MadSci Network: Chemistry
Query:

Re: What chemical reactions occur in the Winkler method dissolved oxygen test?

Date: Tue Jun 2 09:02:36 1998
Posted By: David Kopaska-Merkel, Staff Hydrogeology Division, Geological Survey of Alabama
Area of science: Chemistry
ID: 896660248.Ch
Message:

Jessi--

There are several varieties of the Winkler method; I found the chemical 
reactions for one variant, which is called the Alsterberg-azide 
modification. This method forms a precipitate of manganous hydroxide, which 
absorbs dissolved oxygen, and then uses iodine to measure the amount. The 
explanation comes from an old version of the U.S. Geological Survey's 
"Methods for determination of inorganic substances in water and fluvial 
sediments, book 5, chapter A1." I know it was published after 1976, but the 
page with the publication date is missing.

Here are the equations:

MnSO4 + 2KOH --> Mn(OH)2ppt + K2SO4

2Mn(OH)2ppt + O2 --> 2MnO(OH)2ppt

Then you acidify the mixture with iodine, which is released in a quantity 
equivalent to the dissolved Oxygen present:

MnO(OH)2ppt + 2KI + H2O -->(with H+) Mn(OH)2ppt + I2 + 2KOH

Titrate the iodine with sodium thiosulfate standard solution with use of 
starch indicator:

I2 + 2S2O3-2 --> S4O6-2 + 2I-1

The book cites this reference:

Adams, R. C., Barnett, R. D., and Keller, D. E., Jr., 1943, Field and 
laboratory determination of dissolved oxygen: American Society for Testing 
and Materials, Proc. 43.

I hope this information helps you out. If you have any more questions, 
please do not hesitate to ask.

Sincerely,

David C. Kopaska-Merkel
Geological Survey of Alabama
PO Box O, Tuscaloosa AL 35486
(205) 349-2852
Email: davidkm@ogb.gsa.tuscaloosa.al.us


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