WO2013109816A1 - Low-conductivity contacting-type conductivity measurement - Google Patents

Low-conductivity contacting-type conductivity measurement Download PDF

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Publication number
WO2013109816A1
WO2013109816A1 PCT/US2013/022042 US2013022042W WO2013109816A1 WO 2013109816 A1 WO2013109816 A1 WO 2013109816A1 US 2013022042 W US2013022042 W US 2013022042W WO 2013109816 A1 WO2013109816 A1 WO 2013109816A1
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Prior art keywords
conductivity
voltage
excitation current
contacting
drive frequency
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Ceased
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PCT/US2013/022042
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French (fr)
Inventor
Behzad Rezvani
Jeffrey Lomibao
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Rosemount Inc
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Rosemount Analytical Inc
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Application filed by Rosemount Analytical Inc filed Critical Rosemount Analytical Inc
Priority to ES13702542T priority Critical patent/ES2736050T3/en
Priority to CA2862183A priority patent/CA2862183C/en
Priority to AU2013209704A priority patent/AU2013209704B2/en
Priority to EP13702542.5A priority patent/EP2805154B1/en
Priority to CN201380005980.8A priority patent/CN104067113B/en
Publication of WO2013109816A1 publication Critical patent/WO2013109816A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid

Definitions

  • Liquid conductivity measurement systems are used for the measurement of conductivity of water and aqueous or non-aqueous solutions in environmental, medical, industrial, and other applications where an indication of the ionic content of the liquid is required.
  • Liquid conductivity is measured in a variety of contexts to provide a relatively inexpensive parameter that can be sometimes related to bulk ionic concentration. In situations where a single type of ion is present, the conductivity can actually be related to specific ionic concentration. Even in situations where a number of different ionic compounds are present, the measurement of bulk liquid conductivity can still provide very useful information. Accordingly, there has been widespread adoption and utilization of conductivity measurement by the industry for a variety of different purposes. Given the variety of different applications for such systems, it is expected that some will be employed to provide conductivity measurements for low-conductivity liquids, while others will be employed to provide conductivity measurements for high-conductivity liquids.
  • contact-based conductivity measurement systems typically include a conductivity sensor or cell and an associated conductivity analyzer or meter.
  • FIG. 1 illustrates such a system.
  • a conductivity meter generates an AC current through electrodes of the conductivity cell.
  • the meter then senses the resultant voltage between the electrodes of the cell. This voltage is generally a function of the conductivity of the liquid to which the cell is exposed.
  • the voltage between the electrodes depends not only on the solution conductivity, but also on the length, surface area, and geometry of the sensor electrodes.
  • the probe constant also called sensor constant or cell constant
  • the probe constant is a measure of the response of a sensor to a conductive solution, due to the sensor's dimensions and geometry. Its units are cm “1 (length divided by area), and the probe constant necessary for a given conductivity range is based on the particular conductivity analyzer's measuring circuitry. Probe constants can vary from 0.01 cm “1 to 50 cm “1 and, in general, the higher the conductivity, the larger the probe constant necessary.
  • a method of measuring low conductivity of a liquid sample using a contacting-type conductivity sensor includes applying a first excitation current to a contacting-type conductivity sensor at a first drive frequency. A first voltage response to the first excitation current is determined. A second excitation current is applied to the contacting-type conductivity sensor at a second drive frequency higher than the first drive frequency. A second voltage response to the second excitation current is determined. A conductivity output is provided based, at least in part, on the first and second voltage responses.
  • a system for measuring conductivity of a liquid at or below 100 ⁇ 8/ ⁇ is also provided.
  • FIG. 1 is a diagrammatic view of a contacting-type conductivity measurement system.
  • FIG. 2 is a diagrammatic view of a four-electrode contacting-type conductivity measurement system with which embodiments of the present invention are particularly useful.
  • FIG. 3A is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency Fl.
  • FIG. 3B is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency F2.
  • FIG. 4 is a flow diagram of a method of determining a low-conductivity value in accordance with an embodiment of the present invention.
  • Electrodes conductivity sensors are typically used for high conductivity measurements, but they become excessively nonlinear at low conductivities. Two of the electrodes are used to drive a current through the liquid. The other two electrodes are used to sense the voltage developed across the liquid. Generally a four-electrode conductivity sensor connects to a conductivity analyzer or other suitable instrument via a multi-conductor cable. When measuring low conductivities (100 ⁇ 8/ ⁇ or lower), the source impedance of the solution and the capacitance of the cable distort the voltage waveform and cause significant error in the measurement. The voltage waveform distortion is related to the time constant formed by the source impedance R and the cable capacitance C.
