Conductivity

Module Outline

Topics
 Fundamental principles of a conductivity
measurement
 Fundamentals of conductivity calibration
and cell constant
– How should it be calibrated, order of operations

 What is detectable by a conductivity measuring

system
– Unique conductivity measurements in high-purity
water
– Value of on-line conductivity measurements in
high-purity water

 Principal of temperature compensation

 USP <644> and <1644> (for non-
pharmaceutical waters)
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© 2021 USP
Module 2—Water, Water Systems and Water Chemistry 101

What is conductivity?
• Where does it come from?
• How is it measured?

How is conductivity calibrated?

What are the special properties of

pharmaceutical waters?

What is temperature compensation?

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Electrical Conductivity

What is conductivity?

 Conductivity is the measurement of the ability of a fluid to conduct electricity via

the chemical ions in that fluid
 Ions permit the flow of “current” according to its ion mobility in the media of
interest
 The ion mobility is impacted by:
– Temperature
– Type of ion (not size)
– Media
– Concentration of the ions (at high concentrations)

For general information about Conductivity, see USP <644> CONDUCTIVITY OF SOLUTIONS and USP <1644> THEORY AND PRACTICE OF ELECTRICAL CONDUCTIVITY
MEASUREMENTS OF SOLUTIONS

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Ionic Conductance

The ions in water are conductive ~

AC

O H H
OH-
O H H O H O H
H O H H
O H
Na+ H O H
H
H+ H
O H O H H+ O H
O H
H H Cl- H
H

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Ionic Conductance (cont’d)

The lower the concentration of ions, the lower conductivity

Low High
Conductivity

A-C

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Ionic Conductance (cont’d)

The higher the concentration of ions, the higher conductivity

Low High
Conductivity

A-C

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Conductivity Applications

Conductivity measurements span eight orders of magnitude

Conductivity
(S/cm) 0.01 0.1 1 10 100 1k 10k 100k 1000k
Resistivity 100M 10M 1M 100k 10k 1k 100 10 1
(-cm)
Pure water
Cold Hot
WFI/PW/distilled/polished water
Ultrapure water exposed to air
Application Drinking water
Ranges Waste water
Brackish/Sea water
Ion Regeneration acids/bases
Concentration
(as ppm NaCl) 0.021 0.44 4.6 46 500 5.5k

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Conductivity

What can be conductive?  Typical examples:

– Common ubiquitous (they are everywhere) ions
such as Na+, K+, Ca2+, Mg2+, Cl-, NO3-, SO42-,
HCO3-
– H+ and OH- from the dissociation of water
– H+ and OH- from strong acids and bases
– Ionic portion of weak acids and bases: HCO3-
(bicarbonate), CH3COO- (acetate), NH4+
(ammonium)
 Non-typical examples: not so relevant in
pharmaceutical applications
– Dissociation of ethylene glycol CH2(OH)-
CH2(OH) into H+ and glycolate ion, pKa ~ 15
– Ions in non-aqueous media
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Water- Based Conductivity

 Dissociation of H2O into H+ and OH-

– From the dissociation of water, pKa = 14 at
25°C
– This means “pure water” is [H+] = [OH-] = 10-7
mole/L
 Ions that pass through the water treatment
system
– Common ions in source water: Na+, K+, Ca2+,
Mg2+, Cl-, NO3-, SO42-, HCO3-
– Weak acids/bases from UV generation or
incomplete removal: HCO3- (bicarbonate),
NH4+ (ammonium)

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 Conductivity

What is conductivity measuring? all

ions

 Conductivity is proportional to:  = 1000  Ci  i

i
– Concentration of each ion
– Specific conductance: unique for each ion
 Conductivity is temperature dependent
[H+ ]   + [ OH -
]   + 
 (T ) H + (T ) (T ) OH− (T )

 (T ) = 1000  [Na + ](T )   Na + (T ) + [K + ](T )   K + (T ) + [cation ](T )   cation (T ) + 
 
[Cl− ](T )   Cl - (T ) + [SO 24− ](T )   2 − + [anion ](T )   anion (T ) + 
 SO 4 (T )


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 Conductivity

What is conductivity measuring? all

ions
 = 1000  Ci  i
i

[H+ ]   + [ OH -
]   + 
 (T ) H + (T ) (T ) OH− (T )

 (T ) = 1000  [Na + ](T )   Na + (T ) + [K + ](T )   K + (T ) + [cation ](T )   cation (T ) + 
 
[Cl− ](T )   Cl - (T ) + [SO 24− ](T )   2 − + [anion ](T )   anion (T ) + 
 SO 4 (T )


H2O (25°C) = [10-7 mole/L x 349 S-cm2/mole] + [10-7 mole/L x 199 S-cm2/mole]

H2O (25°C) = 0.0000548 S/cm = 0.0548 S/cm = 18.2 Mohm-cm

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Resistance—Not Resistivity

Apply a voltage (V), measure the

current (I) and calculate the The resistance is inversely
resistance according to R = (V/I) related to the concentration of
• There are variations the ions in the water

Done right?

