Conductivity Measurement in High Purity Water Samples below 10 µSIEMENS/cm - IC Controls


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In order to know the conductivity or resistivity of ultra-pure water it is required to do accurate temperature compensation at very low conductivities, e.g. conductivities below 10 µSiemens/cm. An IC Controls 210-C analyzer in High Purity Water configuration (HPW) is intended for use with a 402 side stream sample sensor, or 403 direct insertion/retractable sensor, with a 0.01/cm cell constant.

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Conductivity Measurement in High Purity Water Samples below 10 µSIEMENS/cm - IC Controls

CONDUCTIVITY MEASUREMENT IN HIGH PURITY WATER SAMPLES below 10 µSIEMENS/cm High Purity Water Resistivity/ Conductivity Measurement Ultra-Pure Water without any chemical impurities will still have a conductivity because of the presence of H+ and OH- ions due to the self-ionization of water. Ultra-pure water has a conductivity of 0.055 µSiemens/cm or a resistivity of 18.18 mΩ·cm at 25 °C. In order to know the conductivity or resistivity of ultra-pure water it is required to do accurate temperature compensation at very low conductivities, e.g. conductivities below 10 µSiemens/cm. An IC Controls 210-C analyzer in High Purity Water configuration (HPW) is intended for use with a 402 side stream sample sensor, or 403 direct insertion/retractable sensor, with a 0.01/cm cell constant. It will accurately measure the conductivity (or electrical conductivity) or Illustration 1 conductivity of pure water resistivity (electrical resistivity) of pure water samples below 10 µS/cm in continuous flowing samples. Since pure water conductivity measurement is The self-ionization of water is strongly detecting trace amounts of ionic contaminants temperature-dependent. For accurate in the already temperature dependent self- temperature compensation the conductivity of ionizing water, the installation and calibration the pure solvent must be subtracted from that setup must make special provisions to of the solution to determine the conductivity eliminate or reduce any trace contaminants. of the electrolyte. Simply applying a linear Further, the trace contaminants themselves per-degree-Celsius temperature adjustment exhibit variable temperature coefficients in will not give accurate temperature pure water that can rise as high as 7 % per °C. compensation in high purity waters. Some such as NaOH for instance can cause conductivity at trace levels to go negative by Illustration 1 shows the conductivity of ultra- µ suppressing the conductive H +ions with the pure water in Siemens/cm over the range less conductive OH-ions resulting in a reading 0 °C to 100 °C. below that of theoretically pure water. The IC Controls application Notes Issue 4.2 ©IC Controls 2012 IC Controls 210-C analyzer has different certified cell constant, traceable directly to temperature coefficient algorithms to allow the NIST Standard Reference Material 3191 of user to select for neutral salts, acidic, or basic 100 µS/cm. Alternatively IC Controls can samples (as well as the traditional linear % per factory-certify the sensor cell constant with °C). Standard “D” of ASTM method D1125, Since high-purity water contains little 146.93 µS/cm. dissolved material it is like a dry sponge ready To meet ASTM D5391-99 sensor needs, use to soak up any contaminant it meets. an option -73 flowcell to exclude air contact Absorption of carbon dioxide on exposure to with the sample, followed by a sample take-off air will result in carbonic acid formation and point where an additional sensor can be cause a real change in conductivity of up to 2 installed for calibrations. When installed in a to 3 µS/cm. This fact can be readily shared sample line with pH sensors, the demonstrated by taking a beaker of fresh conductivity sensor should be first, because demin water from a laboratory column, with pH reference electrodes will leak KCl into the conductivity electrode inserted and showing sample, thereby raising its conductivity. The less than 0.5 µS/cm, then bubbling conductivity sensor should be located as near compressed air through it and observing the as possible to the conductivity transmitter, to conductivity reading quickly rise to between 2 minimize any effects of electrical noise and 3 µS/cm. Also if dissolved gases are in the interference. Flow sensors can be in any sample, on exposure to air they may escape orientation but should