  • a reduction in the measurement frequency is used such that the time constant formed by RC is much smaller than the signal period (T). While reducing the drive frequency can reduce such errors, such an approach may not be suitable for all applications. For example, reducing the drive frequency may introduce additional sources of noise in environments with significant 50/60 Hz AC devices or other sources of low-frequency interference.
  • Embodiments of the present invention generally provide a method of providing a more accurate low-conductivity sensor measurement without the necessity of using a lower drive frequency.
  • a "low-conductivity" value is any value that is equal to or less than 100 ⁇ 8/ ⁇ .
  • the source impedance and the cable capacitance are significant sources of error.
  • embodiments of the present invention can be employed to provide a more accurate conductivity measurement without employing a lower frequency drive current.
  • FIG. 2 is a diagrammatic view of a four-electrode contacting-type conductivity measurement system 10 with which embodiments of the present invention are particularly useful.
  • System 10 includes conductivity analyzer 12 coupled to contacting-type four electrode conductivity sensor 14 through cable 16.
  • Sensor 14 includes a pair of electrodes 18, 20 that contact a liquid.
  • Electrodes 18, 20 are coupled to leads 22, 24 that are connected to voltage measurement terminals 26, 28 of analyzer 12, respectively.
  • Electrodes 18, 20 are also coupled to leads 30, 32 which are coupled to current drive terminals 34, 36 of analyzer 12 through cable 16.
  • the various leads and cable 16 are modeled electrically in FIG. 2 as resistances and capacitances. For example, as the insulation between conductors 38 and 40 changes in cable 16, the capacitance of equivalent capacitor 42 will change.
  • analyzer 12 will drive a current through conductors 38, 40 and thus through electrodes 18, 20.
  • the current flow through the liquid sample will generate a voltage across electrodes 18, 20 which is measured by analyzer 12 at terminals 26, 28.
  • the measured voltage is related, by analyzer 12, to conductivity of the liquid sample, and is communicated to a user or control system.
  • Such communication can be via local display and/or over a process communication loop or segment. Additionally, such communication may occur wirelessly, such as by using wireless process communication in accordance with a wireless process communication protocol such as the WirelessHART® standard as set forth at IEC 62591.
  • Suitable examples of analyzer 12 include that sold under the trade designation Model 1066 Two-Wire Analytical Liquid Analyzer available from Rosemount Analytical Inc, an Emerson Process Management Company, of Irvine California. However, other suitable analyzers can be used in accordance with embodiments of the present invention.
  • FIG. 3A is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency Fl.
  • drive current is shown at trace 50 and the voltage response trace is shown at reference numeral 52.
  • trace 52 has not yet reached its final value before drive polarity switches due to the time constant created by the source impedance R and the cable capacitance C.
  • the excitation currents illustrated in FIGS. 3A and 3B are preferably square waves and also preferably pass the current in opposite directions through the liquid sample via the electrodes of the contacting-type conductivity sensor.
  • FIG. 3B is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency F2, which is higher than Fl.
  • drive current is shown at trace 54 and the voltage response trace is shown at reference numeral 56.
  • trace 56 has reached even less of its final value, in comparison to trace 52, before drive polarity switches.
  • the corrected voltage i.e. the voltage that the trace would arrive at if given enough time
  • the correction value is equal to a constant (K) multiplied by the difference between peak-to-peak voltage 58 and peak-to-peak voltage 60.
  • K a constant multiplied by the difference between peak-to-peak voltage 58 and peak-to-peak voltage 60.
  • K a constant
  • Other functions can also be used in accordance with embodiments of the present invention. For example, three voltage measurements could be obtained at three distinct drive frequencies and the corrected voltage could be determined from an exponential curve fit to calculate the final corrected voltage value.
  • FIG. 4 is a flow diagram of a method of determining a low-conductivity value (at or below 100 ⁇ 8/ ⁇ ) in accordance with an embodiment of the present invention.
  • Method 100 begins at block 102 where a first excitation current is applied to the contacting conductivity sensor. The first current induces a voltage within the liquid sample related to the conductivity of the liquid sample.
  • the voltage response across a pair of measuring electrodes of the sensor is determined. This determination may simply be a measurement of the maximum peak-to-peak voltage observed during application of the first excitation current.
  • a second excitation current is applied to the liquid sample. The second excitation current is applied at a frequency that is higher than the first excitation current.
  • the voltage response of the conductivity sensor to the second excitation current is determined.
  • a conductivity output is provided as a function of the first and second voltage responses.
  • the conductivity output can be based on a corrected voltage (VCORRECTED) that is equal to the voltage response determined during the application of the first excitation current (VFO plus a constant (K) multiplied by the difference in the first voltage response (VF from the second voltage response (VK)-
  • (VCORRECTED) (VFO * K((VFI)- (VF 2 )).
  • an additional third excitation current could be used at yet a higher frequency to determine a third voltage response.
  • the three voltage responses could then be fit to an exponential curve to calculate the final conductivity value.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Measurement Of Resistance Or Impedance (AREA)