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Cell Constant

The resistance between two electrodes is proportional to the

distance and inversely proportional to the area

1 cm

1 cm
1 cm

Conductivity Cell Constant = Length = ( d ) = 1 cm = 1.0 cm-1

Area A 1 cm2

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Cell Constant

Move the electrodes closer and the cell constant lowers

1 cm

1 cm
0.1 cm

Conductivity Cell Constant = Length =( d )= 0.1 cm = 0.1 cm-1

Area A 1 cm2

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Today’s Concentric Electrodes

OUTER
ELECTRODE

INNER INSULATOR
ELECTRODE

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Cell Constant

 Resistivity = Resistance/(d/A)
 Conductivity = 1/Resistivity
18.2 MΩ-cm = 0.0550 S/cm
1.0 MΩ-cm = 1.0 S/cm
0.33 MΩ-cm = 3.0 S/cm

All done – right?

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Electrical Characteristics of Measurement

An applied DC voltage will result in collection of ions at each

electrode
 This process immediately reduces the flow of current, interfering with the
measurement
– This is polarization, resulting in an inaccurate measurement
 Cations go to the negative electrode, Anions go to the positive electrode
– The current does not flow
 What should be done?

Low High
Conductivity

A-C
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Apply an Alternating Current/Voltage

This is done inside the conductivity instrument.

 The ions move toward the opposite electrode

 The current is measured during this short cycle (0.1 to 30 msec)
 The voltage is reversed - repeat

Low High
Conductivity

A-C
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Limitations and Benefits of Conductivity Measurements

 Limitation: Conductivity is non-ion-selective

– Measures everything as conductive
– No information about any specific ion

 Benefit: Conductivity is non-ion-selective

– Measures everything as conductive
– Very sensitive, especially in pure waters
– Excellent to measure concentration if the
chemical process is known

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Check Your Knowledge

Conductivity can measure changes in silica

concentration

A. True
False

?
B.
Knowledge Check

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Check Your Knowledge

18.2 Mohm-cm is identified as the resistivity

of “ultrapure water”. What is the
conductivity of this same water?​

A. 0.056 µS/cm

? Knowledge Check

2
B.

C.
0.058 µS/cm
0.055 µS/cm
D. 0.051 µS/cm

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Check Your Knowledge

There is no difference between conductivity

and resistivity.

A. True
False

?
B.
Knowledge Check

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© 2021 USP
Module 2—Water, Water Systems and Water Chemistry 101

What is conductivity?
• Where does it come from?
• How is it measured?

How is conductivity calibrated?

What are the special properties of

pharmaceutical waters?

What is temperature compensation?

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© 2021 USP
Elements to Calibrate

Meter/Electronics Sensor Cable/Patch Cord

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How Is Conductivity Calibrated in a Measuring System and Why?

 Conductivity is the measurement of a resistance in a volume of fluid; thus, the

resistance measuring circuit and the cell constant shall be verified and adjusted,
if necessary

From USP <645> Water Conductivity

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Sequence of Calibration

In general, the sequence of complete

calibration and/or verification is:
 Calibrate measuring electronics
– Circuitry for temperature measurement—
if used
– Circuitry for conductivity/resistivity
measurement
 Calibrate sensor temperature
device—if used
 Calibrate sensor cell constant

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Sequence of Calibration—Meter Electronics

Rrr

Vrr
AC Vcell

 Calibrate/verify all range resistors and internal circuitry

OR
 Calibrate/verify the appropriate range resistors/ciruitry
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Sequence of Calibration—Meter Electronics

This process calibrates the temperature measurement circuitry.

