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Dissolved Oxygen:

The air we breathe contains about 20% oxygen. Fish and other aquatic organisms require
oxygen as well. The term Dissolved Oxygen (DO or D.O.) refers to the amount of free
oxygen dissolved in water which is readily available to respiring aquatic organisms. State
water quality standards often express minimum concentrations of dissolved oxygen which
must be maintained in order to support life as well as be of beneficial use. Levels of
dissolved oxygen below 4-5 milligrams per liter affect fish health and levels below 2
milligrams per liter can be lethal to fish.

Additionally, biochemical oxygen demand (BOD) is commonly used with reference to
effluent discharges and is a common, environmental procedure for determining the extent
to which oxygen within a sample can support microbial life. The test for BOD is especially
important in waste water treatment, food manufacturing, and filtration facilities where the
concentration is crucial to the overall process and end products. High concentrations of DO
predict that oxygen uptake by microorganisms is low along with the required break down of
nutrient sources in the medium.

Basic principles of Polagrography cell:

Liquid and Air state of equilibrium is reached when the partial pressure of oxygen, i.e. the
part of the total pressure that is due to oxygen, is equal in air and in liquid. The liquid is
then saturated with oxygen.




Figure 1.1 Air and liquid oxygen equilibrium




Polargram:

When an electrode of noble metal such as platinum or gold is made 0.6 to 0.8 V negative
with respect to a suitable reference electrode such as AgAgCl or an calomel electrode in a
neutral KCI solution (see Figure 1.2), the oxygen dissolved in the liquid is reduce at the
surface of the noble metal.



Figure 1.2 Polarographhy diagram

This above phenomenon can be observed from a current to voltage diagram called a
polarogram of the electrode. As shown in Figure 1.3a, the negative voltage applied to the
noble metal electrode (called the cathode) is increased, the current increases initially but
soon it becomes saturated. In this plateau region of the polarogram, the reaction of oxygen
at the cathode is so fast that the rate of reaction is limited by the diffusion of oxygen to the
cathode surface. When the negative bias voltage is further increased, the current output of
the electrode increases rapidly due to other reactions, mainly, the reduction of water to
hydrogen. If a fixed voltage in the plateau region (for example, - 0.6V) is applied to the
cathode, the current output of the electrode can be linearly calibrated to the dissolved
oxygen (Figure 1.3b). It has to be noted that the current is proportional not to the actual
concentration but to the activity or equivalent partial pressure of dissolved oxygen, which is
often referred to as oxygen tension. A fixed voltage between -0.6 and -0.8 V is usually
selected as the polarization voltage when using Ag/AgCl as the reference electrode or any
other EID's dissolved oxygen electrodes.

Additionally for physical and chemical correctness, partial pressure in a liquid actually refers
to the fugacity. In the pressure range relevant to the measurements at hand, it is
acceptable to equate the two values and this allows us to restrict the following
considerations to the partial pressure. In dry, atmospheric air, the partial pressure of
oxygen is 20.95% of the air pressure. This value is reduced over a water surface because
water vapor has its own vapor pressure and a corresponding partial pressure.




Figure 1.3 (a) Current to voltage diagram at different oxygen tension; (b)
Calibration obtained at a fixed polarization voltage of 600 mV.

When the cathode, the reference electrode, and the electrolyte are separated from the
measurement medium by a polymer membrane, which is permeable to the dissolved gas
but not to most of the ions and other species, and when most of the mass transfer
resistance is confined in the membrane, EIDs electrode system can measure oxygen
tension in various liquids. This is the basic operating principle of the membrane covered
polarographic Dissolve oxygen probe (Figure 1.4).

