1

SOLIDS DETERMINATION THROUGH WATER ANALYSIS

Dissolved Oxygen Levels in Natural Waters

Claudee Khiarra R. Directo

Jarret Carlo B. Ferrer
Omar Mukhtar Y. Julkipli
Charlene Q. Rabulan
Clint Aldrin A. Valencia
CPE/1 – B12
Electrical, Electronics, and Computer Engineering (EECE) Department
Mapúa University

Rommel Galvan, BSChE, MSIT, MSChE, PhDChE

Instructor, General Chemistry (CM011L)

October 2018
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
Table of Contents

Abstract……………………………………………………………………………………...…….3

Introduction……………………………………………………………………………………......4

Methods……………………………………………………………………………………...…….5

Results…………………………………………………………………………..………….....….13

Discussions…………………………………………………………………………..…….....….15

Conclusions…………………………………………………………………………………...….16

Appendices………………………………………………………...……………………….....….17

References………………………………………………………...…….………………….....….18

Abstract
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
Bodies of water such as streams, rivers, lakes, and oceans are significant in sustaining life here

on Earth. Consequently, this signifies that water quality is essential to promote a healthy cycle in

the system of organisms and the environment. This can be measured through the amount of

dissolved oxygen, as it supplies the needs of many living organisms. The experiment was

transpired using the Winkler method of analysis for dissolved oxygen. It is important to

determine the dissolved oxygen concentration in waters, and, by using the Winkler method, the

amount of dissolved oxygen in a given sample will be identified. Based on the results, it was

concluded that the standardized sodium thiosulfate (Na2S2O3) solution with the presence of starch

as an indicator that determines the amount of I3- . In addition to that, the amount of I3- was the one

that provided the concentration of dissolved oxygen in the water sample.

Keywords: Winkler method, dissolved oxygen, concentration

Dissolved Oxygen Levels in Natural Waters

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
Dissolved oxygen (DO) levels in environmental water depend on the physiochemical and

biochemical activities in water body and it is an important useful in pollution and waste

treatment process control. Two methods are commonly used to determine DO concentration: (1)

The iodometric method which is a titration-based method and depends on oxidizing property of

DO and (2) The membrane electrode procedure, which works based on the rate of diffusion of

molecular oxygen across a membrane.

In the Iodometric method, divalent manganese solution is added to the solution, followed

by addition of strong alkali in a glass-stopper bottle. DO rapidly oxidize an equivalent amount of

the dispersed divalent manganese hydroxide precipitates to hydroxides of higher valence states.

In the presence of iodide ions in an acidic solution, the oxidized manganese reverts to the

divalent state, with the liberation of iodine equivalent of the original DO content. The iodine is

then titrated with a stranded solution of thiosulfate. The titration end point can be detected

visually with a starch indicator. Some oxidizing and reducing agents present in solution can

interfere with the iodometric method. Oxidizing agents liberate iodine from iodides (positive

interference) and some reducing agents reduce iodine to iodide (negative interference). Also,

organic matter present in solution can be oxidized partially in the presence of oxidized

manganese precipitate, thus causing negative errors. Thus, some modification of procedure is

required.

The dissolved oxygen content is an important index when considering its suitability for

town supply. A good clean potable water will give dissolved oxygen value close to the

theoretical value for the saturated solution of oxygen in water. When there is pollution from

organic matter and other trade effluents, the dissolved oxygen is up in various biochemical

oxidation processes and it is only slowly replaced through surface absorption. Such water will
5
SOLIDS DETERMINATION THROUGH WATER ANALYSIS
give a low dissolved oxygen content until oxidation is completed. Adequate dissolved oxygen is

necessary for the life of fish and other aquatic organisms.

In summation and in theory, it is based on oxidation of potassium iodide. The liberated

iodine is titrated against standard hypo solution using starch as a final indicator. Since oxygen in

water is in molecular state and not capable to react with KI, an oxygen carrier manganese

hydroxide is used to bring about the reaction between KI and O2.Manganous hydroxide is

produced by the action of potassium hydroxide and manganous sulphate.

