Technical Notes

Dissolved Oxygen General Theory

What is Dissolved Oxygen?
Dissolved oxygen is the term used for the amount of gaseous oxygen,
which is dissolved or trapped in liquid medium. The solubility of oxygen
changes for different liquid substances and different temperatures.
When a liquid solution holds all the dissolved oxygen it can hold at a
given temperature, it is said to be 100% saturated. If the liquid
substance holds half-as-much oxygen as it can hold at a given
temperature, it is 50% saturated. The units can also be reported in
ppm if solubility information is available.

How do you measure Dissolved Oxygen?

Electrochemical cell-type sensors (Polarographic, galvanic,
colourometric) can be typically used to measure oxygen in the vapor
phase or dissolved in a liquid substance. The most commonly used
dissolved oxygen (DO) probe is the Polarographic type. The electrodes
consume such a small amount of oxygen that the electrodes can be
used a very low flow rates.
Polarographic Cell
The basic Polarographic cell is very
similar to the galvanic cell discussed
later. However, the Polarographic cell has
two noble-metal electrodes and requires
a polarizing voltage to reduce the
oxygen. The dissolved oxygen in the
sample diffuses through the membrane
into the electrolyte, which usually is an
aqueous KCI solution. If there is a
constant polarizing voltage across the
electrodes, the oxygen is reduced at the
cathode and the resulting current flow is
directly proportional to the oxygen
content of the electrolyte. The oxidationreduction reactions, in the case of a goldsilver cell with KCI electrolyte, are as follows:

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Technical Notes
At the gold cathode: O5 + 2H2O + 4 electrons 4(OH-)
At the silver anode: 4Ag + 4(Cl-) + AgCl + 4 electrons
The life of this type of cell is highly dependent upon the amount of
oxygen the cell comes in contact with and the process conditions. Life
expectancies can be as low as a couple of months to as long as 18months. Some Polarographic cells are designed to be field rebuild able
to minimize maintenance costs.
The Polarographic cell, like the galvanic cells, is affected by
temperature. Therefore, either controlled sample temperature or
temperature compensation is required to attain high precision
measurements. Expected accuracy is in the range of I to 2% of fullscale reading. If the sample temperature is not controlled or
compensated for the measured reading could have an inaccuracy of up
to 10% of full-scale reading.
Both the galvanic and the Polarographic can operate under very low
sample flow. Flow is only needed to eliminate stagnant layers of
sample over the membrane.
Galvanic Cell
The majority of the dissolved oxygen sensors is installed in dirty water,
and therefore they require special cleaners, agitators, and specialized
sample systems.
The ranges of the galvanic cell dissolved oxygen analyzer can be as
low as 0 to 20 ppb for applications such as the measurement of
dissolved oxygen (DO) content in boiler feed water. All galvanic cells
consist of an electrolyte and two electrodes (Figure 41c). The oxygen
content of the electrolyte is brought into equilibrium with that of the
sample. The electrodes are polarized by an applied voltage, which
causes electrochemical reactions to take place when oxygen contacts
the electrodes. In this reaction, the cathode reduces the oxygen into
hydroxide, thus releasing four electrons for each molecule of oxygen.
These electrons cause a current flow through the electrolyte, the
magnitude of which is in proportion to the oxygen concentration in the
electrolyte.
The most common electrode materials are gold, silver, copper, or lead,
and the most frequently used electrolyte is potassium hydroxide (KOH).
The cathode must be noble (silver or gold) in order for the cathode

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Technical Notes
potential to reduce molecular oxygen when the cell circuit is closed.
The anode is selected to be a base metal (lead, cadmium, copper, zinc,
or silver) with good stability and without any tendency toward
passivation. The electrolyte (potassium hydroxide KOH, potassium
chloride (KCI), or potassium bicarbonate (KHCO3) is selected so that it
will not dissolve the anode at a high rate when the cell is open.
In the case of a lead anode, the cell reactions can be expressed as
follows:
Cathode: O2 + 2H2O + 4 electrons <-> 4(OH-)
Anode: 2Pb <-> 2(Pb++) + 4 electrons
The galvanic-cell designs are subject to various degrees of
contamination by background gases in the process stream. As a very
general rule, the following background gases can be considered
harmless: argon, butane, carbon monoxide, ethane, ethylene, helium,
hydrogen, methane, nitrogen, and propane. However, the following
gases are likely to contaminate the cell: chlorine and other halogens,
high concentrations of carbon dioxide, hydrogen sulfide, and sulfur
dioxide. Some cells have been developed to minimize the effect of the
background gases. The galvanic cell typically cannot be rebuilt in the
field as the Polarographic cell can. This is because in making the
oxygen measurement the metal electrode is consumed. It the
Polarographic electrode the electrode is not consumed, but it has a
longer polarization time.
Both of these types of measuring cells are dependent on the partial
pressure of the oxygen in the media that is being measured. This is
due to the diffusion characteristics of the membrane part of the probe.
As the pressure on the membrane changes the amount to oxygen
entering the probe will change. This means he pressure of the
measured media must be held constant or the pressure must be
measured and compensated for its effects.

What is required to Measure Dissolved Oxygen?

In order to measure DO the following equipment is required: A DO
meter, a DO probe, a temperature measuring device (typically part of
the DO probe), a housing to hold the DO probe in the process, and the
connecting cable.

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Technical Notes
How is a Dissolved Oxygen Analyzer Calibrated?
There are several ways that DO meters can be calibrated depending
upon which manufacture is used. The simplest method is the Air
calibration using the known barometric pressure. The electrode can be
zeroed but it is not typically necessary. Evacuating all of the oxygen
from the electrode membrane and electrodes would do zeroing. This
can be done by continually passing an inert gas, which is free from
oxygen by the electrode. The unit would then need to be placed in
ambient air to be spanned. The analyzer would prompt for the
barometric pressure, which would then be entered by the user. The
analyzer then would display the concentration of oxygen in percent,
percent saturation, or ppm.
A second method of calibration available on some manufactures units
is the air calibration by temperature and elevation. The user could zero
the unit if desired by following the procedure discussed above. Then
the electrode would need to be placed in ambient air. The user would
then be required to enter his elevation with respect to sea level and
the local temperature. The analyzer would then calculate the oxygen
concentration and display it as percent, percent saturation, or ppm.
A third method of calibration is to use the Winkler titration. This is a lab
titration that is used to determine the exact concentration of oxygen in
a specific sample. The analyzer could then be standardized to this
value.

Why is Dissolved Oxygen Measured?

Dissolved oxygen is a measurement of water quality

Waste Water
Drinking Water
Natural bodies of water

It is a measurement of hydrocarbon co-monomer quality

Hexane
Decene
Styrene

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Xylene
Octane

Industry

Brewing Industry
Wine Industry
Biotechnology Industry
Boiler Feed-Water (ppb levels)

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