The basic principle underlying the electrochemical determination of oxygen concentration is
the use of membrane covered electrochemical sensors. The main components of the sensors
are the oxygen permeable membrane, the working electrode, the electrolyte solution and a
possible reference electrode. A voltage is applied between the gold (platinum or silver)
cathode and the anode that consists of either lead or silver (AgAgCl), and causes the
oxygen to react electrochemically. The higher the oxygen concentration the higher the
resulting electric current. The current in the sensor is measured and, after calibration,
converted into the concentration of dissolved oxygen.

If the anode is made of silver, the meter applies the required voltage (polarographic
sensor). If it is made of lead, the sensor is self-polarizing, i.e. the voltage is generated in
the sensor by the electrodes themselves, comparable to the process in a battery (galvanic
sensor). The meter merely evaluates the current.



Figure 1.4 Basic Polarographhy electrode




EIDs polaragraphoc dissolved oxygen electrode picture:



EIDs ELECTRODER - ABS body Dissolved Oxygen Sensor (ADO)
EIDs dissolved oxygen, Probe, polaragraphic, ABS body, 12mm * 120mm, with 10K
Negative Temperature Compensation

Figure 1.5 Basic Polarographhy-electrode




Electrode reactions:

For our polarographic electrodes, the reaction proceeds as follows:
Cathodic reaction: 02 + 2H2 0 + 2e
-
H2O2 + 2OH
-

H202 + 2e
-
-> 20H
-

Anodic reaction: Ag + Cl
-
AgCl + e
-

Overall reaction: 4Ag + 02 + 2 H2O + 4 Cl
-
4 AgCl + 4 OH
-

The reaction tends to produce alkalinity in the medium together with a small amount of
hydrogen peroxide.




Number of electrons involved:

Two principal pathways were proposed for the reduction of oxygen at the noble metal
surface. One is a 4-electron pathway where the oxygen in the bulk diffuses to the surface of
the cathode and is converted to H2Ovia H2O2 (path a in Fig. 1.6). The other is a 2-electron
pathway where the intermediate H2O2 diffuses directly out of the cathode surface into the
bulk liquid (path b in Figure 1.6). The oxygen reduction path may change depending on the
surface condition of the noble metal. This is probably the cause for time-dependent current
drift of polarographic sensors. Since the hydroxyl ions are constantly being substituted for
chloride ions as the reaction starts, KCI or NaCl has to be used as the electrolyte. When the
electrolyte is depleted of Cl
-
, it has to be replenished.
2e
-

2e
-
(a) H2O2
O2 O2 H2O2
Diffusion
(b) H2O2

Figure 1.6 alternative pathway of oxygen reduction at cathode surface




Calibration:

Calibration must be carried out for dissolved oxygen measurements on a regular base. This
is because the measuring process consumes the electrolyte solution in the sensor head, as
shown by the electrode reactions presented above. The ions of the electrolyte solution bind
the released metal ions, thereby changing the composition of the solution. The
recommended calibration period depends on the oxygen sensor used and ranges from one
week for pocket instruments to 1-2 months.

Each linear calibration function is defined by at least two points. For dissolved oxygen
measurements with EID meter and/or logger, one of the points on the line is the zero point
of the sensor. At the zero point, the sensor signal obtained in the absence of oxygen lies
below the resolution of the sensor. This point is called the zero-current point of the sensor.
The second point of the calibration line can be set as required. Its position is based on the
fact that, in a state of equilibrium, the partial pressure of oxygen in liquid and air is equal.



Figure 1.4b Two-point calibration

The rate at which oxygen enters a dissolved oxygen probe is a function of:
the concentration of oxygen in the sample
the diffusion coefficient/permeability of the membrane (function of
temperature)
As described above calibration routines for dissolved oxygen probes use a two point linear
calibration where one point is at zero mg/L oxygen and the second point is at saturation or
equilibrium with the atmosphere, C
*
. The zero measurement is not zero volts due to the
conductivity of the electrolyte between the electrodes as well as any errors in the analog signal
conditioning circuit. For the circuit and probe system used in the Environmental lab the
zero measurement is approximately 1 mV (where approximately 200 mV corresponds to
saturation levels of oxygen) and hence the zero measurement is not significant. Thus a single
point calibration is used.

