CHM 101 Experiment 7
Dissolved Oxygen Levels in Natural Waters
Objectives
➢ To learn the chemical reactions involved in fixing and analyzing water sample for
dissolved oxygen using Winkler method.
➢ To determine the dissolved oxygen concentration of a natural water sample.
Introduction
The aesthetic appearance of bodies of water such as the color, surface growth and odor
indicate an immediate perception of the quality of water. Other parameters give clear
description of the quality of a water sample such as: pH, dissolved oxygen, alkalinity and
m
hardness. Alkalinity and hardness levels are determined by titrimetric techniques.
er as
co
The level of dissolved oxygen in a water sample is an important factor for the quality of
eH w
water. Dissolved oxygen refers to the level of free, non-compound oxygen
o.
present in water. Oxygen can slowly diffuse into water from the
rs e
surrounding atmosphere. It is an important parameter in assessing water
ou urc
quality because of its influence on the organisms living within a body of
water. The amount of dissolved oxygen is a measure of the biological
activity in which high oxygen concentrations indicate aerobic conditions:
o
clean, clear and unpolluted. However, low oxygen concentrations indicate
aC s
anaerobic conditions: high turbidity, foul odors and extensive plant
v i y re
growth on the surface. It is used as an indicator of the health of a water
body. The solubility of free oxygen in water is inversely proportional to
temperature and directly proportional to pressure. As the temperature increases, the
ed d
amount of oxygen decreases, however as the pressure increase the dissolved oxygen
ar stu
increases. Dissolved oxygen level is usually reported in milligrams per liter (mg/L) or ppm.
The modern method for dissolved oxygen measurements is done with an instrument
known as Dissolved Oxygen Meter.
sh is
In laboratory, dissolved oxygen is measured by the "Winkler titration method”. This test
Th
was originally developed by Ludwig Winkler, while working at Budapest University on his
doctoral dissertation in 1888. The Winkler method is a titration procedure based on the
oxidizing property of dissolved oxygen. This method has long been the standard for
accuracy and precision when measuring dissolved oxygen. When using this method, the
amount of titrant needed to complete the reaction is proportional to the dissolved oxygen
concentration of the sample.
The Winkler method is based on Redox titration to determine dissolved oxygen in the
water sample. The dissolved oxygen in the sample is "fixed" or locked by adding excess of
manganese(II) salt, iodide (I−) and hydroxide (OH−) ions. This is to prevent the change in
concentration of oxygen due to interaction of oxygen from the atmospheric air or any
alteration in temperature and/or pressure which might also cause change in the level of
dissolved oxygen.
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 1
In this method, dissolved oxygen in a known volume of water, is made to liberate an
equivalent amount of iodine using chemical reactions. The released I2 is estimated by
iodometry titration with a standard thiosulfate (S2O3-2) solution using starch as indicator.
The point of color change is called the "endpoint," which coincides with the dissolved
oxygen concentration in the sample.
The reactions taking place in the “Winkler” method are explained as follows:
1. Dissolved molecular oxygen in water reacts with manganese (II) sulfate in basic
medium to produce manganese (III) hydroxide, Mn(OH)3 an orange brown
precipitate. This process is known as “Fixing”.
4MnSO4(aq) + O2(aq) + 8NaOH(aq) + 2H2O(l) → 4Mn(OH)3(s) + 4Na2SO4(aq) (7.1)
2. Mn(OH)3 then reacts with concentrated sulfuric acid and oxidizes iodide (I−) to
iodine.
m
er as
2Mn(OH)3(s) + 3H2SO4(aq) + KI(aq)→ 2MnSO4(aq) + I2(aq) + 6H2O(l) (7.2)
co
eH w
I2(aq) + I−(aq) I3−(aq) (Iodine Complex Equilibrium) (7.3)
o.
rs e
3. This liberated iodine is then titrated against standard sodium thiosulphate
ou urc
(Na2S2O3) solution using starch as indicator. The starch indicator forms a deep-blue
complex with I3− but is colorless in the presence of I−.
o
4. Thiosulphate reduces iodine to iodide ions and itself gets oxidized to tetrathionate
aC s
ion.
