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Iwc 06-29 Gray Conductivity PDF
Iwc 06-29 Gray Conductivity PDF
ABSTRACT: Conductivity has been the simplest, oldest, most common, most reliable and lowest cost
measurement used for determining water purity. Nevertheless, this lowly measurement has provided the
means for protecting and assuring efficient operation of billions of dollars worth of power and steam
generation equipment throughout the world for over three-quarters of a century. Recent innovations in
measurement accuracy, temperature compensation, and sample conditioning have enabled this basic
detection method to provide more information and to expand its use even further. From the simplest TDS
meter to the most sophisticated ion chromatograph, conductivity measurement is the core technology.
The widespread use of this measurement often outpaces the understanding of it. Provided here
are the fundamentals and application of conductivity measurement as used in power and steam
generation, including ionic conductance, cell constant, measuring techniques and temperature effects. In
addition, various means of sample conditioning are discussed, covering the measurements of cation
conductivity, degassed cation conductivity, pH and CO2 calculations and even TOC (total organic carbon)
measurements. It is hoped this discussion will assist those applying conductivity measurement in any of
its incarnations to have a greater understanding and to obtain better results.
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Equivalent Ionic Conductances
350
300
250
S cm /equivalent
200
150
2
100
50
0
H+ K+ NH4+ 1/2Ca++ Na+ OH- 1/2SO4-- Cl- HCO3- Acetate-
1 cm
1 cm
1 cm
Figure 2a - Cell Constant Derivation Figure 2b - Coaxial Conductivity Sensor
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Presented at the 67th Annual International Water Conference, Engineers Society of Western Pennsylviania, Pittsburgh, Oct 2006
ASTM D1125
Primary Standard Standards Lab Production Cell
and Pure Water Cell Constants Constants
at 15, 25, 40 °C
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verification procedure. Small volume flow exchangers. Conductivity also responds to the
chambers should be used to produce enough treatment chemicals intentionally added.
flow velocity that particles are carried through
the sensor and discharged. If there is some Specific (direct) conductivity measurement in
accumulation, sensors should be cleaned with high pressure boiler cycles is typically
dilute acid on a schedule determined by dominated by treatment chemicals such as
experience. Sample line filters are not ammonia, phosphates, amines, etc. at ppm
recommended since the filtered particles would concentrations which should be well above the
accumulate and act as an ion sponge, greatly ppb concentrations of any contaminants.
slowing response downstream. Therefore, specific conductivity, often with
Cell constant re-verification is also corroboration by pH, is generally used to monitor
necessary. A convenient on-site procedure is and control treatment chemical concentrations.
desirable. This can be done using a "plant
standard" sensor that is kept clean and used Cation (acid) conductivity is the technique of
only for such verifications. A comparison can be continuously conditioning the sample by passing
made using a portable system with the plant it through a hydrogen form cation exchange
standard sensor in a temporary flow chamber cartridge. It enhances the sensitivity to
piped in series with the sensor being verified. contaminants by two means:
However, the standard sensor itself must be • Ammonia or amines that are intentionally
periodically calibrated. It can be returned to the present at ppm levels are removed. This
manufacturer for re-certification or verified in- eliminates their high conductivity. The lower
house. Instruments that provide wide range of ppb concentrations and conductivity of
measurement are most convenient for this. contaminants can then be “seen” by the
Some instrumentation has been measurement.
validated to measure accurately from pure water • Contaminant corrosive salts are converted
to well over 147 µS/cm, the lowest of the ASTM to their respective acids which are typically
standard solutions, with a single cell constant.[5] three times as conductive as the original salt
With such a system, direct calibration is greatly because of the highly conductive hydrogen
simplified. Despite the gap between the ion.
calibration point and the range of measurement, This simplicity and detection sensitivity
this provides the best accuracy. Standards lower have made cation conductivity the most widely
than about 100 µS/cm have too high an used measure of contamination in the cycle. The
uncertainty (as a percentage of their value) due upper left of Figure 5 illustrates the specific
to variable contamination from carbon dioxide in conductivity sample containing the ammonia and
air as well as the container. This uncertainty traces of sodium chloride and bicarbonate as
would generate much larger errors than those typical contaminants. It has a relatively high
caused by the difference between calibration conductivity due to the amount of ammonia
point and measurement range. Conductivity present, represented by the left bar of Figure 6.
