〈645〉 WATER CONDUCTIVITY
Antonio Hernandez-Cardoso Most Recently Appeared In:
Senior Scientific Liaison Pharmacopeial Forum: Volume No. 45(3)
By Mubashir Hussain
Content:-
• INTRODUCTION
• INSTRUMENT SPECIFICATIONS AND OPERATING
PARAMETERS
• Cell Constant
• Resistance Measurement
• System Verification
• Temperature Compensation and Temperature Measurements
• BULK WATER
• Procedure
• STERILE WATER
• Procedure
INTRODUCTION
Electrical conductivity in water is a measure of the ion-facilitated electron flow
through it.
Water molecules dissociate into ions as a function of pH and temperature and
result in a very predictable conductivity.
Some gases, most notably carbon dioxide, readily dissolve in water and interact
to form ions, which predictably affect conductivity also.
For the purpose of this discussion, these ions and their resulting conductivity can
be considered intrinsic to the water.
• Water conductivity is also affected by the presence of extraneous ions.
• The extraneous ions used in modeling the conductivity specifications described below are the
chloride and ammonia ions.
• The conductivity of the ubiquitous chloride ion (at the theoretical endpoint concentration of 0.47 ppm
when chloride was a required attribute test in USP 22 and earlier revisions) and the ammonium ion (at
the limit of 0.3 ppm) represents a major portion of the allowed water ionic impurity level.
• A balancing quantity of anions (such as chloride, to counter the ammonium ion) and cations (such as
sodium, to counter the chloride ion) is included in this allowed impurity level to maintain
electroneutrality.
• Extraneous ions such as these may have a significant effect on the water’s chemical purity and
suitability for use in pharmaceutical applications.
The procedure in the section Bulk Water is specified for measuring
the conductivity of waters such as Purified Water,
Water for Injection, Water for Hemodialysis, and the condensate of
Pure Steam.
The procedure in the section Sterile Water is specified for
measuring the conductivity of waters such as Sterile Purified Water
, Sterile Water for Injection, Sterile Water for Inhalation, and
Sterile Water for Irrigation.
The procedures below shall be performed using instrumentation that has been calibrated, has
conductivity sensor cell constants that have been accurately determined, and has a
temperature compensation function that has been disabled for Bulk Water Stage 1 testing.
For both online and offline measurements, the suitability of instrumentation for quality control
testing is also dependent on the sampling location(s) in the water system.
The selected sampling instrument location(s) must reflect the quality of the water used.
INSTRUMENT
SPECIFICATI
ONS AND
OPERATING
PARAMETERS
conductivity, κ (S/cm) = Θ (cm–1)/R (Ω)
It is the cell constant and the resistance measurement that must be verified and adjusted, if necessary.
Water conductivity must be measured accurately with calibrated instrumentation.
An electrical conductivity measurement consists of the determination of the conductance, G (or its inverse, resistance, R),
of the fluid between and around the electrodes.
The conductance (1/R) is directly affected by the geometrical properties of the electrodes; i.e., the conductance is inversely
proportional to the distance (d) between the electrodes and proportional to the area (A) of the electrodes.
This geometrical ratio (d/A) is known as the cell constant, Θ.
Thus, the measured conductance is normalized for the cell constant to determine the conductivity, κ, according to the
following equation:
The cell constant must be known within ±2%.
The cell constant can be verified directly by using a solution of known or
traceable conductivity, or indirectly by comparing the instrument
reading taken with the conductivity sensor in question to readings from
a conductivity sensor of known or traceable cell constant.
Cell Constant If necessary, adjust the cell constant following the manufacturer′s
instrument protocol.
The frequency of verification/calibration is a function of the sensor
design.
Resistance Measurement
Calibration (or verification) of the resistance measurement is accomplished by replacing the conductivity sensor electrodes with
precision resistors having standards traceable to NIST or equivalent national authorities in other countries (accurate to ±0.1% of the
stated value) to give a predicted instrument conductivity response.
The accuracy of the resistance measurement is acceptable if the measured conductivity with the traceable resistor is within ±0.1 µS/cm
of the calculated value according to the equation above.
For example, the traceable resistor is 50 kΩ, and the cell constant, Θ, is 0.10 cm–1.
The calculated value is 2.0 × 10–6 S/cm or 2.0 µS/cm.
The measured value should be 2.0 ± 0.1 µS/cm.
The instrument must have a minimum resolution of 0.1 µS/cm on the lowest range.
The target conductivity value(s) should be based on the type of water to be
analyzed, and it should be equal to or less than the water conductivity limit for
that type of water.
Multiple measuring circuits may be embedded in the meter or the sensor, and
each circuit may require separate verification or calibration before use.
The frequency of recalibration is a function of instrument system design.
System Verification
The cell constant of the user’s sensor can be determined with the user’s resistance measurement system, or the cell constant can be
determined with an independent resistance measurement system.
If the cell constant is determined with an independent resistance measurement system, it is recommended that the user verify that the sensor
has been properly connected to the resistance measurement system to ensure proper performance.
Verification can be made by comparing the conductivity (or resistivity) values displayed by the measuring equipment with those of an external
calibrated conductivity-measuring device.
The two non–temperature-compensated conductivity (or resistivity) values should be equivalent to or within ±5% of each other, or should have
a difference that is acceptable on the basis of product water criticality and/or the water conductivity ranges in which the measurements are
taken.
The two conductivity sensors should be positioned close enough together to measure the same water sample at the same temperature and
water quality.
Temperature Compensation and
Temperature Measurements
• Because temperature has a substantial effect on conductivity readings of specimens at
high and low temperatures, many instruments automatically correct the actual reading to
display the value that theoretically would be observed at the nominal temperature of 25°.
