Winkler test for dissolved oxygen

The Winkler test is used to determine the concentration 70%) is added to create a pinkish-brown precipitate. In
of dissolved oxygen in water samples. Dissolved oxygen the alkaline solution, dissolved oxygen will oxidize man-
(D.O.) is widely used in water quality studies and routine ganese(II) ions to the tetravalent state.
operation of water reclamation facilities. An excess of
manganese(II) salt, iodide (I ) and hydroxide (OH ) ions
2 MnSO4 (s) + O2 (aq) 2 MnO(OH)2 (s)
is added to a water sample causing a white precipitate of
Mn(OH)2 to form. This precipitate is then oxidized by
the dissolved oxygen in the water sample into a brown MnO(OH)2 appears as a brown precipitate. There is
manganese precipitate. In the next step, a strong acid (ei- some confusion about whether the oxidised manganese
ther hydrochloric acid or sulfuric acid) is added to acid- is tetravalent or trivalent. Some sources claim that
ify the solution. The brown precipitate then converts the Mn(OH)3 is the brown precipitate, but hydrated MnO2
iodide ion (I ) to iodine. The amount of dissolved oxy- may also give the brown colour.
gen is directly proportional to the titration of iodine with
a thiosulfate solution.[1] Today, the method is eectively 4 Mn(OH)2 (s) + O2 (aq) + 2 H2 O 4
used as its colorimetric modication, where the trivalent Mn(OH)3 (s)
manganese produced on acidifying the brown suspension
is directly reacted with EDTA to give a pink color.[2] As
manganese is the only common metal giving a color reac- The second part of the Winkler test reduces (acidies)
tion with EDTA, it has the added eect of masking other the solution. The precipitate will dissolve back into so-
metals as colorless complexes. lution. The acid facilitates the conversion by the brown,
Manganese-containing precipitate of the Iodide ion into
elemental Iodine.
1 History The Mn(SO4 )2 formed by the acid converts the io-
dide ions into iodine, itself being reduced back to man-
ganese(II) ions in an acidic medium.
The test was originally developed by Ludwig Wilhelm
Winkler, in later literature referred to as Lajos Winkler,
while working at Budapest University on his doctoral dis- Mn(SO4 )2 + 2 I (aq) Mn2+ (aq) + I2 (aq) +
sertation in 1888.[3] The amount of dissolved oxygen is 2 SO4 2 (aq)
a measure of the biological activity of the water masses.
Phytoplankton and macroalgae present in the water mass-
Thiosulfate is used, with a starch indicator, to titrate the
produce oxygen by way of photosynthesis. Bacteria and
iodine.
eukaryotic organisms (zooplankton,sh) consume this
oxygen through cellular respiration. The result of these
two mechanisms determines the concentration of dis- 2 S2 O3 2 (aq) + I2 S4 O6 2 (aq) + 2 I (aq)
solved oxygen, which in turn indicates the production of
biomass. The dierence between the physical concentra-
tion of oxygen in the water (or the theoretical concentra-
tion if there were no living organisms) and the actual con-
3 Analysis
centration of oxygen is called the biochemical demand in
oxygen. The Winkler test is often controversial as it is From the above stoichiometric equations, we can nd
not 100% accurate and the oxygen levels may uctuate that:
from test to test despite using the same constant sample.
1 mole of O2 2 moles of MnO(OH)2 2
mole of I2 4 mole of S2 O3 2
2 Sample method
Therefore, after determining the number of moles of io-
In the rst step, manganese(II) sulfate (at 48% of the dine produced, we can work out the number of moles of
total volume) is added to an environmental water sam- oxygen molecules present in the original water sample.
ple. Next, potassium iodide (15% in potassium hydroxide The oxygen content is usually presented as mg/dm3 .

1
2 9 FURTHER READING

4 Limitations [3] Lajos Winkler (1888). Die Bestimmung des

The success of this method is critically dependent upon
the manner in which the sample is manipulated. At all
stages, steps must be taken to ensure that oxygen is neither
introduced to nor lost from the sample. Furthermore, the
water sample must be free of any solutes that will oxidize
or reduce iodine.
Instrumental methods for measurement of dissolved oxy-
gen have widely supplanted the routine use of the Winkler
test, although the test is still used to check instrument cal-
ibration.
5 BOD5
To determine ve-day biochemical oxygen demand
(BOD5 ), several dilutions of a sample are analyzed for
dissolved oxygen before and after a ve-day incubation
period at 20 C in the dark. In some cases, bacteria are
used to provide a standardized community to uptake oxy-
gen while consuming the organic matter in the sample;
these bacteria are known as seed. The dierence in DO
and the dilution factor are used to calculated BOD5 . The
resulting number (usually reported in parts per million or
milligrams per liter) is useful in determining the relative
organic strength of sewage or other polluted waters.
The BOD5 test is an example of analysis that determines
classes of materials in a sample.
in Wasser Gelsten Sauerstoes. Berichte der
Deutschen Chemischen Gesellschaft 21 (2): 2843
2855. doi:10.1002/cber.188802102122.
[4] Whitney King, Winkler titrations measuring dissolved
oxygen, Colby at Sea, 11 February 2011, retrieved and
archived 11 July 2012.
9 Further reading
Moran, Joseph M.; Morgan, Michael D., &
Wiersma, James H. (1980). Introduction to Environ-
mental Science (2nd ed.). W.H. Freeman and Com-
pany, New York, NY ISBN 0-7167-1020-X
Standard Methods for the Examination of Water and
Wastewater 20th Edition ISBN 0-87553-235-7.
This is also available on CD-ROM and online by
subscription
http://www.ecy.wa.gov/programs/wq/plants/
management/joysmanual/4oxygen.html
Y.C. Wong & C.T. Wong. New Way Chemistry for
Hong Kong A-Level Volume 4, p. 248. ISBN 962-
342-535-X
Manganese (III) consistently claimed (NB: Gives
unbalanced equation for formation of MnO(OH)2 ).
Claims manganese (III)

Gives manganese (IV) consistently

6 Winkler bottle
A Winkler bottle is a piece of laboratory glassware
specically made for carrying out the Winkler test. These
bottles have conical tops and a close tting stopper to aid
in the exclusion of air bubbles when the top is sealed. This
is important because oxygen in trapped air would be in-
cluded in the measurement and would aect the accuracy
of the test.[4]

7 See also
Oxygen saturation

8 References
[1] Chiya Numako and Izumi Nakai (1995). XAFS studies
of some precipitation and coloration reaction used in an-
alytical chemistry. Physica B: Condensed Matter. 208
209: 387388. doi:10.1016/0921-4526(94)00706-2.

[2] A. H. de Carvalho, J. G. Calado and M. L. Moura, Rev.

Port. Quim., 1963, 5, 15
 3

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