standard solutions are available from many The conductivity due to sodium chloride (or
sources. Care should be taken in selecting and other contaminants) is almost insignificant. The
using standards to obtain reliable results. sample passes through the cation exchanger
and the resin “R” retains the ammonia, sodium
CONDUCTIVITY APPLICATIONS and any other cations, but always with an
excess of resin in the hydrogen form near the
Conductivity measurement responds to outlet. The exiting sample consists of very dilute
all ionic contaminants in a sample, whether they hydrochloric, carbonic (and other) acids and
are minerals or dissolved gases such as carbon yields the cation conductivity value represented
dioxide (in the form of carbonic acid, bicarbonate by the middle bar in Figure 6. A comparison of
or carbonate). Contaminants come from many the two bars shows the enhanced sensitivity for
sources. They can be deionizer regenerant contaminant detection noted above.
chemicals or other materials leaching from Although cation conductivity is widely
inadequately rinsed or fouled resins, air applied, there has been little standardization of
(including CO2) not completely removed by the cation exchange cartridge and this can add
deaerators, carry-over from drum boilers or many variables to the measurement. In
leaks from condensers or other heat particular, the sample flow velocity through the
cartridge must be high enough to promote
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turbulent flow and good exchange. If the technique have been defined in an ASTM
exchange is not complete, the measurement can standard.[6]
be ambiguous. Reasonable guidelines for the
Cation
H , Cl , CO2, HCO3-, OH-
+ -
3
Conductivity (µS/cm)
NH3
1
NaCl HCl HCl
CO2 CO2
0
Specific Cation Degassed Cation
Degassed cation conductivity is useful in drive off the carbon dioxide, with a sparging
plants where carbon dioxide is present in the scheme which flows pure nitrogen gas across a
sample and cation conductivity limits are thin film of the sample or with a membrane
especially low. A degas unit allows contactor that pulls the carbon dioxide through a
measurement of cation conductivity with the membrane. Recent studies have been made on
carbon dioxide removed as shown on the right the performance of “reboilers” that showed good
side of Figure 5. Carbon dioxide is results. [7] One evaluation compared
acknowledged to be far less corrosive than other performance of reboiler, nitrogen sparger, and
contaminants. Degassing can be done with a membrane systems for carbon dioxide removal
“reboiler” which heats the sample to boiling to and they all performed reasonably well.[8]
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Where a reboiler is used and the sample is effects can produce temperature coefficients as
measured near 100 °C, extremely accurate high as 5 to 7% of conductivity value per °C.
temperature compensation is required. Some Because of this, guidelines and specifications
systems re-cool the sample to near 25 °C for reference conductivity values to 25 °C which
this reason. Although not a precise dictates sample temperature control and/or
measurement, degassed cation conductivity compensation. The relationship is shown in
does serve a very useful purpose. Figure 7, for neutral salt contaminants
exemplified by sodium chloride. Conductivity
TEMPERATURE COMPENSATION increases with increasing amounts of sodium
chloride. However, the temperature coefficient
Temperature Compensation is required (slope) of the curves increases with decreasing
because conductivity is greatly influenced by sodium chloride concentration. Also, it can be
temperature. All dissolved ions become more seen that at conductivity values above 5 µS/cm,
mobile and conductive at higher temperatures the ionization of the water is insignificant and all
largely because water becomes less viscous. curves above that are parallel at about 2% per
The increase is at a rate of approximately 2% of °C. Below that, the non-linearity with both
conductivity value per °C for most ions. In concentration and temperature requires
addition, in pure waters the increasing ionization specialized temperature compensation. It should
of the water itself with temperature is be noted that very few laboratory instruments
significant—there are more hydrogen and have more than rudimentary 2% per °C
hydroxide ions to conduct at higher temperature compensation that is unsuitable for
temperatures. The combination of these two low conductivity samples.
2289 ppb
1131 ppb
Conductivity (µS/cm)
1.00
Resistivity (Mohm-cm)
437 ppb
1
2 06 ppb
90 ppb
0.10 10
21 ppb
0 p pb
NaCl Concentrations
0.01 100
0 10 20 30 40 50 60 70 80 90 100
Temperature (°C)
Figure 7 – Figure 7 - Temperature Effects on Pure Water with Neutral Salt Contamination
High purity water compensation has solutions. The combination of these independent
traditionally been recognized as consisting of effects was quantified decades ago by General
two separate components: the properties of the Electric for use with nuclear boiling water reactor
pure water and the properties of the impurities in (BWR) measurements where no treatment
the water. This is appropriate for neutral salt chemicals were added. It must be noted that this
impurities since the ionization of water changes compensation is appropriate only for BWR
only with temperature, not with dilute salt samples and for polished makeup water where
concentration. Similarly, the mobility of salt ions low levels of neutral salts are the anticipated
varies with temperature, independent of the contaminants.
ionization of water. A quick visualization of these
effects is given by equations 1 and 2 which take Conventional pure water sample
place independently of each other in very dilute H2O ↔ H+ + OH- (1)
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NaCl → Na+ + Cl- (2) conductivity samples because the hydrogen ion
has the dominant concentration and the
dominant ionic conductance. The anion is of
secondary importance. Thus sulfuric, formic,
CATION CONDUCTIVITY TEMPERATURE acetic, carbonic and other acids would have
COMPENSATION essentially the same conductivity temperature
characteristics.
