DISSOLVED OXYGEN

(Winkler Titration)
I.

Data and Results

Standardization of Thiosulfate
Primary Standard used: K2Cr2O7
Formula mass of 1O standard: 294.185 g
% Purity of 1O standard: 99.8%
Trials
Weight of K2Cr2O7 (g)
Corrected Weight of K2Cr2O7 (g)

Table 1: Standardization of Thiosulfate

1
2
0.1016 g
0.1012 g
0.1014 g
0.1010 g

Final Reading Na2S2O3 (ml)

Initial Reading Na2S2O3 (ml)
Volume Na2S2O3used (ml)

84.3 ml
0 ml
84.3 ml

83.1 ml
0 ml
83.1 ml

84.0 ml
0 ml
84.0 ml

Corrected Vol. of Na2S2O3, mL

82.4 ml

81.2 ml

82.1 ml

8.366 x 10-3 M

8.456 x 10-3 M
8.417 x 10-3 M
0.0168 N

8.430x 10-3 M

Molarity of Na2S2O3
Ave. Molarity of Na2S2O3
Ave Normality of Na2S2O3

Table 2: Indicator Blank

Trials
1
Before Addition of Starch Solution
Final volume Na2S2O3(ml)
1.9 ml
Trials
1
Initial volume Na2S2O3(ml)
0 ml
of the sample ( ml)
100 ml
Net Volume NaVolume
1.9 ml
2S2O3 (ml)
Ave. volume of Na2S2O3 (ml)
1.9 ml
Final volume Na2S2O3 (ml)
2.3 ml
Initial volume Na2S2O3 (ml)
0 ml
Net Volume Na2S2O3 (ml)
2.3 ml
Corrected volume of Na2S2O3 (ml)
0.4 ml
mg Cr2O7 of unknown
% Cr2O7 of unknown
Average % Cr2O7 of unknown
DO (mg/L)

II.

3
01020 g
0.1018 g

Table 3: Sample Analysis

2
100 ml
2.4 ml
0 ml
2.4 ml
0.5 ml

Calculations
Standardization of Thiosulfate
6KI + 7H2SO4 + K2Cr2O7 Cr2 (SO4)3 + 3I2 + 7H2O + 4K2 + SO4
2Na2S2O3 + I2 Na2S4O6 + 2NaI
6KI + 7H2SO4 + K2Cr2O7 + 2Na2S2O3 + I2 Cr2 (SO4)3 + 3I2 + 7H2O + 4K2 + SO4 + Na2S4O6 +
2NaI

Corrected Weight. of K2Cr2O7

Formula: Mass K2Cr2O7 x percent purity

Trial 1: 0.1016 g x

99.8
100

= 0.1014 g K2Cr2O7

Trial 2: 0.1012 g x

99.8
100

= 0.1010 g K2Cr2O7

Trial 3: 0.1020 g x

99.8
100

= 0.1018 g K2Cr2O7

Corrected Volume of Na2S2O3

Formula: ml Na2S2O3= Volume Na2S2O3 used - Ave. volume of Na2S2O3
Trial 1: ml Na2S2O3= 84.3 ml 1.9 ml = 82.4 ml Na2S2O3
Trial 2: ml Na2S2O3 = 83.1 ml 1.9 ml = 81.2 ml Na2S2O3
Trial 3: ml Na2S2O3= 84.0 ml 1.9 ml = 82.1 ml Na2S2O3

Molarity of Na2S2O3
Formula: M Na2S2O3 =

corrected weight K 2 Cr 2 O7 x FW K 2 Cr 2 O7 x stoichiometric ratio

corrected volume of Na 2 S 2 O3
1 mol K 2 Cr 2 O7
2 mol Na 2 S 2 O3
x
294.185 g K 2 Cr2 O 7 1 mol K 2 Cr 2 O7
1L
82.4 ml Na 2 S 2 O3 x
1000ml

0.1014 g K 2 Cr 2 O7 x
Trial 1: M Na2S2O3 =

8.366 x 10-3 M Na2S2O3

1mol K 2 Cr 2 O7
2mol Na2 S 2 O3
x
294.185 g K 2 Cr 2 O7 1mol K 2 Cr 2 O7
1L
81.2 ml Na 2 S2 O3 x
1000 ml

