6/4/2021 USP-NF 〈644〉 Conductivity of Solutions

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〈644〉 CONDUCTIVITY OF SOLUTIONS

Portions of the chapter text that are national USP text and are not part of the harmonized text, are marked with symbols (◆◆) to
specify this fact.

INTRODUCTION
This chapter provides information on how to apply electrical conductivity measurements (hereafter referred to as “conductivity”) of
uid solutions, including pure uids. ◆This chapter does not replace the o cial Water Conductivity 〈645〉 procedure, which is used to
ensure the ionic purity of compendial waters such as Water for Injection, Puri ed Water, Pure Steam condensate, and Sterile Water for
Injection, among others.◆ This chapter is intended for ◆other◆ uid applications when conductivity is used to measure, monitor, or
control chemical dispensing, chemical purity, ionic concentration, and other applications where the ionic character of the uid needs
to be known or controlled.
Applications include, but are not limited to, solutions that may be used in clean-in-place, chromatography detection, ionic solution
preparations, endpoint detection, dosing, fermentation, and buffer production. In some cases, conductivity measurements can be
extended to pure organic uids such as alcohols and glycols where a weak conductivity signal exists, and the signal can be

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signi cantly increased if the organics become contaminated with water or salts. ◆[NOTE—For additional background information, see
Theory and Practice of Electrical Conductivity Measurements of Solutions 〈1644〉.]◆
Conductivity is the measurement of the ability of a uid to conduct electricity via its chemical ions. The ability of any ion to
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electrically conduct is directly related to its ion mobility. Conductivity is directly proportional to the concentrations of ions in the uid,
according to Equation 1:

all ions
κ = 1000 ∑ Ci λi
i
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κ = conductivity (S/cm)

Ci = concentration of chemical ion i (mol/L)

λi = speci c molar conductance of ion i (S · cm2/mol)

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Although the SI unit S/m is the appropriate SI unit for conductivity, historically the unit S/cm has been selected by industry as the
accepted unit.
On the basis of Equation 1, conductivity is not ion selective because it responds to all ions. Furthermore, the speci c molar
conductance of each ion is different. As a result, unless the percentage composition of ions of the solution is limited and known, the
precise concentrations of ionic species cannot be determined from conductivity measurements. However, for examples such as a
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solution of a single salt or acid or base, such as a caustic solution used in cleaning, the precise concentration can be directly
determined. Despite the lack of ionic speci city, conductivity is a valuable laboratory and process tool for measurement and control
of total ionic content because it is proportional to the sum of the concentrations of all ionic species (anions and cations) for diluted
solutions as described in Equation 1. At higher concentrations, conductivity measurements are not perfectly linear with concentration.
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Conductivity measurements cannot be applied to solids or gases, but they can be applied to the condensate of gases.
Another variable that in uences conductivity measurements is the uid temperature. As the uid temperature increases, the ion
conductance increases, making this physicochemical phenomenon the predominant reason for the temperature-compensation
requirement when testing conductive uids.
The conductivity, κ, is proportional to the conductance, G (S), of a uid between two electrodes (Equation 2):

d
κ = G × ( ) = G × K
A
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κ = conductivity (S/cm)

G = conductance (S)

d = distance between the electrodes (cm)

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6/4/2021 USP-NF 〈644〉 Conductivity of Solutions
A = area of the conducting electrodes (cm2)

K = cell constant (cm−1), which also equals the ratio of d/A

The resistivity p (Ω-cm) of the uid is, by de nition, the reciprocal of the conductivity (Equation 3):

ρ = 1/κ = 1/(G x K) = R/K

ρ = resistivity (Ω-cm)

κ = conductivity (S/cm)

G = conductance (S)

K = cell constant (cm−1)

R = resistance (Ω), which is the reciprocal of the conductance, G

APPARATUS
An electrical conductivity measurement consists of the determination of resistance of the uid between and around the electrodes
of the conductivity sensor. To achieve this measurement, the primary instrumentation is the resistance-measuring circuit and the
conductivity sensor, and they are usually connected by a cable when the sensor and the user interface are separated.
The resistance measurement is made by applying an alternating current (AC, meaning the ow of electric charge periodically
reverses direction) voltage (or current) to the electrodes, measuring the current (or voltage), and calculating the resistance according
to Ohm’s law. The alternating source is used to prevent the polarization (collection of ions) at the electrodes. Depending on the
instrument, the measuring frequency of the measuring system adjusts automatically according to the measuring conditions of the
instrument, and there may be multiple resistance-measuring circuits embedded in the measuring system. The resistance-

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measurement circuit may be embedded in the transmitter or in the sensor.
The conductivity sensor consists of at least two electrical conductors of a xed size and geometry, separated by an electrical
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insulator. The electrodes, insulator, and any other wetted materials should be constructed of materials that are unreactive to uids
with which they may come into contact. Also, the sensor construction should withstand the environmental conditions (process or
ambient temperature, pressure, cleaning applications) that it would be subjected to.
Most conductivity sensors have temperature devices such as a platinum resistance temperature device (RTD) or negative
temperature coe cient (NTC) thermistor embedded inside the sensor, although external temperature measurement is possible. The
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purpose of the temperature measurement is for temperature compensation of the conductivity measurement.

CELL CONSTANT DETERMINATION

The purpose of the sensor’s cell constant is to normalize the conductance (or resistance) measurement for the geometrical
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construction of the two electrodes.

