CONDUCTIVITY MEASUREMENT

AND ITS CALIBRATION Leif Jensen, Insatech A/S

Agenda
• Conductivity – what is it ? how/why it is measured

• Conductivity – why is it important ? performance and

regulatory requirements

• Conductivity – the importance of temperature and its

compensation

• Conductivity – how to calibrate

• Quality assurance
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What is Conductivity in Liquids?
• Conductive liquids are
called electrolytes

• Electrolytes have positively

and negatively charged
particles called ions.

• Positive charged Ions are

Cations and Negatively
charged ions are Anions

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Conductivity – What is it?
• Conductivity is a measurement of how well electrical
signals pass through a liquid

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Conductivity – what is it?
• Conductivity is a measurement of how well
electrical signals pass through a liquid

• Used to measure

 Chemical concentration

 Control of water purification plant –

Water for injection and purified water
systems

 Concentration of dissolved solids

 Interface detection – is it clean or dirty

 Heat exchanger breakthrough detection

 Defined as reciprocal of resistance, The SI unit of conductivity is S/m

and, unless otherwise qualified, it
 Unit of measurement - Siemens – refers to 25 °C (standard
nS,uS,mS nano,micro,milli
temperature)

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Cell Constant
• To make a measurement of current flow and
the unit siemens useful, it is necessary to
define what is being measured.

• The unit Specific Conductivity defined as

conductivity of a liquid column with a length
of 1cm and a cross section of 1cm
S/cm = S * Length cm / Area cm2

• All sensors are supplied with a cell constant,

a factoring number derived from the
relationship between the size of the contacts
and their distance apart.
CC = Length cm / Area cm2

• The SI unit of conductivity is S/m and,

unless otherwise qualified, it refers to 25 °C
(standard temperature)

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Conductivity – How is it
Measured?
• It is measured with a transmitter and
a sensor that has a defined cell
Constant! Or an Installation Factor

• The sensor and transmitter will have built in

temperature compensation – incredibly
important due to the temperature effect on
Conductivity measurement

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Conductivity – How is it
Measured?
• Two methods of measurement

 1 - Contacting- specific closed cell design & 4 electrode OPEN cells.

 2 - Inductive – Toroidal.
In a Pharmaceutical manufacturing environment both methods are used

Typically polished sanitary sensors - pure waters and CIP

 Closed cell design for water purity /steam condensate – WFI systems –UP systems
 Range is usually 0.056 uS to 100 uS
 New Open sensor design – wide range from 100uS to 200mS

Toroidal/open cell for concentration - Typically CIP only

 Usually CIP/SIP skids and dilution applications – washers
 Range is typically 1000uS (1mS) to 200mS

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MEASURING PRONCIPLE vs.
CONDUCTIVITY RANGE
How each Measuring Principle is applied currently

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Conductivity – Why is it
important? WFI UPW
For purified Water and Water for Injection (WFI), the USP defines the following conductivity requirements:

• The USP <645> calibration and performance requirements

• Meter reports uncompensated conductivity or uncompensated resistivity.

• The display resolution is 0.1 μS/cm or better.

• The meter reads accurately to ±0.1 μS/cm when a 0.1% precision resistor replaces the sensor
(to calibrate/verify the meter).

• The sensor cell constant is calibrated/verified to ±2%

• Temperature accurate to 2°C (effective USP 28)

• Appropriate dynamic range to meet the above requirements. There are no specific requirements for the
dynamic range of the conductivity system, but the conductivity system operate in pharmaceutical waters
typically 0.2 to 4 μS/cm and in the fluid that the sensor is calibrated in (ASTM D1125 solution D, 146.9
µS/cm)

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Conductivity – Why is it
important? CIP
For CIP Clean In Place - it is imperative that the correct cleaning is carried out using the correct
conductivity measurement

• Correct measurement leads to correct concentrations at high temperature - 1% Caustic at 80

degC for example

• The incorrect Temperature Compensation will typically cause 20%-30% more Chemical use

• For higher Concentration Aggressive washes – 4% Caustic – 3% Nitric , you will damage your
plant – Diaphragms seal, Valves etc by constantly being at high temperature and larger
concentrations than you think .