Description

LOW-CONDUCTIVITY CONTACTING-TYPE CONDUCTIVITY
MEASUREMENT
BACKGROUND
[0001] Liquid conductivity measurement systems are used for the measurement of conductivity of water and aqueous or non-aqueous solutions in environmental, medical, industrial, and other applications where an indication of the ionic content of the liquid is required.
[0002] Liquid conductivity is measured in a variety of contexts to provide a relatively inexpensive parameter that can be sometimes related to bulk ionic concentration. In situations where a single type of ion is present, the conductivity can actually be related to specific ionic concentration. Even in situations where a number of different ionic compounds are present, the measurement of bulk liquid conductivity can still provide very useful information. Accordingly, there has been widespread adoption and utilization of conductivity measurement by the industry for a variety of different purposes. Given the variety of different applications for such systems, it is expected that some will be employed to provide conductivity measurements for low-conductivity liquids, while others will be employed to provide conductivity measurements for high-conductivity liquids.
[0003] Typically, contact-based conductivity measurement systems include a conductivity sensor or cell and an associated conductivity analyzer or meter. FIG. 1 illustrates such a system. A conductivity meter generates an AC current through electrodes of the conductivity cell. The meter then senses the resultant voltage between the electrodes of the cell. This voltage is generally a function of the conductivity of the liquid to which the cell is exposed.
[0004] The voltage between the electrodes depends not only on the solution conductivity, but also on the length, surface area, and geometry of the sensor electrodes. The probe constant (also called sensor constant or cell constant) is a measure of the response of a sensor to a conductive solution, due to the sensor's dimensions and geometry. Its units are cm"1 (length divided by area), and the probe constant necessary for a given conductivity range is based on the particular conductivity analyzer's measuring circuitry. Probe constants can vary from 0.01 cm"1 to 50 cm"1 and, in general, the higher the conductivity, the larger the probe constant necessary. SUMMARY
[0005] A method of measuring low conductivity of a liquid sample using a contacting-type conductivity sensor is provided. The method includes applying a first excitation current to a contacting-type conductivity sensor at a first drive frequency. A first voltage response to the first excitation current is determined. A second excitation current is applied to the contacting-type conductivity sensor at a second drive frequency higher than the first drive frequency. A second voltage response to the second excitation current is determined. A conductivity output is provided based, at least in part, on the first and second voltage responses. A system for measuring conductivity of a liquid at or below 100 μ8/α is also provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a diagrammatic view of a contacting-type conductivity measurement system.
[0007] FIG. 2 is a diagrammatic view of a four-electrode contacting-type conductivity measurement system with which embodiments of the present invention are particularly useful.
[0008] FIG. 3A is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency Fl.
[0009] FIG. 3B is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency F2.
[0010] FIG. 4 is a flow diagram of a method of determining a low-conductivity value in accordance with an embodiment of the present invention.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[0011] Four electrode conductivity sensors are typically used for high conductivity measurements, but they become excessively nonlinear at low conductivities. Two of the electrodes are used to drive a current through the liquid. The other two electrodes are used to sense the voltage developed across the liquid. Generally a four-electrode conductivity sensor connects to a conductivity analyzer or other suitable instrument via a multi-conductor cable. When measuring low conductivities (100 μ8/α or lower), the source impedance of the solution and the capacitance of the cable distort the voltage waveform and cause significant error in the measurement. The voltage waveform distortion is related to the time constant formed by the source impedance R and the cable capacitance C. In some cases, a reduction in the measurement frequency is used such that the time constant formed by RC is much smaller than the signal period (T). While reducing the drive frequency can reduce such errors, such an approach may not be suitable for all applications. For example, reducing the drive frequency may introduce additional sources of noise in environments with significant 50/60 Hz AC devices or other sources of low-frequency interference.
[0012] Embodiments of the present invention generally provide a method of providing a more accurate low-conductivity sensor measurement without the necessity of using a lower drive frequency. As used herein, a "low-conductivity" value is any value that is equal to or less than 100 μ8/α . As set forth above, for such low measurements, the source impedance and the cable capacitance are significant sources of error. In such instances, embodiments of the present invention can be employed to provide a more accurate conductivity measurement without employing a lower frequency drive current.