Methods

Materials and Procedures

The following are used in the experiment:

Burette

Pipette

Flask

Beaker

Graduated cylinder

Chemicals required are: MnSO4, KOH, KI, Na2S2O3, Starch, and NaN3

Standard 0.025 M Na2S2O3 Solution

Preparation and standardization of 0.1 M Na2S2O3 solution. For the preparation and

standardization of a 0.1 M Na2S2O3 solution. Prepare only 100 mL of the Na2S2O3 of the

solution described in Experiment 29, Part B.1 and standardize the solution using KIO3 as the

primary standard solution.

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
Preparation of a standard 0.025 M Na2S2O3 solution. Using a pipet and 100-mL

volumetric flask, prepare a 0.025 M Na2S2O3 solution from the standardized 0.1 M Na2S2O3.

Collection of Water Sample

Prepare the flask for sampling. Thoroughly clean and rinse at least three 250-mL

Erlenmeyer flasks and rubber stoppers to fit. Allow to air dry.

Collect the water sample. Gently lay the flask along the horizontal surface of the water.

Slowly and gradually turn the flask upright as the flask fills being careful not to allow any air

bubbles to form in the flask. Fill the flask to overflowing.

“Fix” the dissolved oxygen. Below the surface of the water sample, pipet ~1 mL of the

basic 2.1 M MnSO4 solution into the sample (some overflowing will occur). Similarly pipet ~1

mL of the basic KI-NaN3 solution. A precipitate should form.

Secure the sample. (a) Carefully stopper the sample to ensure that no air bubbles become

entrapped beneath the stopper in the water sample. Again, some overflowing will occur. (b)

Invert and roll the flask to thoroughly mix the reagents. Once the precipitate settles, repeat the

mixing process. (c) Label the sample number for each of the flasks. Store the sample in the dark

and, preferably, in a cool or cold location or on ice.

Temperature. Read and record the temperature of the water at the sample site. Also, write

a brief description of the sample site.

Sample Analysis

Prepare the titrant. Prepare a clean buret. Add 3 to 5 mL of the standard Na2S2O3

solution to the buret, roll the solution to wet the wall of the buret, and dispense through the buret

tip and discard. Use a clean funnel to fill the buret—dispense a small portion through the buret
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
tip. Read and record the volume of Na2S2O3 solution in the buret (Technique 16A.2), using all

certain digits plus one uncertain digit. Place a white sheet of paper beneath the receiving flask.

Prepare Sample. (a) Remove the stopper from the 250-mL Erlenmeyer flask. To the

collected water sample, add ~1 mL of conc H2SO4 and stir or swirl to dissolve any precipitate.

The sample can now be handled in open vessels. (b) Transfer a known, measured but exact

volume (~200 mL, ±0.1 mL) to a receiving flask (either a beaker or Erlenmeyer flask) for the

titrimetric analysis.

Titrate water sample. Slowly dispense the Na2S2O3 titrant into the water sample. Swirl

the flask as titrant is added. When the color of the analyte fades to a light yellow-brown, add ~1

mL of the starch solution. Continue slowly adding titrant—when one drop (ideally, half-drop)

results in the disappearance of the deep-blue color of the I3–•starch complex, stop the titration

and again (after ~15 seconds) read and record the volume of titrant in the burette.

Pre-Laboratory Assignment

1. For a natural water sample, what range of dissolved oxygen concentrations may you

expect? Explain your reasoning.

Dissolved oxygen can range from zero up to saturation for the temperature of the

water. The greater the contact with air, the more turbulence in water then the

greater dissolved oxygen.

2. How does the dissolved oxygen concentration in a water sample change (if at all) with

a. Ambient temperature changes?

Solubility of oxygen decrease as temperature increase, therefore the warmer the

surface of water, the less it requires dissolved oxygen.

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
b. Atmospheric pressure changes?

Water at lower altitudes can hold more dissolved oxygen, therefore, the higher

atmospheric pressure, and the lower dissolved oxygen.

c. The volume of the flask containing the water sample?