• To ensure the Final rinse has been successful

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Sensor Geometry – specific or
contact sensors
In practice sensors do not use flat
plate construction

• Rod within tube

• Rings
• Facing electrodes
• Polished sanitary type 316L

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Open Sensors
• Measuring range from 0.1 to
1,000,000µS/cm
• Suitable for pure water and
chemical concentration
• Easy clean construction
• Polished surface finish
• However – very, very challenging
to calibrate!

4 pole cell

Field

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INDUCTIVE –
PRINCIPLE OF OPERATION

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What is the transmitter doing?
DC Voltage Excitation

• If a dc excitation voltage is used then the electrically charged ions will gather at the
oppositely charged plate forming a non conductive layer.
• This is called polarisation.
• Electrochemical reactions can also take place (eg electro plating is carried out in this
way).

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Ac Voltage Excitation

• When an ac voltage is used the ions move alternately towards first one plate and
then the other.
• Therefore min. polarization occurs (assuming the correct frequency is used).
• All manufacturers uses square signals with changing polarity in complex ways.

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Temperature Effect
• Temperature has a very pronounced effect on the conductivity of a solution.
The magnitude of this effect is variable with:-
Solution type
Solution concentration
Temperature
Temperature change

• Temperature effect is typically non linear – this makes complex matrices or

calibration correction quite challenging.

• Temperature effect can be as large as 7-10% per Degree C – especially in

purer solutions!

• The SI unit of conductivity is S/m and, unless otherwise qualified, it refers to

25 °C (standard temperature)

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Cause of temperature
dependence
Zi · e
• Speed of ionic travel ni = 6 · π · h · ri ·E

• Dissociation. Variable up to 10%/°C

Water = H2O non conductive
Dissociated H+ OH- conductive

• At higher concentrations is the effect of “speed of ionic travel” is much

greater than the dissociation effect, but in pure water dissociation is the
dominant effect

• NOTE: Generally a 10°C temperature increase will improve

• cleaning efficiency by 50% (above 30°C) – this is why CIP is usually at
80 degC

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Review of importance of
temperature
• If temperature compensation is turned on,
temperature sensors should be calibrated within the
conductivity sensor
• If temperature compensation is used , choose the
correct algorithm for compensation – it could save you
30% on your chemical costs , and save your plant
• If Temperature compensation is Turned OFF , you
must report the temperature with the conductivity
value
• Do an audit of all instruments before commissioning

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Look at the varying
temperatures in a cycle

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Temperature Compensation
UPS

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NaOH matrix

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If you only have 1 transmitter
doing two jobs which curve?
Sample % per °C from 25C
• Salt solution (sodium chloride) 2.12%
• 5% NaOH (sodium hydroxide) 1.72%
• Dilute ammonia solution 1.88%
• 10% HC1 (hydrochloric acid) 1.32%
• 5% sulfuric acid 0.96%
• 98% sulfuric acid 2.84%
• Sugar syrup 5.64%
• 10% KC1 (potassium chloride) 1.88%

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Incorrect Compensation effects
– NAOH 1%
Incorrect Compensation effects – NAOH 1%
With NaC1 comp v NaOH or base comp

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Incorrect Compensation effects
– Phosphoric acid1%
Incorrect Compensation effects – Phosphoric1%
With NaC1 comp v Matrix or Acid comp

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Conductivity Calibration
TWO METHODS ARE TYPICALLY USED IN
CONDUCTIVITY CALIBRATION