Of greatest importance is the The first cation conductivity temperature
temperature compensation accuracy of cation compensation was developed using the best
conductivity which has become more critical with curve matching that could be developed at that
the wide acceptance of equilibrium phosphate time.[9] In the intervening years, a number of
and oxygenated treatment chemistries. The other attempts have been made at providing this
benefits of both of these treatments depend compensation but most have failed to achieve
heavily on maintaining very low cation reasonable accuracy. A very close curve match
conductivity levels. to hydrochloric acid in pure water across the full
The challenge of pure water ranges of temperature and concentration was
temperature compensation is to provide finally developed at Thornton. A comparison of
conductivity readout referenced to 25 °C the compensation of several instrument
regardless of the actual sample temperature. algorithms, with hydrochloric acid data as the
This can eliminate the cost of expensive and reference, is given in Figure 8. A vast
occasionally unreliable secondary sample improvement was achieved, indicated by the
cooling equipment and can preserve the results with Instrument E.[10] It is apparent that
measurement if a chiller fails. temperature compensation is by far the greatest
source of error in cation conductivity
Cation conductivity sample measurement with most instruments installed in
U.S. power plants today.
H2O ↔ H+ + OH- (3)
Temperature compensation algorithms
HCl → H+ + Cl- (4) have also been developed for specific
conductivity samples dominated by ammonia or
A cation conductivity sample behaves amines, and various instruments were
differently from makeup water. It has had evaluated. Similar wide variations in
ammonia and/or amines removed and any salts performance were again observed.[11]
converted to acids as noted previously. The While temperature compensation with
ionization of acids and water cannot be neatly accurate algorithms can eliminate substantial
separated for compensation since they have the errors in the measurement, it should be stressed
hydrogen ion in common. See equations 3 and that sample temperature is still important. Since
4. The additional hydrogen ions from the acid the sample first passes through a cation
suppress the hydroxide ion of water. This exchange cartridge, the consistent performance
interaction between water and acid ionization of that exchange is critical. The flow rate and
and its variation with temperature require an temperature ranges of the sample and the
entirely different approach to temperature dimensions of the cartridge, as well as the type
compensation. The relationship for of resin can all influence cation conductivity
compensation is much more complex and has results. Note that the cation conductivity
pushed the limits of mathematical modeling for a temperature compensation algorithm is also
number of years. The standard is to be able to appropriate for degassed cation conductivity
compensate trace hydrochloric acid in pure since carbonic is just one more of the acids that
water across the ranges of concentration and may be present and all have similar temperature
temperature to obtain the value at 25 °C. effects.
Hydrochloric acid is representative of cation
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% Error
25
20
15
10
5
0
-5
-10 Instrument A
Instrument B
-15 Instrument C
Instrument D
-20
Compensated Conductivity Error (%) Instrument E
-25
0 10 20 30 40 50 60 70 80 90 100
Temperature (°C)
-8-
operation goes well outside normal operating conditions outside the range for accurate pH
conditions. calculation as well as conditions exceeding cycle
To eliminate this risk, multi-channel, chemistry guidelines.
multi-parameter instrumentation can measure The availability of both calculated and
specific and cation conductivities, compute pH electrode pH measurements allows more
from them, and simultaneously measure from a accurate calibration of the electrode
pH electrode as shown in Figure 9. This kind of measurement when operation is within the
instrumentation covers both situations: it conditions for accurate computation of pH. The
provides highly accurate calculated pH electrode system should previously have been
measurement under normal conditions and can calibrated at two points using buffer solutions to
give a warning based on a pH electrode set up the span response. The final one-point
measurement when conditions become trim calibration eliminates variations in electrode
abnormal. diaphragm/junction potential in buffer solutions
The multi-parameter instrument can also and can easily be done more frequently. It
display and alarm on the difference between the greatly enhances the accuracy, reliability and
calculated and the measured pH values. This diagnostic capability of the electrode
kind of diagnostic can identify the need for pH measurement, as well as saving considerable
electrode maintenance or calibration, or warn of time.
Figure 9 - Two pages of the display of a multi-parameter instrument configured with sensors for Specific,
Cation and Degassed Cation Conductivity plus a direct pH electrode
CALCULATED CARBON DIOXIDE & ANIONS tables in memory easily makes the conversion to
FROM CONDUCTIVITY display, alarm and output ppb concentrations of
chlorides or sulfates.
