Simple conductivity sensors are constructed of an insulating material imbedded with platinum, graphite, stainless steel or other metallic pieces. These metal contacts serve as sensing elements and are placed at a fixed distance apart to make contact with a solution whose conductivity is to be determined. The length between the sensing elements, as well as the surface area of the metallic piece, determine the electrode cell constant, defined as length/area. The cell constant is a critical parameter affecting the conductance value produced by the cell and handled by the electronic circuitry.
A cell constant of 1.0 will produce a conductance reading approximately equal to the solution conductivity. For solutions of low conductivity, the sensing electrodes can be placed closer together, reducing the length between them and producing cell constants of 0.1 or 0.01. This will raise the conductance reading by a factor of 10 to 100 to offset the low solution conductivity and give a better signal to the conductivity meter. On the other hand, the sensing electrodes can be placed farther apart to create cell constants of 10 or 100 for use in highly conductive solutions. This also produces a conductance acceptable to the meter by reducing the conductance reading by a factor of 10 to 100.
In order to produce a measuring signal acceptable to the conductivity meter, it is highly important that the user choose a conductivity electrode with a cell constant appropriate for his sample. The table below lists the optimum conductivity range for cells with different cell constants.
Cell Constant
OptimumConductivityRange
0.01
0.055 - 20 ¥ìS/cm
0.1
0.5 - 200 ¥ìS/cm
1.0
0.01 - 2 mS/cm
10.0
1 - 200 mS/cm
Effects of polarization
When a DC voltage is applied across the electrodes of a conductivity cell, the ions present in solution will be discharged onto the electrodes and by surrendering or accepting electrons, be changed into molecular form. The flow of ions will then virtually cease within a very short time, and consequently, the current will decrease to virtually zero. Therefore, an AC voltage is used for conductivity measurements. Polarization, however, can still actually take place during a half cycle of one polarity, causing a space charge buildup around the electrodes, resulting in a loss of current flow. In addition to polarization effects, conductivity cells with higher cell constants require long, narrow passages to obtain these constants, which make the electrode contacts more susceptible to coating by oils, slurries, or sludges commonly found in streams of high conductivity.
Platinization
Platinization, or depositing a layer of black platinum on the electrode cells, results in a decreased polarization resistance. The platinum black catalyzes the electrochemical reaction rate, reducing the current density on the electrode cells and the reduction overvoltage for H+ ions.
How 4 cell conductivity probe eliminates polarization and contact coating effects
The 4 cell conductivity probe consists of 4 bands along a measuring column or sets of concentric rings opposite each other. An AC voltage is applied across the two outermost bands, which causes a current flow through the measuring cell. Located between this pair of electrodes is a second pair of bands. These bands measure the voltage generated across the liquid . The measured voltage across the outer bands is compared with the voltage measured by the inner bands. Any difference between the measured voltages of the two pairs of bands (whether the conductivity of the solution changes, or changes due to polarization or coating effects) initiates correcting action for the voltage across the outer bands. The correcting action remains until the current through the cell will generate a voltage across the outer bands which equal the voltage between the inner bands. Therefore, the four-band conductivity cell can correct for any fouling or polarization which may occur.
Choice of Conductivity Cell Design: 2-Cell or 4-Cell?
How 2-Cell and 4-Cell Electrodes Compare
-- > 2-Cell Electrodes Offer:
-- > 4-Cell Electrodes Offer:
Reduced cost of purchase and easy maintenance Direct access to cell plates facilitates cleaning.
Improved accuracy over a wide range The improved circuitry eliminates error due to polarization effect. Analysts achieve accurate calibration with just one standard.
Compatibility with sample changers Applications requiring a sampler changer will do better with a 2-electrode cell, which requires minimal insertion depth - allowing quick readings.
Flexibility for high or low range measurement One cell and one calibration provides testing capability over several decades of conductivity.
-- > Limitation of 2-Cell Electrodes:
-- > Limitation of 4-Cell Electrodes:
MeasurementRange Accurate conductivity measurement range tops out at about 50 mS/cm.
Critical Minimum Immersion Depth Minimum immersion depth is 3 to 4 cm.
Operating Instructions
Before use, soak the conductivity electrode in distilled or deionized water for 5 to 10 minutes. Connect the conductivity cell to the conductivity meter and follow the meter manual instructions for standardizing the cell for use at a given temperature. Rinse the conductivity cell sensing elements with distilled or deionized water between samples. Note: Each conductivity cell has a cell constant which is predetermined by the manufacturer and often indicated on the electrode upon shipment. The cell constant may change slightly during shipping and storage and should be remeasured on the user's conductivity meter before initial use. Measure the cell constant according to the meter instruction manual. Because temperature has a large effect on conductivity measurements allow probe to sit in solution until a stable temperature reading is obtained before taking measurements.
Cleaning
The single most important requirement of accurate and reproducible results in conductivity measurement is a clean cell. A dirty cell will contaminate the solution and cause the conductivity to change. Grease, oil, fingerprints, and other contaminants on the sensing elements can cause erroneous measurements and sporadic responses.
Cleaning Methods
1. For most applications, hot water with domestic cleaning detergent can be used for cleaning. 2. For lime and other hydroxide containing solutions, clean with a 5-10% solution of hydrochloric acid. 3. For solutions containing arganic fouling agents (fats, oils, etc.), clean probe with acetone. 4. For algae and bacteria containing solutions, clean probe with a bleach containing liquid.
Clean cells by dipping or filling the cell with cleaning solution and agitating for two or three minutes. When a stronger cleaning solution is required, try concentrated hydrochloric acid mixed into 50% isopropanol. Rinse the cell several times with distilled or deionized water and remeasure the cell constant before use.
Storage
It is best to store cells so that the electrodes are immersed in deionized water. Any cell that has been stored dry should be soaked in distilled water for 5 to 10 minutes before use to assure complete wetting of the electrodes.
Some platinum conductivity cells are coated with platinum black before calibration. This coating is extremely important to cell operation, especially in solutions of high conductivity. Electrodes are platinized to avoid errors due to polarization. Cells should be inspected periodically and after each cleaning. If the black coating appears to be wearing or flaking off the electrodes or if the cell constant has changed by 50%, the cell should be cleaned and the electrodes replatinized.
Replatinizing
The platinum electrode should first be cleaned thoroughly in aqua regia being careful not to dissolve the platinum. If cell remains too long in aqua regia the platinum elements will dissolve completely. Prepare a solution of 0.025 N HCl with 3% chloroplatinic acid (H2PtCl6) and 0.025% lead acetate. Connect the cell to a rheostat or 3-4 V battery to which a variable resistor has been connected. Immerse cell in the chloroplatinic acid solution and electrolyze at 10 mA/cm for 10-15 minutes. Reverse the polarity to the cell every 30 seconds until both electrodes are covered with a thin black layer. Disconnect the cell and save the platinizing solution. It may be reused many times and should not be discarded as it is expensive to make. Rinse the electrode with tap water for 1 to 2 minutes, followed by distilled or deionized water. Store in distilled or deionized water until ready for use.