• Comparison to another instrument (calibration reference

system-Insacal) usually accredited

• Use a known value standard solution (standard solution)

usually traceable

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MANGLER OVERSKRIFT
• TRACEABLE CALIBRATION
The term ”measurement traceability” is used to refer to an unbroken
chain of comparisons relation an instrument’s measurements to a
known standard. Calibration to a traceable standard can be used to
determine an instrument’s bias, precision, and accuracy.
• ACCREDITED CALIBRATION
What is Accreditation? – Accreditation is a voluntary, third party-reciewed
process. As part og accredtitation, a laboratory’s quality management
system is thoroughly evalutated on a regular basis to ensure continued
technical competence and compliance with ISO/IEC 17025. Laboratory
accreditation can only be granted by an accreditation body, or AB. Although
there are a number of accreditation bodies in the US, customers should
choose calibration and testing laboratories accredited by Abs having an
MRA with ILAC. In Singapore this is the Singapore Accreditation Council
(Singlas)

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COMPARISON VS.
STANDARD
Comparison Calibration (Insacal)
 In-line – while the sensors is in-situ
 At-line – simulate installation
 Laboratory – controlled environment
Standard Solutions
 Stabile conditions required -especially below 100uS
Uncontrolled environment
Variations in temperature

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Comparison Calibration
Calibration against
Another SUPERIOR
calibrated MASTER
METER- INSACAL

Advantages
• Multi-point Cell Constant calibration in a agitated homogenous mix
• Multi-point temperature calibration possible
• Accurate and 4:1 test accuracy achievable
• It doesn’t matter what value or purity of the solution as it effects both Master and UUT in
same way

Disadvantage
• Cell needs to be taken out of the process – unless a single pint verification method is
used

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More examples

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More examples

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Conductivity Calibration
• Using a Standard Solution compared to a Master
Calibration Reference Standard
Let us look at some of the issues
• Ease of use
• Uncertainty
• Traceability
• Process
• Cost

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Ease of use
STANDARD SOLUTIONS
• Standard solutions are sensitive to temperature  INSACALTM Master
changes –typically 2% per degC – this means a
temperature change of 1 degC can add 2% to
Reference Standard
the reading – so temperature changes account  Hook up the rig l and place sensor and UUT in
for almost all the allowable uncertainty of USP an aggitated solution of nominal value ( 1.3 -5-
10 uS ) and then wait for the temperature to
• The temperature of the standard solution must stabilise and read the conductivity and
be measured, and the temperature influence temperature.
must be defined in order to compensate for this
influence.

• Some solutions are only defined at a fixed

temperature, in these cases the standard
solution has to be placed in a temperature
controlled bath at the fixed temperature.
• Some low conductivity solutions are also
influenced by ambient CO2 and/or humidity,
these problems are normally solved by limiting
the time the solutions are exposed to ambient
air. (Time has to be defined)

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Ease of use
STANDARD SOLUTIONS
• Before any calibration is performed the sensor  INSACALTM Master
under test has to be thoroughly cleaned as any
contamination of the standard solution will
Reference Standard
influence the conductivity, even clean/pure  Hook up the rig l and place sensor and UUT in
water will dilute the standard solution. an aggitated solution of nominal value ( 1.3 -5-
10 uS ) and then wait for the temperature to
• The temperature compensation in the stabilise and read the conductivity and
transmitter under test has to be switched off or temperature.
adjusted to the coefficient of the standard
solution. (If known)

• If the sensor under test is of the open or

inductive type, an highly accurate mock up of
the installation has to be used during the
calibration as these types are influenced by the
physical installation.