There will be more air present in a bigger flask, therefore, the bigger the volume

of the flask, the more dissolved oxygen.

d. The amount of organic matter in the water sample?

The more amount of organic matter, the lower the dissolved oxygen.

e. The depth of the body of water (e.g. lake, river, or ocean)?

The deeper we go in a body of water, the less oxygen will be present, therefore,

the deeper the body of water the less oxygen dissolved.

3. Experimental Procedure, Part A.1, A 100-mL volume of a primary standard 0.0110 M

KIO, solution is prepared. A 25.0-mL aliquot of this solution is used to standardize a

prepared Na2S2O3 solution. A 15.6-mL volume of the Na2S2O solution titrated the KIO3

solution to the starch endpoint. What is the molar concentration of the Na2S2O3 solution?

IO3 – (aq) + 8 I– (aq) + 6 H+(aq) —› 3 I3 – (aq) + 3 H2O(l)

3 (I3 – (aq) + 2 S2O3 2– (aq) —› 3 I– (aq) + S4O6 2– (aq))

6 S2O3 2- + 1O3 - + SI +6H —› 3H2O + 3 S4O6 2-

1O3 + 6 NaH + 6 Na3S2O3 —› 3 H2O + KI + 3 Na3S2O3

0.0110 mol 6 mol Na 2 S2 O 2 −6

0.0289 × × =1.65 x 10 m Na2 S 2 O 3
1L 1 mol KI 03

1.65× 103 m
=0.106 M Na2 S 2 O 3
0.0156
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS

4. Experimental Procedure, Part A.2. What is the procedure for preparing 250 mL of 0.0210

M Na2S2O3 for this experiment from a 100-mL volume of standard 0.106 M Na2S2O3?

M 1V 1
V 2=
M2  Dilute the 43.5 mL of 0.106
M of Na2S2O3
250 mL ( 0.0210 M )
V 2=¿
0.1

V 2=49.5 mL

5. An analysis of a water sample for dissolved oxygen levels provided the data in the

following table. Complete the analysis for Trial 1 (See Report Sheet.) of the water

sample. Record the calculated values with the correct number of significant figures

A. Standard 0.025 M Na2S2O3

1. Sample Volume (mL) 200 mL

2. Buret reading, initial (mL) 3.85 mL

3. Buret reading, final (mL) 18.25 mL

4. Volume Na2S2O3 dispensed (mL) 14.40 mL

5. Average Molar Concentration of Na2S2O3 (mol/L) 0.0213 mol/L

6. Moles of Na2S2O3 dispensed (mol) 3.07 x 10-4 mol

7. Moles of I3- reduced by S2O32- (mol) 1.53 x 10-7 mol

8. Moles of O2 (mol) 7.67 x10-5 mol

9. Mass of O2 (mg) 2.40 mg

10. Dissolved Oxygen ppm O2 (mg/L) 6.965 mg/L

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS

Solutions

6. mol Na2S2O3 dispensed

mole
mol Na 2 S 2 O 3 dispensed= =0.0213
2.0144 L

mol=3.07 ×10−4

7. Moles of I3- reduced by S2O32-

Moles of I 3−, reduced by S 2 O 2−¿ −4 I 3−¿

3 =3.07 × 10 ×1 mol ¿¿
2 mol Na2 S 2 O3

−4 I 3−¿
¿ 1.7416 ×10 mol ×1 mol ¿
2mol Na2 S 2 O 3

¿ 1.53 ×10−4 mol

8. Moles of O2

−4 2 mol Mn(OH )2
Moles of O 2=1.53 ×10 ×
1mol O 2
1 mol I 3−¿ × ¿
4 mole Mn(OH )2

2 mol Mn ( OH )2
¿ 8.708 ×10−5 mol ×
1 mol O 2
1 mol I 3−¿ × ¿
4 mole Mn (OH )2

¿ 7.67 ×10−5 mol

9. Mass of O2

mass O 2=mol O 2 ×molar mass O 2

−5 32 g O 2 −3
¿ 7.67 ×10 mol × × 2.45× 10
1 mol O 2

¿ 2.45 mg
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS

10. Dissolved Oxygen ppm O2

mgO 2
Dissolved O 2=
L sample

2.85 mg
¿
1L
200 mL ×
1000mL

¿ 12.3 ppm O 2

5.b. For Trials 2 and 3, the dissolved oxygen levels were 10.9 ppm and 11.1 ppm respectively.

a. What is the average dissolved oxygen level in the water sample?