C* is a function of the atmospheric pressure and temperature. The functional relationship
with temperature is implemented using a lookup table (based on equilibrium at atmospheric
pressure) with interpolation. The effect of atmospheric pressure is implemented as shown
(Equation 1 below).

P
C
*
=------- f (T)
P
atm


The permeability of the membrane increases about 5% per C degree. I chose to use 25 C as
the reference temperature and thus K
membrane(
T
ref)
has a value of 1. The following (equation
2) creates a coefficient that describes this variation.

K
membrane
(T)
=
K
membrane(
T
ref)e
0.05(T-Tref)


The slope of the linear fit (k) can be calculated after the voltage corresponding to saturation
oxygen is measured (Equation 3 below).

C
*
cal
K
membrane

C =------------------
V
*
cal


The slope coefficient is placed in the polynomial array.

The equation for the dissolved oxygen concentration illustrates that the predicted
concentration is a function of sample temperature because K
membrane
varies with
temperature. The coefficient, k, should be independent of temperature but will vary as a
membrane fouls (Equation 4 below)

KV
C=-----------
K
membrane


Pressure

The constituents of air have been well defined, and it is known that air contains 20.946%
oxygen. Since the total pressure in the air is the sum of all of the partial pressures (Daltons
Law), an atmospheric pressure of 760 millimeters Mercury (mmHg) in dry air will contain a
partial pressure of oxygen (pO
2
) of approximately 159 mmHg (760 mmHg *
0.20946). Changes in atmospheric pressure will cause a directly proportional change in the
partial pressure of oxygen in the air. Atmospheric pressures will vary depending upon
altitude and local weather conditions. Some average pressures for varying altitudes are
listed in Table 1 bellow.

The relationship between oxygen partial pressure and total atmospheric pressure should be
understood and incorporated into the air calibration in order to minimize calibration error,
which could be as high as 5-10% dependent upon altitude and local weather
conditions. Most dissolved oxygen meters that have any sort of advanced air calibration
(such as temperature compensation, which will be discussed in a later section) will be based
upon an atmospheric pressure of 760 mmHg. Most tables of oxygen solubility are
referenced to this value. Because of the change in oxygen partial pressure with changes in
atmospheric pressure, a correction must be made when the pressure varies from this
value. A simple means of incorporating pressure changes is listed in the correction factor
shown in Table 1 bellow. The value listed is a rough multiplier, which can be used once the
initial oxygen concentration is determined based upon temperature and relative humidity. A
more accurate calculation for incorporating pressure will be discussed after relative humidity
and temperature effects are investigated.

Some EIDs dissolved oxygen meters contain a pressure sensing device which provides
compensation for pressure effects when an air calibration is performed. If you use our
electrode on not-EID-meter, since most meters do not have this, it is usually necessary to
note the average pressure in the local vicinity of the probe, which will be mostly altitude-
based, and adjust the calibration using the simple correction factor or the more complex
calculation performed later. A mercury barometer located in the immediate vicinity of the
meter will give a relatively accurate measurement of the local atmospheric pressure if an
older meter with no pressure sensor is used.

Altitude
(ft)
Pressure
(mm Hg)
Correction Calibration
Correction Factor
-540 775 1.02
Sea Level 760 1
500 746 0.98
1000 732 0.96
1500 720 0.95
2000 707 0.93
2500 694 0.91
3000 681 0.9
3500 668 0.88
4000 656 0.86
4500 644 0.85
5000 632 0.83
5500 621 0.82
6000 609 0.8

Table 1: Oxygen Value Corrected for Pressure (25 C)

Relative Humidity and temperature effect and Temperature compensation

If desired the Eid's probes can be coupled with a temperature thermistor (10K Ohms) to
achieve temperature compensation since K
membrane
varies with temperature.