be mounted tip down at (similar to opening a bottle of pop). Similarly an angle anywhere from 15° above horizontal air exposure will allow CO2 and other soluble to vertical, 15° above horizontal is best gases to dissolve into the sample raising the because entrained bubbles will rise to the top conductivity. Clearly, calibrations using open and grit will sink. containers of high purity water will have Stainless steel sample lines are recommended problems that the same samples in for pure water samples to maintain their continuously flowing enclosed tubing should integrity. The sensors can handle pressures up not encounter. to 100 psi. Any sample flow rate will work, however 2 meters per second (6 feet per Designed to meet ASTM D5391- second) has been found to minimize iron oxide 99 and be Traceable to NIST grit buildups. The IC Controls 210-C analyzer together with The low-level sensor signals should be run a model 402 or 403 sensor with cell constant through a dedicated conduit. Take care to route 0.01/cm and -73 flow cell is designed to meet the signal wiring away from AC power lines, the requirements of ASTM D5391-99 for to minimize unwanted electrical interference. Flowing High Purity Water Samples (less than When installing sensor cable in conduit, use 10 µS/cm), when calibrated with A1100161 caution to avoid scraping or cutting the cable NIST traceable 100 µS/cm standard or insulation, the resulting short of the cable’s A1100232 conductivity standard “D” internal driven shield will cause conductivity 146.93 µS/cm. To obtain the full benefits, the errors. Avoid twisting the sensor lead, to user should acquire a copy of the standard and minimize possibilities for broken wire. Sensor ensure sampling and calibration techniques connections need to be clean and tight. used on site meet the requirements of the standard. Pure Water Formula Selection The IC Controls 402-0.01 conductivity sensor Much work has been done over the years to (or the 403) can be provided with factory- IC Controls application Notes Issue 4.2 ©IC Controls 2012 establish the temperature dependence of pure water. Early analog implementations used °C µS/cm MΩ·cm thermistors to achieve temperature 0 0.01165 85.841 compensation, but may not have been very accurate. Current microprocessor technology, 5 0.01661 60.217 such as in the 210-C, allows for accurate, 10 0.02310 43.297 continuous compensation over the entire 15 0.03143 31.820 temperature range 0-100°C. 20 0.04194 23.844 The earliest widely-used pure water equation was developed at the General Electric 25 0.05501 18.180 Vallecitos Nuclear Training Center. This 30 0.07101 14.082 formula still agrees to within 1% with today’s formulas over the range of 15 to 67°C. 35 0.09037 11.065 Illustration 1 shows the temperature 40 0.11351 8.810 dependence of pure water. The conductivity or 45 0.14082 7.101 resistivity of pure water without any impurities 50 0.17269 5.791 is very dependent on temperature. At low temperatures close to 0°C the change in 55 0.20945 4.774 conductivity is about 7% per degree Celsius. 60 0.25140 3.978 Clearly, the implementation of pure water temperature correction is important. Since 65 0.29875 3.347 work in this area is still ongoing, the 210-C 70 0.35164 2.844 analyzer allows the selection of two pure water 75 0.41017 2.438 temperature compensation formulas, ASTM 1125 or later ASTM D5391-99 with selectable 80 0.47438 2.108 TC compensation for Acids or Alkalies or 85 0.54440 1.837 Neutral Salts. 90 0.62046 1.612 ASTM 1125 TC Formula 95 0.70303 1.422 This curve is the default curve implemented in 100 0.79303 1.261 the 210-C analyzer. Work done in the 1980’s led to the development of these generally- Table 1 ASTM 1125 data accepted Pure Water Temperature compensation values, that were included into ASTM standard D 1125-95 (1999). IC Controls application Notes Issue 4.2 ©IC Controls 2012 Later TC Formula Solute Algorithm Selection Ongoing work produced later data published The temperature compensation of high-purity in ULTRA PURE WATER in December 1994. water changes depending on the chemistry of This data presents slightly refined data based the traces of salts or impurities present in it. on new research. To give you the greatest To properly correct for this you should select flexibility possible the 210-C includes this the solute compensation algorithm that best data as a selectable option. matches the chemistry of the water you are measuring. Examples; a) Cation Demineralizer effluent application would use the Acidic algorithm, b) Boiler water with treatment byproduct ammonia would use the Basic °C µS/cm MΩ·cm algorithm, c) Mixed bed polisher product 0 0.01162 86.072 water with only traces of salts left would use the Neutral salt algorithm. 