Dissolved Oxygen Background Mn4+, which precipitates as a brown hydrated oxide.

This reaction is relatively slow and

All aquatic life depends on the availability of dissolved oxygen (DO) in water. the solution must be shaken several ties to complete the reaction. The following equations

While terrestrial organisms live in an atmosphere composed of approximately 20% represent this reaction:

oxygen, aquatic organisms must work with considerably less oxygen. The solubility of 2Mn2+ + 4OH- 2MnO2 + 2H2O
o o
oxygen in fresh water ranges from 14.6 mg/L at 0 C to approximately 7.0 mg/L at 35 C
2Mn(OH)2 2MnO2 + 2H2O
And
under one atmosphere of pressure. The dissolved oxygen concentration in water is
After the MnO2 precipitate settles to the bottom of the flask, sulfuric acid is added
governed by Henry’s law, which is an equilibrium relationship between the partial
to make the solution acidic. Under these low pH conditions, the MnO2 oxidizes the I- to
pressure of oxygen in the atmosphere and the concentration of oxygen in the water.
free I2 through the following reaction
Additional factors influencing the concentration of oxygen in water are the barometric
MnO2 +2I- + 4H+ Mn2+ +I 2 +H20
pressure of the atmosphere (and therefore elevation above sea level), the salt content, and

the temperature of the water. A table of aqueous oxygen saturation levels (in mg/L) as a Now the sample is ready for titration with sodium thiosulfate (Na2S2O3:5H2O). In this

function of temperature is given in this module. Respiration can greatly reduce dissolved reaction thiosulfate ion is quantitatively added in order to convert the I2 back to I-.

oxygen in natural water bodies, microbial respiration, the most significant of these Because the amount of I2 present at this stage in the procedure is directly related to the

processes results from the degradation of organic waste. amount of Oxygen present in the original sample, we can use this volume to find the

Two methods are commonly used to determine the concentration of dissolved original dissolved oxygen concentration. This reaction can be represented by

oxygen in water samples: the Winkler Titration (iodometric method) and the membrane 2S2O32- +I2 S4O62- +2I-

electrode technique. Details on each of these methods can be found in Standard Methods The titration is complete when all of the I2 has been converted to I-. The endpoint of this

(1995) and Chemistry for Environmental Engineering (1978). The idiometric method will titration can be determined through potentiometry or by using calorimetric indicators.

be discussed first. The most common indicator is starch which turns from deep blue to clear.

The iodometric method, the more accurate of the two, determines the dissolved The dissolved oxygen concentration can be determined using the following
2+
oxygen concentration through a series of oxidation-reduction reactions. First Mn (as equation that reflects the series of reduction-oxidation reactions in the equations given

MnSO4) is added to a 250 mL sample. Next the Alkali-iodide reagent (KI in NaOH) is above.
2+
added. Under these caustic conditions, any present oxygen will oxidize the Mn to
 titration method, including speed, elimination or minimization of interferences, field
O2 conc. (mg/L) =
( )( )(
[(Volume S2O32-)(Conc. S 2O32-)] I2
S2O32-
MnO2
I2
O2
)(
2 MnO2 )(
32 g O2
mol O2 )
1000 mg
1g
compatibility, continuous monitoring and in situ measurement. However, there is some
Volume of original sample
loss in accuracy. Modern electrodes rely on a selectively permeable membrane, which
Several modifications of the Winkler method have been developed to overcome
allows dissolved oxygen to enter the measurement cell, thus eliminating most
interferences in the method. The most common modification, which uses azide,
interferences. The calibration and measurement is relatively simple and a direct readout
effectively removes interference from nitrite, which is commonly present in water
of the oxygen concentration is usually given. Refer to Sawyer and McCarty (1978) for
samples from biologically treated wastewater effluents and incubated biochemical
the operation of the electrodes.
oxygen demand samples. Nitrite interferes by converting I- to I2, thus overestimating the

dissolved oxygen in the sample. This is illustrated in the following equations:

And N2O2 +1/2 O2 + H20 2NO2- +2H+ McGraw-Hill Book Company, New York, 1978.

Note that the in the second reaction N2O2 is oxidized by oxygen, which enters the sample

during the titration procedure, and is converted to NO2-, establishing a cyclic reaction that

can lead to erroneously high results. Nitrite contamination thus results in a final

concentration far in excess of the amounts that would be expected.

Nitrite interference can be easily overcome through the addition of sodium azide

(NaN3). Azide is usually added with the alkali- KI reagent, and when the sulfuric acid is

added, it results in the removal of NO2- , as shown in the following reaction series:

NaN3 + H+ HN3 + Na+

HN3 + NO2- +H+ N2 +N2O + H2O

Other methods can also be used to remove the ferrous iron (the permanganate

modification), ferric iron (potassium fluoride modification), and suspended solids (alum

flocculation modification). The electrode method offers several advantages over the