v i y re
2S2O32-(aq) + I3−(aq) → 3I−(aq) + S4O62-(aq) (7.4)
ed d
ar stu
➢ Overall Net Ionic Equation and Stoichiometry:
½ O2 + 2H+ + 2I- → H2O + I2
sh is
I2+ I-→ I3-
Th
2S2O32- + I3-→ 3I- +S4O62-
[½ O2 + 2H+ + 2S2O32- → H2O + S4O62- ] .... x 2
O2 + 4H+ + 4S2O32- → 2H2O + 2S4O62- (7.5)
(Ratio 1:4, 1 mole of O2 : 2 mole of I2 : 4 mole of S2O32− )
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 2
Calculations
Step 1: Determine the volume of Na2S2O3 dispensed (mL)
VNaOH Dispensed = Final Burette Reading (Vf ) – Initial Burette Reading (Vi ) (7.6)
Step 2: Determine the number of moles of Na2S2O3 dispensed (mol)
Number of moles (mol) = Molarity (mol/L) x Volume (L) (7.7)
Note: Do not forget to convert the volume from mL to L!
Step 3: Determine the number of moles of I3- reduced by S2O32-
𝒎𝒐𝒍 𝑺𝟐 𝑶𝟐− (7.8)
m
𝟑
𝒎𝒐𝒍 𝐼3− =
er as
𝟐
co
eH w
Note: S2O32-(aq) is the same as Na2S2O3(aq) so your labwrite-up uses them interchangeably. (The
o.
2 Na+ ions are “spectator ions” so they are not involved in the reaction that occurs.)
rs e
ou urc
Step 4: Determine the number of moles of O2
o
aC s
𝒎𝒐𝒍 𝐼3−
v i y re
𝒎𝒐𝒍 𝑶𝟐 = (7.9)
𝟐
ed d
Step 5: Determine the mass of O2 (milligrams)
ar stu
Use the # moles of O2, the molar mass of O2 and the following unit conversion: 1 g = 1000
mg, to find the mass of O2 in (mg):
sh is
Th
𝟑𝟐. 𝟎𝟎 𝒈 𝑶𝟐 𝟏𝟎𝟎𝟎 𝒎𝒈 (7.10)
𝒎𝒈 𝑶𝟐 = 𝒎𝒐𝒍 𝑶𝟐 × ×
𝒎𝒐𝒍 𝒈
Step 6: Determine the ppm of dissolved oxygen (O2) in the sample
Divide the mass of O2 obtained by the volume of the water sample in “L”:
𝒎𝒈 𝑶𝟐 (7.11)
𝒑𝒑𝒎 𝑶𝟐 =
𝑽𝒘𝒂𝒕𝒆𝒓 𝒔𝒂𝒎𝒑𝒍𝒆 (𝑳)
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 3
Step 7: Determine the average dissolved oxygen in ppm O2
𝒑𝒑𝒎 𝒇𝒐𝒓 𝑻𝒓𝒊𝒂𝒍 𝟏 + 𝒑𝒑𝒎 𝒇𝒐𝒓 𝑻𝒓𝒊𝒂𝒍 𝟐 + 𝒑𝒑𝒎 𝒇𝒐𝒓 𝑻𝒓𝒊𝒂𝒍 𝟑 (7.12)
𝑨𝒗𝒆𝒓𝒂𝒈𝒆 𝒑𝒑𝒎 =
𝟑
Apparatus/Reagents Required:
Electronic balance, 50mL Burettete, Burette clamp,10 mL Pipet, Beakers (50 mL and 150mL),
Erlenmeyer flasks (250 mL), sodium thiosulfate standardized solution (Na2S2O3), potassium
iodide (KI), starch indicator, fixed water sample and 6 M sulfuric acid (H2SO4).
Caution!
• Lab coat and safety glasses must be worn at all times in the laboratory.
• Concentrated sulfuric acid (H2SO4) is severely corrosive, hazardous, strong oxidizing
m
agent, and toxic by ingestion and inhalation. It produces severe burns on the skin!
er as
You should work with sulfuric acid in the fume hood.
co
• Clean up any spills on the lab bench, electronic balance and/or floor.
eH w
• Use pipet filler for pipetting solutions.
o.
rs e
• Dispose the analyzed solutions in labeled waste bottles.
ou urc
Clean Up:
o
• Discard all reaction mixtures into a waste bottle provided.
aC s
• Wash all the glass apparatus with tap water and then rinse with distilled water. Clamp the
v i y re
clean burette inverted and place other glassware on your lab bench for drying.