5 0.01659 60.266 10 0.02312 43.256 15 0.03150 31.751 20 0.04205 23.782 25 0.05512 18.143 30 0.07105 14.074 35 0.09022 11.084 40 0.11298 8.851 45 0.13970 7.158 Illustration 2 Additive sample chemistry compensation 50 0.17071 5.858 Illustration 2 shows how significant the non- 55 0.20637 4.846 linear dependence on temperature for the 60 0.24697 4.049 different solute compensation algorithms can be, that are additive to the Pure Water Formula 65 0.29280 3.415 selected above. 70 0.34410 2.906 Temperature has a BIG impact on conductivity 75 0.40110 2.493 readings. At the historical rate, of 2% change 80 0.46392 2.156 per °C, a 25°C temperature shift can produce a 50% error if the reading is not compensated. 85 0.53276 1.877 Since the conductivity of high-purity water has 90 0.60775 1.645 larger, and non-linear, temperature dependence the errors could be huge. For the IC Controls 95 0.68908 1.451 210-C HPW (High Purity Water) analyzer, the 100 0.77697 1.287 default TC correction is Auto, Pure Water Formula for ASTM 1125, Chemical Solute Table 2 Later data, 1994 Algorithm for NaCl (in theory pure water is neutral). Both for high accuracy work and high purity water applications IC Controls recommends the user check the actual IC Controls application Notes Issue 4.2 ©IC Controls 2012 chemicals involved and change the solute Linear TC selection setting if necessary. The historical temperature compensation is Neutral Salt = Default for HPW linear at 2.00%/°C compensation, or can be edited to a different value. The LTCC Linear The 210-C Pure Water Conductivity Analyzer Temperature Compensation Constant can be default temperature compensation is for edited to any desired value. Neutral Salt (in theory pure water is neutral). Samples with a neutral pH close to 7 can select 210-C Start-up Settings the sodium chloride compensation algorithm. In a neutral salt solution the number of The 210-C HPW conductivity analyzer's hydrogen and hydroxyl ions are approximately default assumes a sensor with a cell constant equal. of 0.01/cm which is stored in its memory. By default, the analyzer comes up reading This algorithm is usually satisfactory for conductivity in µS/cm. The cell constant of the monitoring the effluent of mixed bed ion sensor must match the cell constant stored in exchange. Neutral compensation is also the analyzer memory. If other than a 0.01/cm applicable to boiling water reactor water cell constant is used, change the constant samples because they are normally close to stored by the analyzer so that the analyzer will neutral pH. Makeup water and nuclear boiling read properly. water reactor plant water are untreated and neutral mineral traces are the most common contaminants. PURE WATER CALIBRATION Acidic / Cation Effluent Samples TRACEABLE TO NIST Samples with strongly dissociating acid traces Conductivity sensor effective surface areas can such as hydrochloric acid which completely be changed by contact with the process. At dissociates in water should use the acidic high-purity water measurement conditions algorithm. cabling capacitance and resistance sometimes Cation exchangers used by the power industry influence the readings. IC Controls remove chemicals not of interest, and recommends both an air zero calibration and a substitute the far more conductive hydrogen. standard calibration of the conductivity sensor Electronics rinse after etch, also results in an to determine the effective cell constant. This acidic sample, which requires use of acid procedure requires a conductivity or resistivity compensation to achieve accuracy. Cation standard from which the effective sensor cell conductivity analyzers should also use this constant can be determined, or a second solute selection. calibrated sensor and analyzer. The 210-C HPW conductivity sensor analyzer Basic for many Boiler Waters system is most easily calibrated using 100 Samples with strong base such as sodium µS/cm standard conductivity solution. hydroxide which completely dissociates in Alternatively grab-sample analysis verses a water should use the basic algorithm. Boiler previously calibrated reference conductivity water with treatment byproduct ammonia or meter using an in line flow conductivity sensor morpholine would