The discussion of pressure effects were based upon atmospheric pressure with dry air (no
moisture content). Whenever air contains a certain amount of moisture, the atmospheric
pressure contains another source of partial pressure -- water vapor. If a comparison of the
oxygen partial pressure in air with 100% relative humidity and air with 0% relative humidity
is done while both are at the same atmospheric pressure, the air with 100% relative
humidity will have a lower oxygen partial pressure due to the presence of the water vapor
pressure (pH
2
O). Water vapor pressure in air varies with temperature, and is well
defined. The effect of temperature on oxygen partial pressure in moist air is such that
higher temperatures yield lower oxygen partial pressure, while lower temperatures yield
higher pressures. Note that the effects of relative humidity and temperature can cause
errors when air calibration is performed in dry air, since most of the current tables and
meter temperature compensations are based on air containing 100% relative
humidity. Table 2 bellow shows both the oxygen concentration, which is linear with the
partial pressure of oxygen, that would be present at 100% relative humidity and 0%
relative humidity. The values only differ by a few percent in ambient air conditions, and
thus is generally ignored. Most dissolved oxygen meters have temperature compensation for
air at 100% relative humidity, and no manual correction is necessary. However, many older
meters do not have temperature compensation included, and therefore this calculation must
be done manually. If temperature is not compensated for in the calibration, the error can
be as much as 20 to 30 % for every 10 degrees difference from 25 C, and therefore
temperature compensation is standard on most dissolved oxygen meters today. Since the
effects of relative humidity is minimal at all but the highest temperatures, no current
dissolved oxygen meters incorporate any kind of relative humidity sensing device.

In order to ensure an accurate temperature and current reading, the probe must be
exposed to the air for enough time to allow thermal equilibrium to occur. There are often
significant temperature differences between the process water and the ambient air. Larger
temperature gradients between the two necessitate additional time for thermal equilibrium
to take place. For instance, a 20 C difference between ambient air and process water can
cause a calibration delay of about 30 minutes in many probes for the probe to fully
equilibrate to ambient temperature. Since most temperature gradients will not be this
large, allowing approximately 15 minutes is usually a safe assumption. It is common for
users to calibrate the unit before the dissolved oxygen meter is reading the stabilized
temperature and current value, which can cause significant error since a difference of even
5 C from actual can cause the reading be off by 5 to 10%. It is often useful to have a
calibrated temperature sensor, accurate to 1 C or better, at the calibration location to know
when the probe temperature is reading the correct ambient air temperature.

It is useful to have an equation which can be used to determine oxygen concentrations in
air based upon temperature, relative humidity, and pressure. Since the full equation is quite
lengthy and complex, two easier versions are presented to the user, along with Table 2
bellow, to determine the correct oxygen concentration in air. Equation 5 bellow should be
used with air with 100% relative humidity, and Equation 6 should be used for air with 0%
relative humidity.

Equation 5 (100% Relative Humidity): OS = (OS) * (P - p) / (760 - p)

where:

OS = Oxygen solubility at barometric pressure of interest
OS = Oxygen in saturation at one atmosphere (760 mmHg) at a given temperature
P = Barometric pressure of interest
p = Vapor pressure of water at the temperature of interest

Example 1:

The user wishes to calibrate a dissolved oxygen probe in air at an altitude of 3500 feet. The
temperature is 30C, and the relative humidity is 100%.

At an altitude of 3500 feet, the atmosphere pressure will usually be about 668 mmHg (Table
1 above). The sample temperature is 30 C, and the relative humidity is 100%. From
water vapor pressure tables, the water vapor pressure at 30 C is 31.8 mmHg. The oxygen
saturation level at 760 mmHg and 30 C is 7.54 ppm (Table 2 bellow). Substituting these
values in the above (equation 5) gives the following:

OS = (7.54) * (668 - 31.8) / (760 - 31.8) = 6.59 ppm

Example 2:

Assume the same conditions as in example 1, but with a relative humidity of 0%. In this
case, the value used for the oxygen saturation level would be 7.87 (Table 2 bellow), not
7.54. The calculation will change since there will be no water vapor pressure.

