

The composition of FRISCOLYT B is 2:1 mixture of:

 Glycerol (2 part)
 3 mol/L KCl in water (1 part)

The difference between FRISCOLYT-B (MT pH Lab) and FRISCOLYT-C (MT Process) is the
ratio between glycerol and water. Both can be used as reference electrolytes for pH
electrodes. Although allowing for measurement at an overall temperature range of -30 to
130 °C, FRISCOLIYT solutions are mainly used for measurements at low temperatures (e.g.
with InLab Cool, to measure below 0°C) and for samples containing organic compounds
(oils, proteins, etc.).
9. What is the difference between Technical, NIST/DIN and Certified pH buffer solutions?

- Technical buffers:
The METTLER TOLEDO standard buffer solutions come with a certificate from the production
plant (METTLER TOLEDO Process Analytics). Precision is ± 0.02 pH units.

- NIST/DIN buffers:
Buffers prepared according to the recommendation of the National Institute of Standards
and Technology (NIST) and the German Institute for Standardization (DIN). They also have
a certificate from the production plant (METTLER TOLEDO Process Analytics). Precision is ±
0.02 pH units.

- Certified buffers:
Selection of METTLER TOLEDO standard buffers that are verified and certified by an
independent laboratory (DKD = Deutscher Kalibrierdienst = German Calibration Service).
Precision is ± 0.02 pH units.

10. Are all pH calibration buffers from METTLER TOLEDO NIST compliant?

All of our pH buffers are NIST traceable and hence NIST compliant. Please read the
following citation of our calibration certificate:

 For the calibration of the pH value of our buffer solutions, the measuring
instruments were calibrated using two different reference buffer solutions, based on
primary pH reference materials of the NIST1.
 The National Metrology Institutes compare their measurement capabilities
periodically in keycomparisons within the CIPM-MRA2.
 The international comparability, harmonization and the equivalence of their
measurement capabilities are therefore guaranteed.
 This ensures a flawless traceability of the certified pH buffer solution values to NIST
along with our Quality Management System. The certification is done for each lot.