As noted previously, plants may have
carbon dioxide present in steam and condensate TOTAL ORGANIC CARBON FROM
samples and it is worthwhile to distinguish it CONDUCTIVITY
from more corrosive contributors to the cation
conductivity. Degassed cation conductivity Most organics are nonconductive and
provides this. Taken a step further, carbon cannot be sensed by conductivity alone.
dioxide concentration can be inferred from the Nevertheless, organics frequently foul resins
difference between cation conductivity and and can be corrosive and need therefore to be
degassed cation conductivity.[13] Again, detected and removed. The simplest method for
mutiparameter instrumentation can combine the TOC (total organic carbon) detection is based on
measurements by interpolating ASTM standard high intensity ultraviolet oxidation of a
tables in its memory to provide display and continuously flowing sample. Organics are
output signals for carbon dioxide as shown in oxidized to carbon dioxide. Conductivity
the second screen of Figure 9. measurements are made both upstream and
Yet another parameter that can be downstream of the UV lamp. The first
obtained is the anion concentration in the measurement accounts for any conductive
degassed cation conductivity sample. If the contaminants already in the sample while the
conductivity at that point is assumed to be all second measurement detects the increased
due to chlorides or sulfates, a conversion to conductivity due to added carbon dioxide. The
concentration can be done. The same conductivity measurements and their difference
instrumentation including ASTM conversion
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are compared using a correlation curve to than the TOC concentration since the carbon
produce a consistent TOC measurement. dioxide oxidation product would otherwise be
neutralized by alkaline materials and would not
Figure 10 shows the flow path of this produce the expected increase in conductivity.
kind of TOC sensor. Oxidation takes place in a For these reasons this technology has been
quartz coil surrounding the high intensity UV recommended primarily for the clean end of
lamp. It can be seen that the sample flows makeup water treatment systems.[14] However,
continuously and there are no solenoid valves, more recent evaluations on ammonia-treated
moving parts, membranes or reagents. cycle chemistry samples measuring after a
Response time is particularly fast, taking less cation exchange cartridge show promising
than 60 seconds for the sample to pass from the results with a direct conductivity TOC sensor.
inlet to the final conductivity sensor. The simple Clean cation resin allows organics to pass
design reduces maintenance to simple through and lowers the pH and conductivity to a
replacement of the UV lamp on an annual basis. range where this TOC measurement technique
This technology does have application excels. This type of TOC sensor is also available
limitations. It is used only on pure water samples for use with the multiparameter instrumentation
with conductivity 2 µS/cm and TOC of 0.05 - previously noted.
1000 ppb. Also, alkalinity should be much less
REFERENCES
1. Standard Test Methods for Electrical Conductivity and Resistivity of Water, D1125, American Society
for Testing and Materials, W. Conshohocken, PA, 1999.
3. K. Griffiths, D. Gray, A. Bevilacqua, and T. Light, "Ultrapure Water as a Fundamental Standard for the
Calibration of Conductivity/Resistivity Systems," Eskom Power Plant Chemistry Conference,
Johannesburg, South Africa, November, 1997.
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4. T. Light, S.Licht, A. Bevilacqua, K. Morash, “The Fundamental Conductivity and Resistivity of Water,”
Electrochemical and Solid-State Letters, 8 (1) E16-E19, 2005.
5. D. Gray and A. Bevilacqua, "Calibration, Validation and Verification of On-line Conductivity Systems,
NUS International Water Chemistry Instrumentation Seminar, November 1996.
6. Standard Practice for On-Line Determination of Cation Conductivity in High Purity Water, D6504,
American Society for Testing and Materials, W. Conshohocken, PA, 2000.
10. D. Gray and A. Bevilacqua, "Cation Conductivity Temperature Compensation," International Water
Conference, paper IWC 97-48, November 1997.
11. D. Gray and A. Bevilacqua, "Specific Conductivity Temperature Compensation," International Water
Conference, paper IWC-99-76, Pittsburgh, October 1999.
12. D. Gray "pH and CO2 Determinations Based on Power Plant Conductivity Measurements",
International Water Conference, paper IWC-04-43, Pittsburgh, PA, October 2004.
13. “Standard Test Method for Determination of Anions and Carbon Dioxide in High Purity Water by
Cation Exchange and Degassed Cation Conductivity,” D4519, ASTM International, W.
Conshohocken, PA (2005).
14. D. Gray, “Measurement of Organics in Power Plant Make-Up Water Treatment,” PowerPlant
Chemistry, 7(12), December 2005.
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