• This is typically done using a temperature sensor embedded in the conductivity sensor
and a software algorithm embedded in the instrument.
• This temperature compensation algorithm may not be accurate for the various water types
and impurities.
• For this reason, conductivity values used in the Stage 1 test for Bulk Water are non–
temperature-compensated measurements.
• Other conductivity tests that are specified for measurement at 25° can use either
temperature-compensated or non–temperature-compensated measurements.
• A temperature measurement is required for the Stage 1 test or for the other tests at 25°.
• It may be made using the temperature sensor embedded in the conductivity cell sensor.
• An external temperature sensor positioned near the conductivity sensor is also acceptable.
Accuracy of the temperature measurement must be ±2°.
BULK WATER
The procedure and test limits in this section are intended for Purified Water, Water for Injection,
Water for Hemodialysis, the condensate of Pure Steam, and any other monographs that specify this section.
This is a three-stage test method to accommodate online or offline testing. Online conductivity testing provides
real-time measurements and opportunities for real-time process control, decision, and intervention.
Precautions should be taken while collecting water samples for offline conductivity measurements.
The sample may be affected by the sampling method, the sampling container, and environmental factors such
as ambient carbon dioxide concentration and organic vapors.
This procedure can be started at Stage 2 if offline testing is preferred.
Procedure
• stage 1
• stage 2
• stage 3
Stage 1 is intended for online measurement or may be performed offline
in a suitable container.
1. Determine the temperature of the water and the conductivity of the
water with a non–temperature-compensated conductivity reading.
2. Using Table 1, find the temperature value that is NMT the measured
temperature, i.e., the next lower temperature.
stage 1
The corresponding conductivity value on this table is the limit.
[Note—Do not interpolate.]
3. If the measured conductivity is NMT the table value determined in
step 2, the water meets the requirements of the test for conductivity.
If the conductivity is higher than the table value, proceed with Stage 2.
Temperature Conductivity Requirement (µS/cm)
0 0.6
Table 1. Stage 1— 5
10
0.8
0.9
Temperature and 15
20
1.0
1.1
Conductivity Requirements 25
30
1.3
1.4
(for non–temperature-
35 1.5
40 1.7
compensated conductivity
45 1.8
50 1.9
55 2.1
measurements only) 60
65
2.2
2.4
70 2.5
75 2.7
80 2.7
85 2.7
90 2.7
95 2.9
100 3.1
stage 2
4. Transfer a sufficient amount of water to a suitable container, and stir the test specimen.
Adjust the temperature, if necessary, and, while maintaining it at 25 ± 1°, begin vigorously agitating the test
specimen while periodically observing the conductivity.
When the change in conductivity (due to uptake of atmospheric carbon dioxide) is less than a net of 0.1 µS/cm per 5
min, note the conductivity.
[Note—Conductivity measurements at this stage may be temperature-compensated to 25° or non–temperature-
compensated.]
5. If the conductivity is not greater than 2.1 µS/cm, the water meets the requirements of the test for conductivity.
If the conductivity is greater than 2.1 µS/cm, proceed with Stage 3.
stage 3
6. Perform this test within approximately 5 min of the conductivity determination in step 5, while
maintaining the sample temperature at 25 ± 1°.
Add a saturated potassium chloride solution to the same water sample (0.3 mL per 100 mL of the
test specimen), and determine the pH to the nearest 0.1 pH unit, as directed in pH 〈791〉.
7. Referring to Table 2, determine the conductivity limit at the measured pH value.
If the measured conductivity in step 4 is NMT the table value determined in step 6, the water meets
the requirements of the test for conductivity.
If either the measured conductivity is greater than this value or the pH is outside the range of 5.0–
7.0, the water does not meet the requirements of the test for conductivity.
Table 2. Stage 3—pH and pH
5.0
Conductivity Requirement (µS/cm)
4.7
Conductivity
5.1 4.1
5.2 3.6
5.3 3.3
Requirements 5.4
5.5
3.0
2.8
(for atmosphere- and
5.6 2.6
5.7 2.5
5.8 2.4
temperature-equilibrated 5.9
6.0
2.4
2.4
samples only)
6.1 2.4
6.2 2.5
6.3 2.4
6.4 2.3
6.5 2.2
6.6 2.1
6.7 2.6
6.8 3.1
6.9 3.8
7.0 4.6
STERILE
WATER
The procedure and test limits are intended for Sterile Purified Water, Sterile Water for Injection,
Sterile Water for Inhalation, and Sterile Water for Irrigation, and any other monographs that specify this
section.
The sterile waters are derived from Purified Water or Water for Injection, and therefore have been
determined to be compliant with the Bulk Water requirements before being stored in the container.
The specification provided represents the maximum allowable conductivity value, taking into
consideration the limitation of the measurement method and reasonable container leaching.
Such specification and the sampling volume choices should be defined and validated on the basis of the
intended purpose of the water.
Procedure
Obtain a sample that suitably reflects the quality of water used. Before opening, vigorously agitate the package to
homogenize the water sample.
Several packages may be required to collect sufficient water for analysis.
Transfer a sufficient amount of water to a suitable container, and stir the test specimen.
Adjust the temperature, if necessary, and, while maintaining it at 25 ± 1°, begin vigorously agitating the test specimen
while periodically observing the conductivity.
When the change in conductivity (due to uptake of ambient carbon dioxide) is less than a net of 0.1 µS/cm per 5 min,
note the conductivity.
For containers with a nominal volume of 10 mL or less, if the conductivity is NMT 25 µS/cm, the water meets the
requirements.
For containers with a nominal volume greater than 10 mL, if the conductivity is NMT 5 µS/cm, the water meets the
requirements.
THE END