12.3+10.4+11.5
Average Dissolved Oxygen Level=
3

¿ 11.4 ppm

b. What are the standard deviation and the relative standard deviation (%RSD) of the dissolved

oxygen level in the water sample?

x x̅ x - x̅ σ

1.15
12.3 11.4 0.810
√ 3−1
=0.758

0.758
10.9 11.4 0.250 %RSD ¿ ×100=6.65 %
11.4

1.1 11.4 0.090

Laboratory Questions

1. Part B. The water chemist waits until returning to the laboratory to fix the water sample

for the dissolved oxygen analysis. Will the reported dissolved oxygen concentration be

reported as too high, too low, or remain unchanged? Explain.

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
The reported dissolved oxygen concentration will remain unaffected since there is

time to be followed which is, within 48 hours the remainder of the dissolved oxygen

analysis is completed in the laboratory.

2. Part B.3. A solution of MnSO4 is added to fix the dissolved oxygen in the collected

sample.

a. What is the meaning of the expression, “fix the dissolved oxygen,” and why is it so

important for the analysis of dissolved oxygen in a water sample?

It means that dissolved oxygen is converted to a compound that is restricted to

escape from the solution. It is important for the analysis of dissolved oxygen in a water

sample because the dissolved oxygen is kept all throughout after fixation for it cannot

escape from the solution and that there is conversion of dissolved oxygen towards Mn

(OH3) in quantity.

b. Only an approximate volume (~1 mL) of MnSO4 is required for fixing the dissolved

oxygen in the sample. Explain why an exact volume is not critical.

An exact volume is not critical because MnSO 4 acts as the excess reactant whilst

the dissolved oxygen is the limiting reactant.

3. Part B.4. No precipitate forms! Assuming the reagents were properly prepared and

dispensed into the sample, what might be predicted about its dissolved oxygen

concentration? Explain.

Its dissolved oxygen concentration is too low since dissolved oxygen causes the

occurrence of precipitation, therefore it can be assumed that there is barely dissolved

oxygen.
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS

4. Part B.5. A water chemist measured and recorded the air temperature at 27°C when he

should have measured the water temperature, which was only 21°C. Because of this error,

will the dissolved oxygen concentration be reported as being higher or lower than it

should be? Explain.

The dissolved oxygen concentration will be reported as lower than it should be

mainly because the air temperature is higher than the water temperature in which the

higher the water temperature means the lower the dissolved oxygen concentration. As

mentioned before, water temperature is inversely proportional to dissolved oxygen

concentration.

5. Part C.3. The colour of the analyte did not fade to form the light yellow-brown colour but

remained intense even after the addition of a full burette of the S 2O32– titrant, even though

a precipitate formed in Part B.4. What can be stated about the dissolved oxygen

concentration of the sample? Explain.

About the dissolved oxygen concentration of the sample, it can be stated that there

is increase of dissolved oxygen after adding a burette filled with S 2O32- titrant since the

sample is acidify with sulfuric acid to dissolve any precipitate.

6. Assuming a dissolved oxygen concentration of 7.0 ppm (mg/L) in a 200-mL water

sample,

a. how many moles of Mn (OH)3 will be produced with the addition of the MnSO4

solution?
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
With the addition of the MnSO4 solution, there will be 2.97 x 10-5 moles of Mn

(OH)3 Produced.

b. How many moles of I3– will be produced when the KI-NaN3 solution is added to the

above solution?

When the KI-NaN3 solution is added to the above solution, there will be 3.68 x

10-6 moles of I3-produced.

c. how many moles of S2O32– will be needed to react with the I3– that is generated?

