Water Qualit)' Monitoring: Total Dissolved Oxygen Assessment in

DilTerent Water Samples by Winkler's Method

I. Importance of Dissoh•cd Oxygen (DO): Knowledge of DO conccntrntion in seawater is

often necessary in env ironmenta l and marine sc iences. It is used by oceanographers to study
w:1tcr masses in the ocean. It provides the marine biologist a means to measure primary
production. panicularly in labor.itory cu hurcs. For the marine chemist, it provides a measure
uf the rcdox potcnti:11 of the water column. DO is also an important factor in corrosion.
Oxygen is poorly so luble in water. The solubility of oxygen decreases with increase in
concentration of the sa lt and hence. sol ubilit y of DO is lesser in saline water. The amoun t of
DO at 100% saturation at sea level is 9.03 mg/L (at 20 °C) and is sufficient to sustain aquatic
life. DO is used as an indicator of the water body' s health. where higher DO concentrations
arc correlated with high productivity and little pollution. Dissolved oxygen is usually
determined by Winklcr's method.

2. How does the Winkler Method work? Winkler"s Method uses titration to detennine DO
in water sample. A sample boltlc is filled completely with water (no air is left to skew the
results). DO in the sample is then "fixed" by adding a series of reagents that fonn an acid
compound that is then titrated with a neutralizing compound that results in a colour change.
The point of colour change is called the "end•poi nt." which coincides with the DO
concentration in the sample. DO analysis is best done in the field. as the sample will be less
altered by atmospheric equilibration.

3. Applications:
DO analysis can be used to detennine the health or cleanliness of a lake or stream. amount
and type of biomass a freshwater, the amount of DO that a system can support, and the
amoum~f decomposition occurring in the lake or stream.
 John Ho.91shilh
20BtT0D5S

Date: 8/3/H
Experiment Water Quality Monitoring: Total Dissolved Oxygen Assessment in
Different Water Samples by Winkler's Method
Problem definition
Dissolved oxygen (DO) is essential to living organisms in water but
harmful if present in boiler feed water leading to boiler corrosion.
Methodology Winkler's titration method is used to assess DO in water.
Solution Estimation of total dissolved oxygen in different water samples.
Student learning Students will learn to
outcomes a) perform Winkler's titration method
b) assess the total dissolved oxygen in different water samples

Principle: Estimation of dissolved oxygen (DO) in water is useful in studying corrosion

effect of boiler feed water and in studying water pollution. DO is usually determined by
Winkler's titration method, which is based on the fact that DO oxidize potassium iodide (Kl)
to iodine (Ii). Since DO in water is in molecular state, as such it cannot oxidize KI. Hence.
manganese hydroxide is used as an oxygen carrier to bring about the reaction between KI and
Oxygen. Manganese hydroxide, in tum, is obtained by the action of NaOH on MnS04.

Mnso. + 2NaOH - Mn (OH),+ :\'a, so.

2Mn(OH), +O, 2Mn0(0H),
MnO(OH), +H,SO, +2H1 0+[0]
2KI+H,SO, +H,O+I,
2Na 2 S 2 0 3 + 12 Na,s,o, + 2Nal
Starch + I, ---+ Blue colored complex.

The liberated iodine (12) is titrated against standard sodium thiosulphate (Na,S 20 3) solution
using starch as indicator.

Requirements:

Reagents and solutions: Standard buffer of pH 7, standard potassium dichromatc (0.01 N). sodium
1hiosulpha1e solution, 10% KI solution. alkali KI solution (Kl + KOH in water). cone. H,SO,.
manganese sulphate, starch solution as indicator.
Apparatus: Conical flask. Burette, Measuring flask, Beakers.

7
 John HMi,hilh
20BCf0055

Procedure:
Titration 1: Standardi,.ation of Sodium Thiosulphate
Rinse and fill the bureue with given sodium thiosulphate solution (Bottle B). Pipeue out 20 mL of
0.0IN K2Cr20, solution (Boule A) into a clean conical flask. To this, add 5 mL H2S04 (1/2 T.T.), 5
ml (1/2 T.T.) of 10% Kl, and titrate against sodium thiosulphate solution. When the solution becomes
straw yellow colour, add starch indicator and continue the titration. End point is the disappearance of
bluish brown colour. Repeat the titration to get concordant value.

Titration 2: Estimation of Dissolved Oxygen

Using a measuring cylinder, add 100 mL of sample water in a conical flask. Further, add 2 mL of
MnSO, and 2 mL of alkali KI solution and shake well for the rough mixing of the reagents. Set aside
the flask for few minutes to allow the precipitate to settle down, and then add 2 mL of cone. H,SO,
for complete dissolution of the precipitate. Then, titrate against std. sodium thiosulphate solution.
When the solution tum into light yellow, add starch indicator. End point is the disappearance of bluish
brown colour. Repeat the titration to get the concordant value. Calculate the strength of dissolved
oxygen from the titer value. Based on that, calculate the amount of DO in the given water sample.

OBSERVATION AND CALCULATIONS

Titration - I: Standardization of Sodium Thiosulphate
Burette reading (mL)
Volume of K2Cr20 7 Volume of sodium
S.No.
(V1,mL) Initial Final thiosulphate (V ,, mL)

I. 20 ml
(\ ~t;. c; 1t; c;
2. 20ml
n ~t; t;. 1c; c;
3. - - - -
Concordant value
1C C.-1

Calculations:

Volume of potassium di chromate V 1 = 20 mL

Strength of potassium dichromate N 1 = 0.0 I N .
Volume of sodium thiosulphate V2 = ....1S,S. ..... mL (From Titration - I)
Strength of sodium thiosulphate N2 = ..-:-... ?
V 1N 1 =V 2N2

:. N2 =V,N,N 2
Strength of sodium thiosulphate = N 2 = 20 x 0.01N 2 =..0...0QJS.Y.... N

8
 Joh11 HOhlnith
201mooss

Titration - II: Estimation of Dissolved Oxygen

Surette reading (rnL)

Volume of water sample Volume of sodium
S. No.
(V 1, rnL) Initial Final thiosulphate (V 2, mL)

I. 100ml
(\ H 14
2. 100ml
() H H
3. - - - -
Concordant value
11 M l

Calculation:
Volume of sodium thiosulphate V 2 = .. .1.1 .... mL (From Titration -2)

Strength of sodium thiosulphate N 2 = 0,00.18~ N (From Titration - I calculation)

•
Volume of water sample taken V,= 100 rnL

Strength of given water sample N, =?

V 1N 1 =V 2N2

N 1 =V 2 XN 2/100
= .o. .oo.o.s.L N
Amount of DO (ppm)= normality x equivalent weight of O2 x 1000 mg/L of the given water sample.

= ...0,0.0.Q.gb .... N x 8 x 1000 mg/L

= £t.i,i~1 ________ ppm.

Result: Amount of DO in the given water sample= .. .. 1 ... ppm.

•
hom Tihalien 1,
Shw gH1 aj- sod,~m thi01 Ldp\,e>J£ Nl = V, N,
Vi
V2 = 2.S .SmL
V1=20mt..
N1=0 .0 1N
Nl = 10 -,. 0-01 = 0.007S4 N
15.S
i:=rom Tiholi&ri 2,
shqJ1~th e} woleJz. s~mp ~
V1= II ml.-
V1 = 100ml 9 .
N1= o.c~m)4 N "¥ N,"' ~ "o.oon4 = o.ooO<ob N
100
Amowru, aj, DO = N,..,. ~uiv~ WU<:ihl 6i- 02- x IOOO mg /L = 0.000%1> 'o t l{X:O = Ei.88 Prm
1 ppm