Aim: To determine the dissolved oxygen (DO) in a given water sample by modified Winkler's

method.

Theory: Dissolved oxygen refers to the level of free, non-compound oxygen present in water or
other liquids. It is an important parameter in assessing water quality because of its influence on
the organisms living within abody of water. A dissolved oxygen level that is too high or too low
can harm aquatic life and affect water quality.
The stream system both produces and consumes oxygen. It gains oxygen by diffusion from the
atmosphere and from plants as a result of photosynthesis. Dissolved oxygen is also produced as a
waste product of photosynthesis from phytoplankton, algae, seaweed and other aquatic plants
Respiration by aquatic animals, decomposition and various chemical reactions consume oxygen.
Dissolved oxygen is necessary for life of fish and other aquatic organisms. Oxygen is also
needed to enable bacteria and fungi to oxidise organic matter present in water. Low
concentrationor absence of oxygen is an indicator of pollution in water. When its concentration
is less than 4 ppm, the water system is unsuitable for aquatic life. Further dissolved oxygen in
boiler feed water causes corrosion of boiler plate. Its determination is, therefore, essential. The
DOdetermination measures the amount of dissolved oxygen present in water or waste water.
The concentration of DO in natural water and in waste water is a function of the temperature of
the air and water, the degree of hardness of water and the demand of O2 in the body of water.
Both chemical and instrumental methods are available for determination of D0. There are
sensors available, which could be available into the water sample at any location and which
would rapidly furnish a readout related to the in-situ concentration of oxygen at that exact time
and place. Oxygen electrode also has its limitations and is quite unselective for oxygen in the
presence of other oxidants. There are problems in sampling and storing water for chemical
determination of dissolved oxygen, especially so if microflora remains active in the sample.
Titrimetric procedure is also inconvenient for field work. Winklers azide method for the
determination of dissolved oxygen in water is the most well-known of all the chemical methods
used for estimation of dissolved oxygen in water.
Principle: The principle is based on the modified Winkler's method. It involves introducing first
aconcentrated solution of manganese (1) sulphate, sodium hydroxide, and potassium iodide
azide reagent into the water sample. The white ppt of manganese (II) hydroxide Mn(OH): is
formed, and is oxidized by dissolved oxygen in the water sample to give a brown ppt of
manganese (1) hydroxide, Mn(OH)3. The sample is then said to be fixed and can be stored in
this condition indefinitely. Inthe presence of sulphuric acid manganese (llI) hydroxide dissolves
and liberates free iodine from the potassium iodide added, in an amount exactly equivalent to the
amount of dissolved oxygen inwater sample. In the presence of excess iodide ions, the liberated
iodine is present in the form of I;.The amount of liberated iodine is then estimated by titrating
against sodium thiosulphate using starch as an indicator.
The series of reactions which takes place can be summarized as by following equations:
MnSO4 + 2NaOH ’ Mn(OH)2 + Na2SO4
4Mn(OH)2 + O2 + 2H,0 >4Mn(OH)3
Mn(OH)3 + HSO4 ’ MnSO4 + 2H,0 + 0

2KI+ H,SO4 + 0 ’ KSO4 + H:0 + I2

2NaSO3 + Ih ’ NazS4O% + 2Nal

The above equations implies that two moles of h are liberated per mole of O2 and since each I2
reacts with two S203 , one mole of O2 will be equivalent to four moles of sodiumn thiosulphate
that the stoichiometric ratio between the moles of oxygen in the water sample and moles of
thiosulphate used is 1to 4 i.e.
O = 212= 4S;0;
Hence,

MNazs 0, NazS203 -
MpoVD0

and
The main interference in this process is due to the presence of nitrites. These react with KI
liberate I, according to the following equation:
2HNO2+ H)SO4 + 2KI ’ 2NO + K2SO4 + 2H>0 + I2

The liberated I2 will also use up thiosulphate. Sodium azide is, therefore, used in this process to
when sample is
take care of any nitrite present in the water sample, it destroys the nitrite
acidified.

2NaN3 + H;SO4’ 2HN3 + NaSO4

(Hydrazoicacid)

HNO, + HN3 ’ NO; + N2 + H}0

case
Standardization of sodium thiosulphate solution: This method is based on iodometry. In this
to following
potassium dichromate oxidises iodide to iodine in the acidic medium according
equation:
Cr0, + 14 H' + 6I ’ 2Cr + 312 + 7H;0
The liberated iodine is titrated with sodium thiosulphate according to reaction,
2S>O;? + I; ’ S.O6 + 21
On combining the equations,
Crp0, + 6S;0;+ 14 H ’ 2Cr+ + 3S.06+ 7H,0

Hence. MNaz5203 VNazS,03

MKzCr,0, VK2Cr0,
6
1

Procedure

1. Titration of standard potassium dichromate with given thiosulphate solution

10 mL of standard solution of potassium dichromate was pipetted out in a conical flask. To this,
10mL of 5% KI, a pinch of NaHCO; and 10 mL of dil HTSO4 were added. It was covered and
kept in dark for 2-3 minutes. This was titrated against sodium thiosulphate solution taken in
burette. When the solution acquired a greenish yellow colour, 1 mL of starch was added.
Sodium thiosulphate was added till solution acquired a green colour which indicated end point of
the titration.

2. Titration of water sample

A stoppered bottle of 300 mL capacity was filled with given water sample, pointed the bottle
downstream and filled gradually to avoid adding air to the liquid being collected. The stopper
was removed and 3 mL of water was removed from the bottle using graduated pipette. From
burette, l mL of manganese sulphate and 1 mL of alkali iodide azide solution was added below
the surface of water. Shook the bottle well. The brown ppt was formed which were allowed to
settle down completely for 15 mins. After 15 minutes, I mL of conc H2SO4 was added. Bottle
was again gently shaken to dissolve the ppt. 100 mL of water was transferred into a titration
flask. The liberated la was titrated with standardised sodium thiosulphate tillit acquired pale
colour
yellow colour. At this point starch was added and continued the titration till the blue
disappeared.
Observations and Calculations

1. Titration of standard potassium dichromate with given sodium thiosulphate solution

Volume of potassium dichromate pipetted out = 10mL

Indicator used: Starch
Colour change: Disappearance of blue-violet colour
Volume of sodium
S.No. Burette Reading
 Initial Final thiosulphate/mL
1.
2.
3.

MNazSz03 VNazS203 1
MK2Crz07VK2cr07
mol/L
MNazsz03
2. Titration of water sample with given sodium thiosulphate solution
Volume of water sample taken = 100mL
Indicator used: Starch
Colour change: Disappearance of blue-violet colour
S.No. Burette Reading Volume of sodium
Initial Final thiosulphate/mL
1.
2.
3.

MNa2S203 VNa2S203
MpoVpo
=
4
1

Dissolved oxygen in water sample = MNazSa Oa * molar mass of oxygen * 1000 ppm

Result: The amount of Dissolved Oxygen in the given water sample is ppm

Analytical Signíficance of Dissolved Oxygen: Write Yourself

To refer experiment, watch

https://www.youtube.com/wateh?v=m9XGsEs55Qo