0.1010 g K 2 Cr2 O7 x
Trial 2: M Na2S2O3=

8.456 x 10-3 M Na2S2O3

1mol K 2 Cr 2 O7
2mol Na 2 S 2 O3
x
294.185 g K 2 Cr 2 O7 1mol K 2 Cr 2 O7
1L
82.1 ml Na 2 S2 O3 x
1000 ml

0.1018 g K 2 Cr2 O7 x
Trial 3: M Na2S2O3 =

8.430x 10-3 M Na2S2O3

Ave. Molarity of Na2S2O3

Formula:

xi
n

8.366 x 10
8.456 x 10
8.430 x 10
( 3)
(3)+
3
(3)+

= 8.417 x 10-3 M Na2S2O3

Normality of Na2S2O3
Oxidation: 2S2O32- + I2 S4O62- + 2I + 2eReduction: 6I- + 14H + Cr2O72- + 6e- 2Cr3+ + 3I2 + 7H2O
Redox: 6S2O32- + 3I2 + 6I- + 14H + Cr2O72- 3S4O62- + 6I + 2Cr3+ + 3I2 + 7H2O
Formula: N = M x n, where n is equal to the number of electrons/equivalence
Trial 1: N = ( 8.366 x 10-3 ) x 2 = 0.0167 N
Trial 2: N = ( 8.456 x 10-3 ) x 2 = 0.0169 N
Trial 3: N = ( 8.430x 10-3 ) x 2 = 0.0169 N

Ave Normality of Na2S2O3

Formula:

xi
n

0.0167 N + 0.0169 N + 0.0169 N

3

= 0.0168 N

Sample Analysis

Corrected volume of Na2S2O3

Formula: ml Na2S2O3 = Volume Na2S2O3 used - Ave. volume of Na2S2O3
Trial 1: ml Na2S2O3 = 2.3 ml 1.9 ml = 0.4 ml Na2S2O3
Trial 2: ml Na2S2O3 = 2.4 ml 1.9 ml = 0.5 ml Na2S2O3

mg Cr2O7 of unknown
Formula: M Na2S2O3 x V Na2S2O3 x FW Cr2O7 x stoichiometric ratio

Trial 1: mg Cr2O7 =

mmol Na2 S 2 O3
mg Cr 2 O7
x
0.4
ml
Na
S
O
x
2
2
3
82.4 ml Na 2 S2 O3
1 mmol Cr2 O 7
5 mmol Cr2 O7
2 mmol Na2 S2 O3 =

mmol Na2 S2 O3
mg Cr 2 O7
Trial 2: mg Cr2O7 = 1 ml Na S O
x 0.5 ml Na2S2O3 x 1 mmol Cr2 O 7
2 2 3

5 mmol Cr2 O7
2 mmol Na2 S2 O3 =

% Cr2O7 of unknown
Formula: % Cr2O7 =

massCr 2 O7
volume of unknown sample

1g
1000 mg
Trial 1: % Cr2O7=
100 ml unknown sample
mgCr 2 O7 x

1g
1000 mg
Trial 2: % Cr2O7 =
100 ml unknown sample
mgCr 2 O7 x

x 100% =

x 100% =

Average % Cr2O7 of unknown

Formula:

III.

x 100%

xi
n

Discussion
In this experiment, the amount of dissolved oxygen in a water sample was determined through the
Winkler method. The Winkler method uses titration to determine dissolved oxygen in the water sample. A
DO bottle is filled completely with water (no air is left to skew the results). The dissolved oxygen in the
sample is then "fixed" by adding a series of reagents that form an acid compound that is then titrated with a
neutralizing compound that results in a color change. The point of color change is called the "endpoint,"
which coincides with the dissolved oxygen concentration in the sample.
Dissolved oxygen (DO) refers to the level of free, non compound oxygen present in water or other
liquids. It is a vital parameter in evaluating water quality, where higher dissolved oxygen concentrations are
correlated with high productivity and less contamination. The dissolved oxygen content is affected by the
source, raw water temperature, treatment and chemical and biological processes taking place in the
distribution system. Depletion of dissolved oxygen in water supplies can encourage the microbial reduction
of nitrate to nitrite and sulfate to sulfite.
In this experiment, the basis of the method is the quantitative oxidation of iodide ions to iodine by
the oxygen in the tap water sample. Iodine is a moderately strong oxidizing agent and is useful for titration
of strong reducing agents like dissolved oxygen. While iodide ion is a weak reducing agent and is the basis
of determining the amount of I 3 produced, which is equivalent to the dissolved oxygen using titration with
thiosulfate.
Since thiosulfate solution is not stable, it must be standardized with a primary standard, potassium
dichromate (K2Cr2O7). Standardization is based on the co-proportionation reaction of iodide with