 General procedure: Step 1a

– Detach sensor from meter
– Attach “traceable temperature simulators”— i.e., resistors
– Compare measured temperature to traceable temperature
– Adjust, if necessary, using meter firmware
– Repeat as needed for temperature circuit

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Sequence of Calibration – Meter Electronics

This process calibrates the conductivity measurement circuitry

 General procedure: Step 1b  Transmitter can be

– Attach "traceable resistance simulators" to
calibrated:
simulate a conductivity/resistivity
‒ On-site using your calibrator
– Compare measured resistance to traceable resistors
resistance
‒ On-site using supplier
– Adjust, if necessary, using transmitter calibrator resistors
firmware
‒ At supplier factory
– Repeat as needed for each conductivity
circuit ‒ At calibration laboratory

 Follow protocols from supplier and ‒ By metrology department or

use recommended values service technicians

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Sequence of Calibration—Temperature Sensor

This process calibrates the temperature sensor

 General procedure: Step 2
– Using a reference temperature system, compare measured temperature to reference
temperature
• Use temperature bath or other reference system
• Ice-water, boiling water?
– Adjust, if necessary, using transmitter firmware. The “adjustment” is made to determine
a new calibration factor(s). No physical adjustment is usually required.
– Enter new calibration factors into transmitter, if necessary
 Follow protocols from supplier
 Calibration in the range of normal operation may not be necessary
– Depends on temperature device
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Sequence of Calibration—Cell Constant

This process calibrates the cell constant

 General procedure: Step 3

– Use calibrated transmitter
– Using a reference conductivity system, compare measured conductivity to reference
conductivity
– Adjust, if necessary, using meter firmware. The “adjustment” is made to determine a new cell
constant. Not a physical adjustment.
– Enter new calibration factors into meter, if necessary

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Sequence of Calibration—Cell Constant

 A cell constant requires a single-point calibration

– No zero/span
 Follow protocols from supplier
 Calibration in range of normal operation MAY NOT be necessary
– Depends on meter/sensor capability

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Traditional Sensor Calibration Methods
Calibrate in a solution vs. a
reference sensor
- In the same fluid
- In the same container
- At the same temperature
- Compensation disabled
Calibrate in a solution of
known conductivity
- Procure solution of known conductivity
- Prepare solution of known conductivity,
i.e., ASTM D1125 standard method
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Standard Conductivity Solutions

I bought a “standard” conductivity solution, but whenever I use it to verify the cell
constant, they never agree. I always have to re-calibrate.

Nearly 20%
difference!!!

“Standard
Solution”

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Standard Conductivity Solutions

Conductivity @ Uncertainty
Standard 25°C (µS/cm) Composition (µS/cm) (%)

ASTM D1125 Solution D 146.93* KCl in Water 0.3 0.2

ASTM D1125 Solution C 1408.8* KCl in Water 1 0.07
NIST SRM 3198 5 KCl in 30% Propanol 0.12 2.4
NIST SRM 3199 15 KCl in Water 0.12 0.8
NIST SRM 3191 100 KCl in Water 0.24 0.24

Ultrapure Water at 15°C 0.03138** Ultrapure Water, CO2 free 0.00008 0.25
Ultrapure Water at 25°C 0.05501** Ultrapure Water, CO2 free 0.00013 0.25
Ultrapure Water at 40°C 0.11301** Ultrapure Water, CO2 free 0.00028 0.25

* "Standard Test Method for Electrical Conductivity and Resistivity of Water", American Society for Testing and Materials, D1125-95, 100 Barr Harbor Drive, W. Conshohocken, PA, 19428-2959
(1995).
** Truman S. Light, Stuart Licht, Anthony C. Bevilacqua, and Kenneth R. Morash, “The Fundamental Conductivity and Resistivity of Water”, Electrochemical and Sold-State Letters, 8 (1) 2005.
** K.R. Morash, R.D. Thornton, C.H. Saunders, A.C. Bevilacqua, and T.S. Light, "Measurement of the Resistivity of High Purity Water at Elevated Temperatures", Ultrapure Water, 11(9), pp. 18 26,
December, 1994.

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Long Term Cell Constant

Cell constants do not change over long periods of time!

0.1100
0.1080 18.2 Mohm-cm at 25°C
40 Mohm-cm at 10°C
0.1060 10 Mohm-cm at 37°C
Cell Constant (/cm)

ASTM Solution D at 146.93 uS/cm

0.1040 ASTM Solution C at 1408.8 uS/cm
0.1020 Average

0.1000
0.0980
0.0960
0.0940
0.0920
0.0900
Mar-95 Dec-95 Jun-96 Jan-97 Feb-98 Feb-99 Feb-00
Calibration Date

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How Often to Calibrate

Cell constants do not change over long periods of time!

0.110

0.108

0.106
Cell Constant (1/cm)

0.104

0.102

0.100

0.098

0.096

0.094

0.092

0.090
Jul-98 Dec-99 Apr-01 Sep-02 Jan-04 May-05 Oct-06
Calibration Date

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© 2021 USP
Module 2—Water, Water Systems and Water Chemistry 101

What is conductivity?
• Where does it come from?
• How is it measured?

How is conductivity calibrated?

What are the special properties of

pharmaceutical waters?

What is temperature compensation?