[0013] FIG. 2 is a diagrammatic view of a four-electrode contacting-type conductivity measurement system 10 with which embodiments of the present invention are particularly useful. System 10 includes conductivity analyzer 12 coupled to contacting-type four electrode conductivity sensor 14 through cable 16. Sensor 14 includes a pair of electrodes 18, 20 that contact a liquid. Electrodes 18, 20 are coupled to leads 22, 24 that are connected to voltage measurement terminals 26, 28 of analyzer 12, respectively. Electrodes 18, 20 are also coupled to leads 30, 32 which are coupled to current drive terminals 34, 36 of analyzer 12 through cable 16. The various leads and cable 16 are modeled electrically in FIG. 2 as resistances and capacitances. For example, as the insulation between conductors 38 and 40 changes in cable 16, the capacitance of equivalent capacitor 42 will change.
[0014] In operation, analyzer 12 will drive a current through conductors 38, 40 and thus through electrodes 18, 20. The current flow through the liquid sample will generate a voltage across electrodes 18, 20 which is measured by analyzer 12 at terminals 26, 28. The measured voltage is related, by analyzer 12, to conductivity of the liquid sample, and is communicated to a user or control system. Such communication can be via local display and/or over a process communication loop or segment. Additionally, such communication may occur wirelessly, such as by using wireless process communication in accordance with a wireless process communication protocol such as the WirelessHART® standard as set forth at IEC 62591. Suitable examples of analyzer 12 include that sold under the trade designation Model 1066 Two-Wire Analytical Liquid Analyzer available from Rosemount Analytical Inc, an Emerson Process Management Company, of Irvine California. However, other suitable analyzers can be used in accordance with embodiments of the present invention.
[0015] FIG. 3A is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency Fl. When driven at frequency Fl, drive current is shown at trace 50 and the voltage response trace is shown at reference numeral 52. As indicated, trace 52 has not yet reached its final value before drive polarity switches due to the time constant created by the source impedance R and the cable capacitance C. The excitation currents illustrated in FIGS. 3A and 3B are preferably square waves and also preferably pass the current in opposite directions through the liquid sample via the electrodes of the contacting-type conductivity sensor.
[0016] FIG. 3B is a signal chart illustrating voltage response of a contacting-type conductivity sensor when driven at frequency F2, which is higher than Fl. When driven at frequency F2, drive current is shown at trace 54 and the voltage response trace is shown at reference numeral 56. As indicated, trace 56 has reached even less of its final value, in comparison to trace 52, before drive polarity switches. However, leveraging the two voltage responses allows an accurate calculation of conductivity. In one embodiment, the corrected voltage (i.e. the voltage that the trace would arrive at if given enough time) is calculated as the maximum peak-to-peak voltage measured or otherwise obtained on trace 52, indicated at reference numeral 58 added to a correction value. The correction value is equal to a constant (K) multiplied by the difference between peak-to-peak voltage 58 and peak-to-peak voltage 60. This is simply one function that may be used to provide the corrected voltage. Other functions can also be used in accordance with embodiments of the present invention. For example, three voltage measurements could be obtained at three distinct drive frequencies and the corrected voltage could be determined from an exponential curve fit to calculate the final corrected voltage value.
[0017] FIG. 4 is a flow diagram of a method of determining a low-conductivity value (at or below 100 μ8/ΰΐ ) in accordance with an embodiment of the present invention. Method 100 begins at block 102 where a first excitation current is applied to the contacting conductivity sensor. The first current induces a voltage within the liquid sample related to the conductivity of the liquid sample. At block 104, the voltage response across a pair of measuring electrodes of the sensor is determined. This determination may simply be a measurement of the maximum peak-to-peak voltage observed during application of the first excitation current. Next, at block 106, a second excitation current is applied to the liquid sample. The second excitation current is applied at a frequency that is higher than the first excitation current. At block 108, the voltage response of the conductivity sensor to the second excitation current is determined. Next, at block 110, a conductivity output is provided as a function of the first and second voltage responses. For example, the conductivity output can be based on a corrected voltage (VCORRECTED) that is equal to the voltage response determined during the application of the first excitation current (VFO plus a constant (K) multiplied by the difference in the first voltage response (VF from the second voltage response (VK)- Thus, (VCORRECTED) = (VFO * K((VFI)- (VF2)). For better accuracy yet, an additional third excitation current could be used at yet a higher frequency to determine a third voltage response. The three voltage responses could then be fit to an exponential curve to calculate the final conductivity value.
[0018] Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.