The cell constant is determined by immersing the conductivity sensor in a solution of known conductivity. Solutions of known
conductivity can be obtained by preparation of speci c mixtures according to national authoritative sources or procurement of
commercially available certi ed and traceable standard solutions. These recipes or certi ed solutions can range from 5 to 200,000
µS/cm, depending on the level of accuracy desired. Alternatively the cell constant is determined by comparison to other reference
conductivity measuring systems (also available as an accredited calibration service). [NOTE—Conductivity measurements are not
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perfectly linear with concentration.]

The measured cell constant of the conductivity sensor must be within 5% of the nominal value indicated by the sensor certi cate,
unless otherwise prescribed.
Modern conductivity sensors normally do not change their cell constant over their lifetime. If a change of the cell constant is
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detected during calibration, a cleaning of the sensor is appropriate according to the manufacturer’s recommendations. Following that,
the calibration procedure should be repeated. Sometimes “memory effects” appear, particularly when changing from high to low
concentrations if the sensor is not well ushed.

CALIBRATION OF TEMPERATURE
In addition to verifying the sensor’s cell constant, the embedded temperature device (or external temperature device) should be
appropriately calibrated for the application to apply the temperature compensation algorithm accurately. The temperature accuracy
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that is required depends on the criticality of the temperature to the application. An accuracy of ±1° typically su ces.

CALIBRATION OF MEASUREMENT ELECTRONICS

The measurement circuit of the system is fundamentally an AC resistance measuring device. Appropriate veri cation and/or
calibration of the measuring circuit is required for measurement systems with signal transfer via analog cable. This is accomplished

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6/4/2021 USP-NF 〈644〉 Conductivity of Solutions

by disconnecting the measuring circuit from the sensor’s electrodes, attaching traceable resistors of known value with the cable of
the measurement system to the measuring circuit, and verifying that the measured resistance agrees with the resistor value to an
acceptable level. A typical acceptance criterion for the resistance accuracy is <2% of the reading at resistances >100 Ω, and
increasing to 5% at lower resistances. However, the application criticality should ultimately determine the desired accuracy.
For conductivity systems that cannot have the resistance-measuring circuit disconnected from the electrodes (e.g., measurement
circuit and electrodes in one mutual housing), it may be di cult to directly adjust or verify the circuit accuracy, depending on the
sensor design. An alternative method of verifying the measurement system integrity is a system calibration according to the
procedures for the cell constant determination for each measuring circuit that is intended to be used.
If veri cation/calibration of the sensor’s cell constant, temperature device, and measuring circuit are done at the same service
interval, the measuring circuit should be veri ed rst, the temperature device next, and the cell constant last. Because all of these
parameters are typically very stable due to modern electronics and stable sensor construction, frequent calibration (such as daily) is
not usually required. Comparison to quali ed reference systems is also a proper means of calibration. Calibration is performed at
appropriate intervals as de ned in the quality management system.

Change to read:

TEMPERATURE COMPENSATION
Because the conductivity of a uid is temperature dependent, temperature compensation of the conductivity measurement is
necessary unless otherwise prescribed (e.g., puri ed water, water for injection). An appropriate temperature compensation algorithm
will ensure that changes in the conductivity measurement can be ascribed to concentration changes and not temperature changes.
Conductivity measurements are normally referenced to 25°. A common form of linear temperature compensation uses Equation 4:
κT
κ25 =
[1+α(T −25)]

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κ25 = conductivity compensated to 25°

κT = conductivity at T

T
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= temperature coe cient of the conductivity

= measured temperature
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A temperature coe cient of 2.1% per 1° is commonly used for many salt solutions. Most salt-based solutions have linear
compensation factors ranging from 1.9% to 2.2% per 1°. Depending on the uid samples, other forms of temperature compensation
may be appropriate. Non-linear temperature compensation data for a variety of solutions is widely available (e.g., as described in ISO
7888 Water quality—Determination of electrical conductivity). In cases of very low conductivity (<10 µS/cm), such as puri ed ▲water
for cleaning/rinsing purposes,▲ (USP 1-May-2021) two compensations need to be made. One is for the intrinsic conductivity of water,
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and the other is for the other ionic species in water. These compensations are normally combined and embedded in the
microprocessor-controlled conductivity measurement systems. This is not supplied in all conductivity measurement technologies.

Change to read:

CONDUCTIVITY MEASUREMENT OF FLUIDS

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For off-line ▲or at-line▲ (USP 1-May-2021) batch measurements, rinse the cleaned sensor with the uid to be measured. Then
immerse the sensor in the uid to be measured, and record the temperature and the temperature-compensated conductivity as
required. Be sure that the position of the sensor in the container does not affect the conductivity measurement, because the container
walls can affect the measurement for some electrode designs.
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For continuous on-line or ▲in▲ (USP 1-May-2021)-line measurements, install the cleaned sensor into the pipe, tank, or other
containment vessel, and ush, if necessary. Make sure proper installation procedures are applied to prevent bubbles or particles from
collecting between the electrodes. Be sure that the position of the sensor in the pipe or tank does not affect the conductivity
measurement, because the nearby surfaces can affect the measurement for some electrode designs.
Record the temperature and the temperature-compensated conductivity as required.
For all batch or continuous measurements, ensure that the wetted components of the sensor are compatible with the uid and the
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temperature to be measured.

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6/4/2021 USP-NF 〈644〉 Conductivity of Solutions

Topic/Question Contact Expert Committee

<644> CONDUCTIVITY OF SOLUTIONS Antonio Hernandez-Cardoso GCCA2020 General Chapters - Chemical

Senior Scienti c Liaison Analysis 2020

Most Recently Appeared In:

Pharmacopeial Forum: Volume No. 41(5)

Page Information:

USP43-NF38 - 6868
USP42-NF37 1S - 9015

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