Equation 6 (0% Relative Humidity): OS = (OS) * (P) / (760 mmHg)

Substituting the above values into the equation yields the following:

OS = 7.87 * (668) / (760) = 6.92 ppm

Note: that the multiplier of (668) / (760) is actually the simplified correction factor listed in
Table 1 above for an altitude of 3500 feet (0.88). Table 3 bellow lists calibration values for
varying temperatures pressures at relative humidity levels of 100%.

Temperature
(Celsius)
DO (100% R.H.)
(ppm, mg/L)
DO (0% R.H.)
(ppm, mg/L)
0 14.6 14.66
1 14.19 14.26
2 13.81 13.89
3 13.44 13.53
4 13.09 13.18
5 12.75 12.85
6 12.43 12.54
7 12.12 12.23
8 11.83 11.94
9 11.55 11.66
10 11.27 11.4
11 11.01 11.14
12 10.76 10.9
13 10.52 10.66
14 10.29 10.44
15 10.07 10.22
16 9.85 10.01
17 9.65 9.82
18 9.45 9.63
19 9.26 9.45
20 9.07 9.27
21 8.9 9.11
22 8.72 8.95
23 8.56 8.8
24 8.4 8.65
25 8.24 8.51
26 8.09 8.37
27 7.95 8.24
28 7.81 8.12
29 7.67 8
30 7.54 7.88
31 7.41 7.77
32 7.28 7.66
33 7.16 7.56
34 7.05 7.46
35 6.93 7.37
36 6.82 7.27
37 6.71 7.18
38 6.61 7.1
39 6.51 7.01
40 6.41 6.93
41 6.31 6.85
42 6.22 6.78
43 6.13 6.7
44 6.04 6.63
45 5.95 6.56
46 5.86 6.49
47 5.78 6.43
48 5.7 6.36
49 5.62 6.3
50 5.54 6.24