use the basic algorithm. can be used. Ionic movement, and therefore conductivity, is proportional to temperature. The effect is predictable and repeatable for most chemicals, IC Controls application Notes Issue 4.2 ©IC Controls 2012 although unique to each. In High Purity Water Calibration using 100 µS/cm it is of major importance, and IC Controls Standard recommends the user check the application and ensure the appropriate TC Algorithm is in These instructions use an IC Controls use. Calibration using the wrong HPW A1400051 Low Range Conductivity algorithm can incorporate large errors into the Calibration Kit. results. The A1400051 is a calibration kit containing Overall system accuracy is maintained by solutions and items necessary for calibrating. calibrating the sensor and analyzer together in The kit consists of the following items: a standard close to the expected sample Content Description Qty & Part No. concentration. Calibration determines the Size effective cell constant of the conductivity sensor. The cell constant is affected by the Conductivity standard 2 x 500 A1100161 shape of the sensing surface and electrode 100 µS/cm mL surface characteristics. The effective cell Demin water 4 x 500 A1100192 constant will change over time as deposits mL form, and anything else affects either the controlled volume or the effective electrode Syringe 1 x 10 mL A7400031 surface area. Polyethylene 2 x 100 A1100007 When using IC Controls 210-C. Output hold graduated cylinders, mL goes into effect as soon as a calibration is set of 2. started. The output hold will stay in effect Sensor cleaning 1 A1100016 until a) you select sample, b) no key is pressed brush, ¼ inch for 15 minutes, c) the power is interrupted so the analyzer reboots. Instruction sheet The output hold feature avoids false alarms Instructions for A1400051 Low- and erratic signal output caused by a routine calibration. Range Cond. Calibration Kit 1. Set up the calibration supplies where you Selecting a standard; that is plan to do the calibration. Lay out the two Traceable to NIST graduated cylinders, one for span or high- end standard, one for low-end standard. Set Conductivity standards provide the simplest out the sensor cleaning brush, syringe, method of calibrating the analyzer and standards and rinse solutions. conductivity sensor. The standards most commonly used for calibration are: 100 µS/cm 2. Remove the conductivity sensor from the at 25°C (77°F) and ASTM “D” standard. For process and examine it for deposits. Use NIST Traceability, when ordering also specify demin water to flush away any deposits a A1900333 Trace to NIST Certificate, which within the cell measurement area. will provide the full Quality record from the Tenacious deposits may require chemical Standard purchased to the NIST SRM cleaning, see A1400054 Kit. (Standard Reference Material) and their lot 3. Pour approximately 75 mL of 100 µS/cm number(s). high-end conductivity standard into a graduate so it is about three quarters full. Lower the conductivity cell into the graduate. IC Controls application Notes Issue 4.2 ©IC Controls 2012 conductivity standard. Tip: Ensure there are no air bubbles inside The display stops blinking and shows the the cell, they will cause low conductivity conductivity of the standard. readings. Remove by tapping or alternately Note raise / lower the sensor to flush them out. a) It is possible to repeat or restart the 4. With the conductivity cell centered and no calibration at any time. Simply press air bubbles in the cell, monitor the reading Cancel, then Select to restart or to repeat for stability, then calibrate. the calibration. b)If a problem is detected during Note: The reading may gradually change calibration, a caution or error message will while the sensor equilibrates to the standard be displayed.. temperature (this may take several hours). 