To react with the I3-that is generated, 2.5 x 10-5 moles of S2O32- will be needed.

d. and, assuming the concentration of the S 2O32– titrant to be 0.025 M, how many

millilitres of titrant will be predictably used for the analysis.

0.5 millilitres of titrant will be predictably used for the analysis.

7. A non-scientist brings a water sample to your laboratory and asks you to determine why

there was a fish kill in the nearby lake. Having recently finished this experiment, what

might you tell that person about the legitimacy of a test for dissolved oxygen? What

reasoning would you use to maintain the integrity of your laboratory?

A test for dissolved oxygen focuses on its concentration in the mg/L of a solution.

This is a good head start in determining the reason for the fish kill in the nearby lake. It is

rather unlikely to have oil spills in a lake, so this means that it will be optimal for testing,

first the concentration of dissolved oxygen. This should allow us to know if there is

enough dissolved oxygen in the lake. Since, if there is not enough DO in the lake, it will

affect the living organisms that lies beneath. In addition, at night there is no occurrence

of photosynthesis, therefore, dissolved oxygen reserves are used. And, if there is not
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
enough dissolved oxygen, which in this case, there is a high chance that the fishes were

killed because of the insufficient dissolved oxygen.

8. a. Fish kills are often found near the discharge point of water from cooling waters at

electrical generating power plants. Explain why this occurrence may occur.

Power plants use the cooling water reservoir and generate electricity by

discharging heated water back into the rivers, lakes and other reservoirs. Near the

discharge point of water, there is a high temperature water, which indicates that there will

be less concentration of dissolved oxygen because it is inversely proportional with

temperature. The higher the temperature, the lower the dissolved oxygen will be. This

explains the reason why fish kills are often found at the discharge point of power plants.

b. Fish kills are often found in streams following heavy rainfall in a watershed dominated

by farmland or denuded forestland. Explain why this occurrence may occur.

Suppose, there are farmlands or denuded forestland, and there’s a heavy rainfall.

Most likely, it will run off to the streams. Water flows from the higher ground; organic

matters, parasites, and other naturally toxic compounds such as ammonia and hydrogen

sulfide will flow in streams of water. This will lessen the concentration of dissolved

oxygen and with the addition of organic matters, parasites, and other toxic compounds

artificial or natural, consequently there is a high chance that it can cause fish kills.

9. Explain how the dissolved oxygen concentrations may change starting at the headwaters

of a river and ending at the ocean. Account for the changes.

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
Going from the headwaters of a river, there are higher concentration of dissolved

oxygen, because of the quality of the water having no salinity. However, at the end of the

ocean, there is a high level of salinity which affects the solubility of oxygen, thus,

affecting the amount of dissolved oxygen in the ocean. Because, as the salinity of the

water increases the water solubility of oxygen decreases.

10. Salt (ocean) water generally has a lower dissolved oxygen concentration than freshwater

at a given temperature. Explain why this is generally observed.

There’s a higher surface area that is exposed in direct sunlight in ocean waters but

waters with high salinity has a higher boiling point because of the NaCl. It is already

given that the higher the temperature goes, then there is lesser amount of dissolved

oxygen. Also, a higher salinity of the water, means a lower solubility of oxygen. Thus,

when these two conditions are met, the dissolved oxygen would be at extreme low levels.

In the ocean where there is a high salinity of water, dissolved oxygen is low; and if it is

on higher temperature levels, dissolved oxygen concentration would be lesser.

