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Dissolved Oxygen

Dissolved Oxygen

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Published by: MAX PAYNE on Aug 02, 2010
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Dissolved Oxygen Measurement
Dissolved oxygen is defined as the measure of waterquality indicating free oxygen dissolved in water. Thequantity of dissolved oxygen in water is typicallyexpressed in parts per million (ppm) or milligrams perliter (mg/l). Since oxygen is soluble in water, theamount of dissolved oxygen in water is in the state ofdynamic equilibrium. The solubility of the dissolvedoxygen is proportional to the temperature andpressure of the water.The most common application for dissolved oxygenmeasurement occurs in wastewater treatment.Biochemical breakdown of sewage is achieved bybacterial attack in the presence of oxygen. Thisprocess typically takes place in an aeration basin of awastewater treatment plant, and is accomplished byaerating or bubbling air (or pure oxygen) through thewastewater. Maintaining the proper concentration ofdissolved oxygen in the aeration basin is necessary tokeep microorganisms alive and allow break down oforganic waste. These microorganisms turn organicwastes into inorganic byproducts; specifically, carbondioxide, water and sludge. When the measureddissolved oxygen decreases below a desiredconcentration, the plant control system automaticallyadds air to the aeration basin to provide life-sustainingoxygen for the microorganisms, and to facilitatethorough mixing of the organic waste. Without enoughdissolved oxygen concentration, beneficialmicroorganisms will die while troublesome filamentousmicrobes proliferate, causing sludge settling problems.Conversely, aeration is the largest single operatingexpense, and oxygen levels greater than the requiredoptimum concentrations are wasteful and inefficient.
Typical Membrane Sensor Design
Dissolved oxygen sensors for continuous processmonitoring are usually a membrane-type design. Mostmembrane sensor designs use three basic elements:
Electrodes - The electrodes provide the necessaryreaction site for reduction of oxygen moleculesand generation of electrons.
Membrane - The gas permeable membrane isdesigned to keep the electrolyte around theelectrodes, while allowing only dissolved oxygento diffuse into the measurement cell.
Electrolyte - The electrolyte facilitates dissolvedoxygen migration and provides an electrical pathto complete the current loop. It also removes metaloxides (a by-product of the reaction) from theelectrodes so that their metal surfaces are clean toreact. Electrolyte must be periodically replenishedto insure that the electrodes remain clean.The operational theory of a membrane sensor is thatoxygen in the wastewater diffuses through themembrane into the electrolyte. The concentration ofgases always tends to equalize on both sides of themembrane. When the concentration is not equal, gasmolecules migrate to the membrane side that has alower concentration. When the membrane isfunctioning, dissolved oxygen concentration in theelectrolyte in the measurement cell approximatelyequals the dissolved oxygen concentration of thewastewater contacting the opposite side of themembrane. The diffusion process is extremely critical.The dissolved oxygen must be allowed to migratefreely through the membrane for the sensor to functionproperly.
Dissolved Oxygen Cell Chemistry
Most continuous measurement dissolved oxygensensors in today’s marketplace use galvanic(spontaneous voltage) or electrolytic (applied voltage)measuring cells. In either case, the system measuresan electric current between two electrodes, which isproportional to the dissolved oxygen in the process.
Conventional Galvanic Measuring CellA conventional galvanic cell is illustrated in
Figure 1
. The oxygen content of the electrolyte isbrought into equilibrium with that of the sample.The galvanic cell operates like a battery, twoelectrodes made of dissimilar metals are immersedin a filling solution. This causes an electrochemicalreaction to take place when oxygen comes intocontact with the electrodes. In this reaction, thecathode reduces the oxygen into hydroxide, thusreleasing four electrons for each molecule ofoxygen. These electrons cause a current to flowthrough the electrolyte, the magnitude of which isproportional to the oxygen concentration in theelectrolyte. The most common electrode materialsare gold, silver, copper or lead, and the most
BI International 1 Technical Bulletin: Dissolved Oxygen Measurement
frequently used electrolyte is potassium hydroxide(KOH). The cathode must be a noble metal (silveror gold) for the cathode potential to reducemolecular oxygen when the cell circuit is closed.The anode should be a base metal (iron, lead,cadmium, copper, zinc or silver) with good stabilityand without any tendency toward passivation. Theelectrolyte is selected so that it will not dissolve theanode at a high rate when the cell is open.Oxidation-reduction reactions for an iron anode andsilver cathode are:Reaction at cathode:O
+ 2H
O + 4e
Reaction at anode:2Fe
+ 4e
FIGURE 1 -- Conventional Galvanic Measuring Cell 
The conventional galvanic measuring cell has someinherent disadvantages. It depends on thereduction of oxygen molecules to generate ameasurement voltage, making it susceptible tocontamination of the electrodes and electrolyte. If acontaminating material permeates the membrane, itwill cause the cell potential to shift. This shift will befalsely interpreted as a change in dissolved oxygenconcentration. Another problem occurs at lowoxygen concentration levels. Since the output of agalvanic cell is linearly proportional to the amountof oxygen present, the potential for errors at lowoxygen levels increases due to a low signal-to-noise ratio. Finally, the anode electrode will beconsumed due to the electrochemical reactionnecessary for the dissolved oxygen measurement.
Clark Polarographic Measuring CellA Clark polarographic cell is illustrated in
Figure 2 
.The dissolved oxygen in the sample diffusesthrough the membrane and into the electrolytesolution, typically an aqueous potassium chloride(KCL) solution. When a constant polarizing voltageis applied across the gold and silver electrodes,oxygen will be reduced at the cathode. Theresulting current flow is directly proportional to thedissolved oxygen content of the electrolyte.Oxidation-reduction reactions for the Clark cell are:Reaction at cathode:O
+ 2H
O + 4e
Reaction at anode:4Ag + 4Cl
4AgCl + 4e
FIGURE 2 -- Clark Polarographic Measuring Cell 
The Clark polarographic measuring cell addressessome of the problems associated with aconventional galvanic cell. The polarographic cellrequires a polarization voltage to be applied to theelectrodes. As long as this voltage is maintained ata constant level, the cell will not be as susceptibleto contamination of the electrodes and electrolyteas a galvanic cell. If a contaminating material doespermeate the membrane, the cell potential will notshift. A polarographic cell measures the currentflow that results from reduction of the oxygenmolecules in the cell. Since this current flow islinearly proportional to the amount of oxygenpresent, potential for errors at low oxygen levels isreduced. Finally, the anode electrode will not beconsumed by the electrochemical reaction.
Ross Polarographic Measuring CellAnother variation of the conventional polarographiccell is the Ross polarographic cell, shown in
. The reaction cell, which consists of a workingelectrode (cathode) and a counter electrode(anode), is isolated from the process solution by anoxygen permeable membrane. Like the othermeasurement cells (galvanic and polarographic),oxygen penetrates the membrane and is reduced atthe cathode. Unlike the other measurement cellsthat consume oxygen without replacing it, theelectrochemical reaction of a Ross cell causes theanode to generate an amount of oxygen equal tothe amount consumed by the cathode.Measurement current flow is generated by thissteady-state diffusion of oxygen from the anode tothe cathode. This reaction continues untilequilibrium exists across the boundary between themembrane and its surroundings. When theconcentration of oxygen in the process changes,oxygen will pass into or out of the sensor untilequilibrium is re-established. The new steady-state
BI International 2 Technical Bulletin: Dissolved Oxygen Measurement

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