Table 2 above: Dissolved Oxygen Solubility vs. Temperature

Temperature
(Celsius)
790 775 760 745 730 715 700 685 670 665
0 15.2 14.9 14.6 14.3 14 13.7 13.4 13.2 12.9 12.6
1 14.8 14.5 14.2 13.9 13.6 13.3 13.1 12.8 12.5 12.2
2 14.4 14.1 13.8 13.5 13.3 13 12.7 12.4 12.2 11.9
3 14 13.7 13.4 13.2 12.9 12.6 12.4 12.1 11.8 11.6
4 13.6 13.4 13.1 12.8 12.6 12.3 12.1 11.8 11.5 11.3
5 13.3 13 12.8 12.5 12.2 12 11.7 11.5 11.2 11
6 12.9 12.7 12.4 12.2 11.9 11.7 11.4 11.2 10.9 10.7
7 12.6 12.4 12.1 11.9 11.6 11.4 11.2 10.9 10.7 10.4
8 12.3 12.1 11.8 11.6 11.4 11.1 10.9 10.7 10.4 10.2
9 12 11.8 11.6 11.3 11.1 10.9 10.6 10.4 10.2 9.94
10 11.7 11.5 11.3 11 10.8 10.6 10.4 10.1 9.92 9.69
11 11.5 11.2 11 10.8 10.6 10.4 10.1 9.91 9.69 9.47
12 11.2 11 10.8 10.5 10.3 10.1 9.9 9.68 9.47 9.25
13 10.9 10.7 10.5 10.3 10.1 9.89 9.68 9.47 9.26 9.04
14 10.7 10.5 10.3 10.1 9.88 9.67 9.46 9.26 9.05 8.85
15 10.5 10.3 10.1 9.87 9.67 9.46 9.26 9.06 8.86 8.65
16 10.3 10.1 9.85 9.65 9.45 9.26 9.06 8.86 8.66 8.46
17 10 9.84 9.65 9.46 9.26 9.07 8.87 8.68 8.48 8.29
18 9.83 9.64 9.45 9.26 9.07 8.88 8.69 8.5 8.31 8.12
19 9.63 9.45 9.26 9.07 8.89 8.7 8.51 8.33 8.14 7.95
20 9.44 9.25 9.07 8.89 8.7 8.52 8.34 8.15 7.97 7.79
21 9.26 9.08 8.9 8.72 8.54 8.36 8.18 8 7.82 7.64
22 9.07 8.9 8.72 8.54 8.37 8.19 8.01 7.84 7.66 7.48
23 8.91 8.73 8.56 8.39 8.21 8.04 7.86 7.69 7.52 7.34
24 8.74 8.57 8.4 8.23 8.06 7.89 7.72 7.55 7.38 7.2
25 8.58 8.41 8.24 8.07 7.9 7.74 7.57 7.4 7.23 7.06
26 8.42 8.26 8.09 7.92 7.76 7.59 7.43 7.26 7.1 6.93
27 8.28 8.11 7.95 7.79 7.62 7.46 7.3 7.14 6.97 6.81
28 8.13 7.97 7.81 7.65 7.49 7.33 7.17 7.01 6.85 6.69
29 7.99 7.83 7.67 7.51 7.35 7.2 7.04 6.88 6.72 6.57
30 7.85 7.7 7.54 7.38 7.23 7.07 6.92 6.76 6.61 6.45
31 7.72 7.56 7.41 7.26 7.1 6.95 6.8 6.64 6.49 6.34
32 7.58 7.43 7.28 7.13 6.98 6.83 6.68 6.53 6.38 6.22
33 7.46 7.31 7.16 7.01 6.86 6.71 6.57 6.42 6.27 6.12
34 7.34 7.2 7.05 6.9 6.76 6.61 6.46 6.32 6.17 6.02
35 7.22 7.07 6.93 6.79 6.64 6.5 6.35 6.21 6.06 5.92
36 7.11 6.96 6.82 6.68 6.53 6.39 6.25 6.11 5.96 5.82
37 6.99 6.85 6.71 6.57 6.43 6.29 6.15 6 5.86 5.72
38 6.89 6.75 6.61 6.47 6.33 6.19 6.05 5.91 5.77 5.63
39 6.79 6.65 6.51 6.37 6.23 6.1 5.96 5.82 5.68 5.54
40 6.68 6.55 6.41 6.27 6.14 6 5.86 5.73 5.59 5.45
41 6.58 6.44 6.31 6.18 6.04 5.91 5.77 5.64 5.5 5.3 7
42 6.49 6.35 6.22 6.09 5.95 5.82 5.69 5.55 5.42 5.28
43 6.39 6.26 6.13 6 5.87 5.73 5.6 5.47 5.34 5.2
44 6.3 6.17 6.04 5.91 5.78 5.65 5.52 5.39 5.25 5.12
45 6.21 6.08 5.95 5.82 5.69 5.56 5.43 5.3 5.17 5.04
46 6.12 5.99 5.86 5.73 5.6 5.47 5.35 5.22 5.09 4 .96
47 6.03 5.91 5.78 5.65 5.53 5.4 5.27 5.14 5.02 4.89
48 5.95 5.83 5.7 5.57 5.45 5.32 5.19 5.07 4.94 4.82
49 5.87 5.75 5.62 5.49 5.37 5.24 5.12 4.99 4.87 4.74
50 5.79 5.66 5.54 5.42 5.29 5.17 5.04 4.92 4.79 4.67

Table 3 above: Oxygen concentration (ppm) for varying pressures (mmHg)
and temperatures (degrees Celsius) at 100% relative humidity