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Pharmaceutical Waters are Unique

 Dissolves all gases: N2, O2, CO2, etc.

 Very inert to all gases: no reactivity EXCEPT

H2O + CO2 → H2CO3 → H+ + HCO3-

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Pharmaceutical Waters Are Unique

 At 300 ppm CO2 in the air, this is ~300 ppb CO2 dissolved in water
 <0.1 S/cm water (measured inside the pipe) will result in ~0.8–1.2 S/cm with
no other impurities in the water
1.2

1.0
Conductivity ( S/cm)

0.8

0.6 off-line 2
off-line 1
0.4 on-line 2
on-line 1
0.2

0.0

0 5 10 15 20 25 30 35 40 45 50

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© 2021 USP
Module 2—Water, Water Systems and Water Chemistry 101

What is conductivity?
• Where does it come from?
• How is it measured?

How is conductivity calibrated?

What are the special properties of

pharmaceutical waters?

What is temperature compensation?

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What Is Temperature Compensation?

 The ability to adjust a temperature-dependent physicochemical measurement to

a new value at a universally accepted reference temperature—i.e., 25°C

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Effect of Temperature on Conductivity

Specific conductance (efficiency) of ions varies with temperature

700
H+
Specific Conductivity (S-cm^2/mole)

600 OH-
Cl-
500 NH4+
Na+
400 HCO3-

300

200

100

0
0 10 20 30 40 50 60 70 80 90 100
Temperature (°C)

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Effect of Temperature on Conductivity

Dissociation constant of H2O varies with temperature

1E-12

1E-13
Kw

1E-14

1E-15
0 10 20 30 40 50 60 70 80 90 100

Temperature (°C)

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Effect of Temperature on Conductivity

The conductivity of pure water increases with temperature

0.8

0.7
Conductivity ( S/cm)

0.6

0.5

0.4 0.055 S/cm at 25°C

18.2 M-cm at °C
0.3

0.2

0.1

0
0 10 20 30 40 50 60 70 80 90 100
Temperature (°C)

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Check Your Knowledge

Temperature compensation for conductivity

is best used for process control
measurements​.
.
A. True

? Knowledge Check

4
B. False

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Check Your Knowledge

Conductivity sensors shall be calibrated

every:

A. Daily

? Knowledge Check

5
B.

C.

D.
Once a Week
Once a month
Based on supplier recommendations
E. All of the above

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Use Temperature Compensation for Process Control

Why make a “temperature-compensated” conductivity

measurement?

Process Control
 Eliminates the temperature effect on a measurement
 Provides a fixed threshold for controls/alarms
 Provides a universal reference point, i.e., 0.055 S/cm (18.2 M-cm) for
ultrapure water at 25°C

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Temperature Comp—Process Control

 Example: Water conductivity increases from 0.068 mS/cm uncompensated (14.7

M-cm) at 15°C to 0.500 mS/cm (down to 2.00 M-cm) at 80°C
 Is the water more or less “pure”?
 A more
‒ 0.068 mS/cm at 15°C conductive hot
solution can be
• Equivalent to 0.100 mS/cm at 25°C more pure than a
less conductive
• TDS = 20.7 ppb NaCl
cold solution
‒ 0.500 mS/cm at 80°C

• Equivalent to 0.069 mS/cm at 25°C

• TDS = 6.5 ppb NaCl

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USP <644> Conductivity of Solutions

100% harmonized test with EP and JP

 Does not replace USP <645> Water Conductivity

 Intended for general conductivity use applications
 Official 2019

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USP <1644> Theory and Practice of Electrical Conductivity

 Measurements of solutions
 Published as proposal in PF 37(2), March 2011
 Intended for general conductivity use applications
 Does not replace <645> Water Conductivity
 Official in USP 35–NF20 Supplement 1, 08-01-2012

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USP <1644> Theory and Practice of Electrical Conductivity

 Introduction  Calibration
 Theory of Operation – Instrument Calibration

– AC Measurement Methods – Temperature Measurement and Sensor

Calibration
– Units of Expression
– Cell Constant Calibration
– Cell Constant Determination
 Operational Considerations
– Temperature Compensation
– In-Line, At-Line, and Off-Line Measurements
 Operational Considerations
– Sample Preparation and Off-Line Measurement
– System Components
– In-Line Measurement
– Materials of Construction
– At-Line Measurement
– Other Considerations

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USP <1644> Theory and Practice of Electrical Conductivity

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Summary

 Ions are a class of chemical

impurity that needs to be controlled
 Conductivity is NOT ion-specific
 How to properly calibrate a
conductivity measurement system
 Effect of temperature on
conductivity
 Temperature compensation

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