8. Verify your calibration by: With micro analyzers, the program acts as a) Note the cell constant in menu under cell an expert thermal equilibrium detector and constant, and repeat steps 3)& 4) three flashes its reading until the temperature times, or until three cell constant readings stabilizes. are consistent. b) Rinse the sensor in demin water. c) Check with 10 µS/cm low-end standard at about 10% of scale using the procedure from 3) and 4) above. Calibration Notes • Used conductivity standard should be discarded because exposure to air and contamination causes the conductivity of standards to change. • Make low-end standard by dilution Example: to 100 mL graduated cylinder add 7.5 mL 100 µS/cm standard, then top up to 75 mL to get 10 µS/cm standard. Illustration 3 sensor positioning • CAUTION: low-conductivity water will dissolve CO2 from the air, raising 5. Select from the list, then change the conductivity 1 to 2 µS/cm, plus leach displayed standard value to that of the contaminants in storage from containers, standard you are using. and carry over on the sensor, so 10 µS/cm 6. When using a IC Controls 210-C HPW will likely read 11, 12, or 13 µS/cm Press Right to start the calibration. The (possibly even more). analyzer will display a flashing • If the sensor reads correctly the calibration concentration reading. From here on the and sensor condition are good. If the sensor calibration process is automatic. reads wrong it may have had trapped 7. Acting like an analyzer expert, the analyzer bubbles inside, or traces of 100 µS/cm will wait until the reading has stabilized, standard. Re-test three times, or until three then calculate the cell constant using the readings are consistent; if problem persists, temperature-compensated value of the try chemical cleaning. IC Controls application Notes Issue 4.2 ©IC Controls 2012 • A clean, rinsed and dried conductivity Water), IC Controls recommends use of a sensor should read near zero in air. If it second 210-C HPW analyzer and 402-0.01-73 does not, troubleshoot the sensor, wiring, sensor to determine the actual conductivity of and analyzer. the sample. • Low-conductivity grab samples taken to the 1. Obtain the following materials: a second laboratory for calibration checks are not lab calibrated 210-C HPW and 402-0.01-73 reliable due to CO2 absorption from air. sensor. • CAUTION: Standards less than 10 µS/cm 2. Record the cell constant of the sensor as made in air will dissolve CO2, raising seen by the lab calibrated 210-C HPW conductivity 1 to 2 µS/cm, so are analyzer. The cell constant is displayed by unreliable. Stored demin will also have selecting Cell Constant, in the calibration conductivity readings of 2 or 3 µS/cm due menu. to chemicals dissolved from containers and 3. Tube up the calibration cell (2nd 402) to the should not be used. For 1 µS/cm standards, outlet of your process sensor to get a try first triple rinsing all vessels with representative flowing sample from the sample of less than 1 µS/cm conductivity, process without exposure to air. (In order for then diluting the standard using sample of the procedure to work the sample you are drawing less than 1 µS/cm. must be representative of the sample being measured by the on-line analyzer.) Calibration Using ASTM “D” 4. Record the conductivity/resistivity and ASTM “D” standard with conductivity 146.93 temperature of the sample as displayed by µS/cm at 25 °C can be substituted for 100 the on-line conductivity analyzer. µS/cm standard in the above calibration 5. Measure the conductivity of the sample procedure. When using ASTM “D” Standard using the second 210-C conductivity (P/N A1100232) users may wish to follow the analyzer and record the conductivity procedures outlined in ASTM D1125 and reading and temperature. D5391-99. Note: For accurate results the sample must Calibration by Grab-Sample be at the same temperature and the This modified grab-sample technique is analyzers must use the same temperature quicker and easier if the sensor is not easily compensation method. Allow considerable accessible, and with the high probability that time for the calibration sensor to rinse down pure water samples of less than 10 µS/cm will and equilibration to the sample level (this be changed on exposure to air, it is should be several hours). A stable reading recommended. This procedure describes how close to the on-line sensor reading acts as a to calibrate the analyzer without taking the good indicator. sensor out of the process. To calibrate measure 6. Calculate the new cell constant to be the sample with a second calibrated analyzer entered into the 210-C analyzer using the and flow sensor, similar to ASTM D 5391-99 following formula: for conductivity/resistivity of a flowing high- lab reading purity water sample. Since most portable and new cell const= ×old cell constfield reading laboratory conductivity instruments do not For example, if the 210-C analyzer is have flow sensors and use limited 2% per °C reading 8.2 µS/cm, the cell constant (from temperature compensation (not acceptable step 2) is 0.01/cm, and the reading from the under ASTM D 