• Tidy up your lab station.
ed d
ar stu
Procedure
The water sample is collected and 'fixed' using Mn2+ salt and hydroxide (OH)- by lab staff.
sh is
Th
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Figure 7.1: Dissolved oxygen titration stages
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 4
1. Fill the Na2S2O3 into the burette and keep it ready for titration. Refer to the “Burette
Preparation Procedure” in Experiment 5 Handout.
2. Take a clean, dry 250mL Erlenmeyer flask.
3. Prepare the pipet and pipet 10.00 mL of the 'fixed' water sample. Refer to the “Pipet
Preparation Procedure” in Experiment 5 Handout.
4. Add ~0.2 g of solid potassium iodide (KI). Solution turns to reddish-brown.
5. Acidify the solution by adding 2.0 mL of 6 M H2SO4.
6. Record the initial burette reading (Vi).
7. Titrate slowly, by adding sodium thiosulfate from the burette into the flask.
8. When the color of the solution fades to a light yellow-brown, add ~1 mL (one full
dropper) of Starch Indicator. The starch indicator forms a deep-blue complex with
I3−.
m
9. Stop adding at the end point, when the solution turns colorless.
er as
10. Record the final burette reading (Vf).
co
eH w
11. Repeat the titrations again for a second and third set of data.
o.
rs e
ou urc
o
aC s
v i y re
ed d
ar stu
sh is
Th
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 5
CHM 101 Experiment 7: Pre-Lab Exercise
Dissolved Oxygen in Natural Waters
Name: ID:
Lab Section: Date: Bench No.:
*All answers must be written in ink.
* Show the steps of each calculation and apply the rule for significant figures
1. Why determination of dissolved oxygen concentrations is important? Explain your
reasoning.
2. How does the dissolved oxygen concentration in a water body change if:
m
er as
a) ambient temperature increases:
co
eH w
b) atmospheric pressure decreases:
o.
rs e
ou urc
c) organic matter increases:
o
aC s
3. Explain why is it important to 'fix’ the dissolved oxygen while collecting the water
v i y re
sample?
ed d
ar stu
4. During a titration for the determination of oxygen level in a water sample, 25.0 mL of
water sample consumed 23.8 mL of 0.0248 M thiosulphate solution.
sh is
a) Calculate the moles the thiosulphate consumed.
Th
b) What would be the moles of oxygen?
5. If 1.58x10-4 moles of O2 are present in 10.00mL of sample; calculate the amount of
dissolved oxygen in ppm (mg/L). (Atomic. wt of Oxygen = 16.00)
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 6
6. Name the indicator used and how do you know the end point reached?
7. What chemicals are added to fix the oxygen level?
8. Which of the water body has a higher dissolved oxygen level and why?
a) Sea Water:
b) Lake Water:
m
er as
co
eH w
o.
rs e
ou urc
o
aC s
v i y re
ed d
ar stu
sh is
Th
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 7
CHM 101 Experiment 7: Report Sheet
Dissolved Oxygen in Natural Waters
Name: ID:
Lab Section: Date: Bench No.:
*Lab Report must be written in ink.
*Apply the rule for significant figures in all calculations & write the correct units
Molar concentration of Na2S2O3 Solution: ___________________
Analysis of Water Sample
Sample # : _____________
m
er as
Trial #1 Trial #2 Trial #3
co
1 Water sample volume
eH w
2 Burette reading, initial
o.
3 Burette reading, final
rs e
ou urc
4 Volume of Na2S2O3 dispensed
5 Molar concentration of Na2S2O3
o
*6 Moles of Na2S2O3 dispensed
aC s
v i y re
*7 Moles of I3- reduced by S2O32-
*8 Moles of O2
ed d
*9 Mass of O2
ar stu
*10 Dissolved oxygen, ppm O2
*11 Average dissolved oxygen, ppm O2
sh is
* Show the calculation (s) steps for only one trial:
Th
This study source was downloaded by 100000806051595 from CourseHero.com on 09-28-2021 15:14:42 GMT -05:00
Spring 2021 CHM 101 Experiment # 7
https://www.coursehero.com/file/84831696/Expt7-Dissolved-Oxygen-Level-in-Natural-Waterspdf/ 8
Powered by TCPDF (www.tcpdf.org)