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Ease of use
STANDARD SOLUTIONS
• Wait for the temperature to equalise after the
sensor under test is placed in the solution, then
read temperature and conductivity.
• The conductivity of the standard is then
determined by interpolation or by controlling the
temperature of the bath to a value where the
conductivity of the standard solution is known.
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 INSACALTM Master
Reference Standard
 Hook up the rig l and place sensor and UUT in
an aggitated solution of nominal value ( 1.3 -5-
10 uS ) and then wait for the temperature to
stabilise and read the conductivity and
temperature.
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Uncertainty
STANDARD SOLUTIONS
• Solutions at low conductivity are at best 1%.
When purchased and usually exhibit errors
close to 15 to 20%!!! See Gingerella report and
others – demonstrate – open a new bottle!
• High conductivity solutions have accuracies
from 0,15% and up so not so challenging at the
CIP type applications
• Commercially affordable high conductivity
solutions with uncertainties of 0.5 to 1% are
affordable. But the solution is only a part of the
equation
• Factors are :
• Accuracy of temperature probe
• Temperature homogeneity of the solution.
• Contamination
• Interpolation uncertainty
• Resolution
• Skill
• All these factors to be taken into account!
• The end result can easily be an uncertainty of
several percent.
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 INSACALTM Master
Reference Standard
 In the range of 100µS/cm to 10 mS/cm it is
possible to determine the cell constant with less
than 0,4% uncertainty
 The uncertainty of the transmitter under test
can be enhanced by calibrating the transmitter
with resistors prior to the loop calibration.
 The most important factor is that the reference
cell and the cell under calibration have the
same temperature during the calibration. If not
a temperature compensation has to be
performed adding some uncertainties.
 With a test accuracy ratio of 4:1 from the
master to the UUT ( looking for 2%) then you
can have a high degree of CERTAINTY that a
good calibration has been achieved
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Traceability
STANDARD SOLUTIONS
• There are different levels of traceability
 INSACALTM Master
• Traceable to a standard method
e.g. ASTM 56 or OIML
Reference Standard
 The reference standard is calibrated in an
• Traceable to an accredited institute e.g. accredited Lab
Hamiltons solutions
 First the indicator is electrically calibrated in all
• Made by an institute who is accredited by Sub-ranges, this can be done by an accredited
an organisation which is under the institute.
umbrella of B.I.P.M. eg. NIST, DFM  Secondly indicator and cell are calibrated with a
(Danish accredited institute when it comes standard primary solution.
to conductivity solutions)

• This still leaves no direct line to an  This rig is an accredited calibrator with a high
accredited calibration unless you pay level of accuracy of <0.5% and gives a good
1000s of euro per litre for accredited 4:1 test accuracy directly to the UUT
solutions - and these have a very short
shelf life with only the best lab conditions
allowable to achieve the result

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Process
STANDARD SOLUTIONS
• Cell has to be dismounted for calibration resulting
 INSACALTM Master
in:
• Production interruption.
Reference Standard
• Possible pollution in clean applications  Cell can remain in the process
e.g.
• WFI. Requiring new sterilisation etc.  Calibration can be performed during production
if required – it may only be a 1 point but it is a
great insurance

 If flow outlet of the reference fitting is drained

away, then there can be no pollution of the
process.

 The calibration can be performed in a closed

loop.

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Cost
STANDARD SOLUTIONS
• Depending on conductivity, traceability and
uncertainty, the solutions can cost from 50€ up
to 500 € per bottle
• Over and above the cost of the standard
solution, a considerable cost of labour has to be
added, as well as loss of production and in
some cases cleaning/sterilising cost of the
installation.
 INSACALTM Master
Reference Standard
 Initial cost is considerably higher compared to a
standard solution; but calibrations are
performed faster and require less operator skill.
They do not interfere with production and
decrease contamination risks. Paperwork is
also easier and faster.

• They have a shelf life  The rig offers very low cost of ownership and is
much more efficient (time) than use of solutions.
• They have no Value – they are not reliable –
you are not getting what you are paying for

• What is the cost of having an error on a WFI or

Purified water system???

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Conclusion arguments for
INSACAL
Industrial roughness
Known operator interface
Reliable reference equipment
Easy calibration on-site
Fulfill requirements of pharmaceutical
industry
Comes with Accredited Calibration incl.
documentation
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Examples of customers Rigs
for INSACAL

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Quality assurance
Quality assurance in the pharma industry is made up by
pharmacopeias and metrology!

But –
Pharmacopeia and metrology do not “goes hand in hand”
VS.

Then add guidelines and practices like 1:4 rule( Z540.3)

and other local practices.