5391-99 for High Purity second method is 8.9 µS/cm, then the new IC Controls application Notes Issue 4.2 ©IC Controls 2012 cell constant becomes Maintaining High Purity 8.9 new cell const= ×0.01/cm=0.0109/cm Water 8.2 High Purity Water is expensive to produce, 7. Adjust the cell constant to the new value, which makes recovery and contamination e.g. 0.0109/cm as in the example. The cell prevention important. The largest source of constant is adjusted by selecting cell contamination is Heat Exchanger or constant from the menu. Press Enter to go Condenser Leaks. The IC Controls 210-C-C2 into edit mode, then adjust the displayed with two 401-0.1 sensors in ratio mode value to 0.0109. Press Enter again to exit provides notice of a leak (or pinhole) in edit mode process heat exchangers or condensers. 401 Air Zero Calibration Leak Detector sensors are designed for direct in line hot condensate measurement. Locate It is not necessary to repeat “Air” cal every one 401 probe in the line after the heat time a regular calibration is performed. exchanger or condenser and the other in the An air calibration should be performed line before the heat exchanger or condenser. A anytime a new sensor is installed. When a good exchanger or condenser will have a sensor is in air, the conductivity measured by conductivity ratio of 1:1. A leaking exchanger the sensor is expected to be zero. It is not or condenser will develop a 1:1.5 or 1:2 (or uncommon to find some small conductivity more) ratio. You get early early leak detection signal with the dry sensor in air or even with plus you benefit from an indication of how bad no sensor connected at all. This measurement the leak is, so can schedule a sensible repair can be due to background noise, lead wire time. As well as lower cost to maintain your pickup (antenna effect), grounding problems, High Purity Water purity. etc. The air calibration is designed to subtract This same approach can be used to maintain the small errors of this interference signal from any process area that has a single feed line and the real measurement in order to give a true a single return line. zero reading. 1. Do the zero cal on a new sensor and its wiring. 2. Make sure that the sensor is dry before zeroing. The analyzer should be reading a low conductivity value. 3. From the menu select conductivity, calibrate, air zero. The analyzer will show press enter to confirm. 4. When the sensor is ready to be calibrated, press Enter. 5. Press Sample. With the sensor still dry and in air, the conductivity should read 0.00 µS/cm. IC Controls application Notes Issue 4.2 ©IC Controls 2012 To Order the Systems pictured Specify: High Temperature and Pressure, in line High Purity Water Protection, Leak Detection and Side stream High Purity monitoring sample alarm, system components only: system components only: 210-C HPW-1-8-10-20 (Panel Mount Analyzer) or 210-C HPW-1-8-10-20 (Panel Mount Analyzer) or 210-C HPW-1-9-10-20 (Pipe/surface Mount) 210-C HPW-1-9-10-20 (Pipe/surface Mount) handles up to 400 PSIG at 200°C and 402-0.01-72(3M)-73 sensor and 2 only 401-0.1-62-72(3M) sensor Side stream High Purity monitoring sample Side stream High Purity Water Protection, Leak system assembled on a panel: Detection and alarm, sample system assembled on 402-0.01-25-73 integrated pure water sampling a panel: system with 210-C HPW-1-10-20 on a surface 401-0.1-25-76 integrated leak detection sampling panel system with 210-C HPW-1-10-20 on a surface panel Direct insertion in line, but retractable for A1400051 Low Range Conductivity Calibration calibration, High Purity monitoring system Kit. components only: 210-C HPW-1-8-10-20 (Panel Mount Analyzer) or 210-C HPW-1-9-10-20 (Pipe/surface Mount) A1100161 Conductivity standard 100 µS/cm, and 403-0.01-21-22-72(3M) sensor 500ml bottle. A1100232 ASTM “D” Standard, 500ml bottle. A1100192 Demineralized water, 500ml bottle. Direct in line High Purity Water Protection, Leak Detection and alarm, system components only: 210-C HPW-1-8-10-20 (Panel Mount Analyzer) or A1900333 Trace to NIST, Certificates, records 210-C HPW-1-9-10-20 (Pipe/surface Mount) full calibration to NIST SRM and their lot handles up to 400 PSIG at 100°C numbers. or handles up to 250 PSIG at 150°C *(3M)= 3 meter or 10ft special conductivity cable, suggested length, and 2 only 401-0.1-72(3M) sensors can be customized to suit specific need. IC Controls application Notes Issue 4.2 ©IC Controls 2012 IC Controls application Notes Issue 4.2 ©IC Controls 2012