Claims

WHAT IS CLAIMED IS:
1. A method of measuring low conductivity of a liquid sample using a contacting-type conductivity sensor, the method comprising:
applying a first excitation current to the contacting-type conductivity sensor at a first drive frequency;
determining a first voltage response to the first excitation current;
applying a second excitation current to the contacting-type conductivity sensor at a second drive frequency different than the first drive frequency;
determining a second voltage response to the second excitation current; and providing a conductivity output based, at least in part, on the first and second voltage responses.
2. The method of claim 1, wherein the second drive frequency is higher than the first drive frequency.
3. The method of claim 2, wherein the conductivity is at or below 100 μ8/α .
4. The method of claim 2, wherein providing a conductivity output includes calculating a correction value equal to a difference between the first and second voltage responses multiplied by a constant.
5. The method of claim 4, wherein the conductivity output is calculated by adding the first voltage response to the correction value.
6. The method of claim 2, wherein the first voltage response is a maximum peak-to-peak voltage measured across the conductivity sensor during application of the first excitation current.
7. The method of claim 6, wherein the second voltage response is a maximum peak-to-peak voltage measured across the conductivity sensor during application of the second excitation current.
8. The method of claim 2, wherein at least one of the first and second excitation currents is a square wave.
9. The method of claim 2, and further comprising:
applying a third excitation current to the contacting-type conductivity sensor at a third drive frequency higher than the second drive frequency;
determining a third voltage response to the third excitation current; and providing a conductivity output based, at least in part, on the first, second and third voltage responses.
10. The method of claim 9, wherein providing the conductivity output includes fitting the first, second and third voltage responses to an exponential curve.
11. The method of claim 2, wherein the method is performed by an analyzer.
12. A system for measuring conductivity of a liquid at or below 100 μ8/α , the system comprising:
a contacting-type conductivity sensor having a plurality of electrodes configured to contact the liquid;
an analyzer coupled to the contacting-type conductivity sensor, the analyzer being
configured to:
apply a first excitation current to the contacting-type conductivity sensor at a first drive frequency;
determine a first voltage response of the contacting-type conductivity sensor to the first excitation current;
apply a second excitation current to the contacting-type conductivity sensor at a second drive frequency different than the first drive frequency;
determine a second voltage response to the second excitation current; and provide a conductivity output based, at least in part, on the first and second voltage responses.
13. The system of claim 12, wherein the second drive frequency is higher than the first drive frequency.
14. The system of claim 13, wherein the analyzer is further configured to:
apply a third excitation current to the contacting-type conductivity sensor at a third drive frequency higher than the second drive frequency;
determine a third voltage response to the third excitation current; and
provide a conductivity output based, at least in part, on the first, second and third voltage responses.
15. The method of claim 14, wherein providing the conductivity output includes fitting the first, second and third voltage responses to an exponential curve.
PCT/US2013/022042 2012-01-20 2013-01-18 Low-conductivity contacting-type conductivity measurement Ceased WO2013109816A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES13702542T ES2736050T3 (en) 2012-01-20 2013-01-18 Conductivity measurement of the low conductivity contact type
CA2862183A CA2862183C (en) 2012-01-20 2013-01-18 Low-conductivity contacting-type conductivity measurement
AU2013209704A AU2013209704B2 (en) 2012-01-20 2013-01-18 Low-conductivity contacting-type conductivity measurement
EP13702542.5A EP2805154B1 (en) 2012-01-20 2013-01-18 Low-conductivity contacting-type conductivity measurement
CN201380005980.8A CN104067113B (en) 2012-01-20 2013-01-18 The conductivity type contact test system of low conductivity

Applications Claiming Priority (4)

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US201261588934P 2012-01-20 2012-01-20
US61/588,934 2012-01-20
US13/743,811 2013-01-17
US13/743,811 US9488611B2 (en) 2012-01-20 2013-01-17 Low-conductivity contacting-type conductivity measurement

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US9488611B2 (en) 2016-11-08
CN104067113A (en) 2014-09-24
ES2736050T3 (en) 2019-12-23
AU2013209704B2 (en) 2015-08-20
EP2805154B1 (en) 2019-05-15
CA2862183C (en) 2018-02-13
US20130187673A1 (en) 2013-07-25
CA2862183A1 (en) 2013-07-25
CN104067113B (en) 2017-03-29
AU2013209704A1 (en) 2014-07-24
EP2805154A1 (en) 2014-11-26

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