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Quality assurance
Trademarks of the Ph-Eur & USP for WFI
Celle constant: must be known within±2%
• According to Ph-Eur -determined at max.
1500µS/cm. No recommendation in USP.
• Neither of them has a position on
uncertainties, and how to deal with them.

System calibration – cell & indicator

• Ph-Eur states: accuracy within ±3% ± 0,1µS/cm

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Quality assurance
Conductivity indicator:
• Calibrated by usage of 0,1% resistors.
• Accuracy limit acc. to Ph-Eur & USP is 0,1µS/cm
• Min. display resolution: 0,1µS/cm

Temperature:
• No temperature compensation.
• Accuracy ± 2°C

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Quality assurance
How abort non WFI applikations?
Ph-Eur has an general limit of 5%.

But how about temperature compensations for applications

like:
• Steam?
• CIP?
• Washing machines?
• Reverse osmosis water?
• ect.

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Quality assurance
So how do “we” cope?

Temperatur compensation:
• Some still uses temeratur compensations, even for WFI.
• Some has switch off temperature compensations in more
or less all cases.

Limits:
• Most use: ±2% ± 0,1µS/cm for pure water as a system.

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Quality assurance
How about the 1:4 ratio?

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Quality assurance
How about the 1:4 ratio?

So 1:4 is possible if calibrated correct!

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MANGLER OVERSKRIFT
The most widely debated issue regarding cell constant calibration is "if I calibrate at 147 uS/cm or 0.0550 uS/cm, how do I
know if my sensor is calibrated at 1 uS/cm?". Because of the impact of CO2 on water, there are no standard solutions that can
be prepared accurately and precisely in the 1 uS/cm range. Other than trusting the conductivity manufacturer, how do you
assure yourself? One valid method that meets all of the technical challenges is to determine the cell constant in pure water and
in ASTM solutions. The cell constant is a "geometrical factor" that normalizes the water resistance for the sensor design. The
cell constant is a constant over the linear dynamic range of the system. Therefore, if the cell constant is identical at 0.055 u
S/cm and 147 uS/cm, then it is the same value at 1 uS/cm. To use a pH analogy, if you calibrate a pH sensor at 4 pH and 7 pH,
it may or may not be accurate at 10 pH. However, if you calibrate a pH sensor at 4 pH and 10 pH, it is generally accurate at
7 pH. Although the linearity of the conductivity circuitry is more complex than the circuitry for pH, the same concepts apply.12
A track record of measurement rangability and cell constant consistency has been established for one measuring system.
Table 4 shows a series of conductivity sensors that have been repeatedly calibrated in 5 different "solutions" over the last three
years : ultra pure water at 3 different temperatures and ASTM D1125-95 solutions "C" and "D". The cell constants were
determined by calculating the pure water resistivity based on the temperature which is known to ±0.01°C. The equation relating
the temperature (T, °C) and the resistivity (r, MW-cm) is shown below11.
r = e (a0 + a1 T1 + a2 T2 + a3 T3 + a4 T4 + a5 T5)
where a0 = 4.45656 a1 = -7.33064´10-2 a2 = 5.02097´10-4
a3 = -2.56203´10-6 a4 = 6.43445´10-9 a5 = 1.40405´10-12
The conductivity of the pure water was adjusted from ~0.02 uS/cm to ~0.1 uS/cm (pure water at 15°C to 40°C, respectively).
The ASTM solution conductivities were 147.9 and 1409.8 mS/cm, 1.0 mS/cm greater than the values in the Table 3 above, to
account for the conductivity of the water.
The "constancy" of the cell constants is displayed in a statistical format in Table 5. The last two columns show the relative
standard deviation of the cell constant measurement for all 5 "solutions" (3 pure water and 2 ASTM solutions) and for all
solutions except solution C. Note that the relative error is less than 0.5% from 0.02 to 150 mS/cm, across nearly 4 orders of
magnitude. The relative error is less than 0.75% from 0.02 to 1400 mS/cm, across nearly 5 orders of magnitude.

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INSACAL CUSTOMERS

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