dichromate, thereby forming iodine. KI crystals and sulfuric acid was added to the solution K 2Cr2O7 one
after the other. The resulting solution was titrated right away with sodium thiosulfate (Na 2S2O3) as the
titrant and starch solution as the indicator. The solution was made acidic by the addition of sulfuric acid
(H2SO4) which causes the equilibrium to shift to the left due to the common-ion effect to prevent forward
reaction.
6KI + 7H2SO4 + K2Cr2O7 Cr2 (SO4)3 + 3I2 + 7H2O + 4K2 + SO4
2Na2S2O3 + I2 Na2S4O6 + 2NaI
6KI + 7H2SO4 + K2Cr2O7 + 2Na2S2O3 + I2 Cr2 (SO4)3 + 3I2 + 7H2O + 4K2 + SO4 + Na2S4O6 +
2NaI
The oxidation-recation balanced equations are written below:
Oxidation: 2S2O32- + I2 S4O62- + 2I + 2eReduction: 6I- + 14H + Cr2O72- + 6e- 2Cr3+ + 3I2 + 7H2O
Redox: 6S2O32- + 3I2 + 6I- + 14H + Cr2O72- 3S4O62- + 6I + 2Cr3+ + 3I2 + 7H2O
The endpoint of the reaction is indicated using starch which does not dissolve in solutions but
exists as colloid and is just suspended in the analyte. The starch indicator ought to be added only before the
endpoint or when the yellow iodine color is beginning to fade. The solution exhibits a deep blue color in the
absorption of iodine. When the iodine is converted into iodide ion, the blue color disappears and the
complete disappearance of the color indicates the endpoint.
For the sample analysis, the same concepts apply in the determination of the amount of dissolved
oxygen. Two samples of tap water were collected and were put in DO bottles. 2 mL of manganese sulfate
solution and alkali-iodide-azide reagent was added and brown manganese dioxide was formed which
indicating the presence of oxygen.
Mn+ + 2OH- + O2 = MnO2 + H2O
Iodine was formed by oxidation of iodide through the addition of sulfuric acid.
MnO2 + 4H+ + 2I- = Mn+ + I2 + 2H2O
The liberated iodine was titrated with standard sodium thiosulfate solution until a play straw color
was observed.
2Na2S2O3 + I2 = Na2S4O6 + 2NaI
The addition of starch indicator changes the color of the solution to blue. The titration was
continued until the blue color disappeared. The final readings were then recorded.
IV.

Conclusion
The Winkler Method is commonly used to measure dissolved oxygen (DO). In this method a series
of solutions is added to the tap water samples which react with the dissolved oxygen in the sample to
release free iodine. The quantity of free iodine released is proportional to the amount of free dissolved
oxygen in the original sample. The amount of free iodine in the sample is determined by adding a starch
indicator solution to the sample, which turns blue in the presence of iodine, then titrating with sodium
thiosulfate (Na2S2O3) until a colorless endpoint is reached. The amount of sodium thiosulfate needed to
titrate the iodine is directly proportional to the concentration of dissolved oxygen in the original sample.

V.

References
Chem 28.1 Laboratory Manual
Skoog, D.A., West D.M., Holler, F.J., Crouch, S.R., Fundamental of Analytical Chemistry, 9th
edition, Brooks/Cole, Singapore, 2013.

Determination of the Dissolved Oxygen Concentration. Retrieved from

http://www.chem.science.unideb.hu/Pharm/Environmental%20analytical%20chemistry_1.pdf
Laboratory 12: Dissolved Oxygen. Retrieved from
http://www4.bluevalleyk12.org/bvn/ekessler/eniche/apbiology/ecology/2ActivitiesAssignments/AP
Dissolved
OxygenLab.pdf
The Chemistry of Dissolved Oxygen Measurement. Retrieved from
http://www.cwc.nic.in/main/HP/download/11%20Chemistry%20of%20DO%20measurement.pdf
Buckner, M. (2015). The Winkler Method Measuring Dissolved Oxygen. Retrived from
http://serc.carleton.edu/microbelife/research_methods/environ_sampling/oxygen.html