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS

Results

A. Water Analysis

1. Sample Volume (mL) 200 mL

2. Buret reading, initial (mL) 25 mL

3. Buret reading, final (mL) 18 mL

4. Volume Na2S2O3 dispensed (mL) 7 mL

5. Molar Concentration of Na2S2O3 (mol/L) 0.02488 mol/L

6. Moles of Na2S2O3 dispensed (mol) 1.7416x10-4 mol

7. Moles of I3- reduced by S2O32- (mol) 8.708x10-5 mol

8. Moles of O2 (mol) 4.354x10-5 mol

9. Mass of O2 (mg) 1.393 mg

10. Dissolved Oxygen ppm O2 (mg/L) 6.965 mg/L

Solutions

1. mol Na2S2O3 dispensed

1L 0.02488 mol
mol Na 2 S 2 O 3 dispensed=7 mL × ×
1000 mL 1L

¿ 1.7416 ×10−4 mol

2. Moles of I3- reduced by S2O32-

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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
Moles of I 3−reduced by S 2 O 2−¿ I 3−¿
3 =mol Na2 S 2 O3 dispensed ×1 mol ¿¿
2mol Na2 S 2 O3

−4 I 3−¿
¿ 1.7416 ×10 mol ×1 mol ¿
2mol Na2 S 2 O 3

¿ 8.708 ×10−5 mol

3. Moles of O2
2 mol Mn(OH )2
3−¿reduced × ¿
1 molO 2
3−¿
1mol I × ¿
4 mole Mn (OH )2
Moles of O2=mol I

2 mol Mn ( OH )2
¿ 8.708 ×10−5 mol ×
1 mol O 2
1 mol I 3−¿ × ¿
4 mole Mn (OH )2

¿ 4.354 × 10−5 mol

4. Mass of O2

mass O 2=mol O 2 ×molar mass O 2

32 g 1000 mg
¿ 4.354 × 10−5 mol × ×
1 mol 1g

¿ 1.393 mg

5. Dissolved Oxygen ppm O2

mgO 2
Dissolved O 2=
L sample

1.393 mg
¿
1L
200 mL ×
1000mL
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS
¿ 6.965 mg/ L

Discussions

The 200mL of water sample was carefully collected so that no air bubbles remain trapped

in the plastic bottle. Then, the dissolved oxygen was fixed by pouring it with 1 mL of MnSO 4

creating orange-brown particles within the water. The scientists considered this as the occurrence

of precipitate where it is believed that the more precipitate, the greater the dissolved

concentration it has. Once the precipitate particles settled, 1 mL of KI – NaN 3 was then poured

creating a clear colored orange-brown water sample, repeating the mixing process.

As the scientist wait for the water sample to settle again, the titrant was prepared by

adding 25 ml of the standard Na2S2O3 solution into the buret. The titrant was slowly dispensed to

the water sample until the orange-brown color fades into a light yellow-brown color. A 1 mL of

starch solution was then added to the sample, transforming the color into a deep colored blue.

Then, continue to slowly add drops of Na 2S2O3 solution until the deep-blue color fades away into

a crystal clear water sample. The dissolved oxygen concentration was then calculated expressing

it in ppm O2.
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SOLIDS DETERMINATION THROUGH WATER ANALYSIS

Conclusion

The Winkler method was used in order to analyze the dissolved oxygen. The standard

procedure for this experiment was to collect water sample in the field where the dissolved

oxygen by two reagents which is the 1 mL of MnSO4 and 1 mL of KI – NaN3 that was used in the

experiment.. Based on the results, it was concluded that the standardized sodium thiosulfate

(Na2S2O3) solution with the presence of starch as an indicator that determines the amount of I3- .

In addition to that, the amount of I3- was the one that provided the concentration of dissolved

oxygen in the water sample. From the data collected and analyzed, the moles of O2 is converted

into milligrams and divided by the volume of the water sample in Liters. The results of the

dissolved oxygen concentration is then expressed in ppm (parts per million) or mg/L.
 Appendix A

Documentation
22
CALORIMETRY
23
CALORIMETRY
24
CALORIMETRY

References

APHA. 1975. Method 208D. Total Nonfilterable Residue Dried at 103-105C (Total Suspended

Matter) in Standard Methods for the Examination of Water and Wastewater, 14th Edition.

American Public health Association. Washington, D.C. 460pp.

USEPA 1979 Method No. 160.2 (with slight modification) in Methods for chemical analysis of

water and wastes. United States Environmental Protection Agency, Office of Research

and Development. Cincinnati, Ohio. Report No. EPA-600/4-79-020 March 1979. 1193

pp.W.