UNIVERSITI TEKNOLOGI MARA

FAKULTI KEJURUTERAAN KIMIA

ENGINEERING CHEMISTRY LABORATORY
(CHE485)

NAME :MUHAMMAD FAIZ BIN ISMAIL

STUDENT NO :2010801434
GROUP :EH 2221B
EXPERIMENT :BASIC WATER PROPERTIES ONE
DATE PERFORMED : :20th AUGUST 2010
SEMESTER :1
PROGRAMME / CODE :EH222 / CHE485
SUBMIT TO :MADAM RABIATUL ADAWIYAH BINTI ABDUL AZIZ

No. Title Allocated Marks (%) Marks

1 Abstract/Summary 5
2 Introduction 5
3 Aims 5
4 Theory 5
5 Apparatus 5
6 Methodology/Procedure 10
7 Results 10
8 Calculations 10
9 Discussion 20
10 Conclusion 10
11 Recommendations 5
12 Reference 5
13 Appendix 5
TOTAL MARKS 100

Remarks:

Checked by: Date:

Table of Content

N Title
Pages
O
1 Abstract/ Summary
2 Introduction
3 Theory
4 Aims/Objectives
5 Apparatus
6 Procedures
7 Results
8 Calculations
9 Discussions
10 Conclusions
11 Recommendations
12 References
13 Appendices
Abstract.

In this experiment, we have determined the amount of dissolved oxygen in the water
sample that we had collected in the pond at the Dataran Cendikia. Through observation, we
know that the water sample contained the oxygen by having colour of orange-brown with
precipitate when added with Manganous Sulphate Powder Pillow with Alkali Iodide Azide
Reagent Powder Pillow and it have a colour of yellow when added with sulfonic acid powder.
Both of this proves the existence of oxygen in this water sample. Then, through a series of
calculation, we measured the amount of the dissolved oxygen in the water sample that is 6.34
mg/L and 7.1 mg/L.
Introduction

Dissolved oxygen (DO) level is refers to the amount of oxygen dissolve in water and
is particularly important in aquatic ecology. Without an appreciable level of DO, many kinds
of aquatic organisms cannot exist in water. A high DO level is needed for the aquatic
organism to live and it makes drinking water taste better than usual. High DO level is
important to every living organism. However, industries reduce to least possible amount of
dissolved oxygen in order to reserve it pipeline from corrode.

The level of DO in water is dependent on many physical, chemical, and biochemical

factors—aeration, wind, velocity of water flow, algae, temperature, atmospheric pressure,
organic compounds, salt content, bacteria, and animals. Algae produce oxygen during
photosynthesis under sunlight. However, this process is really not an efficient means of
oxygenating water because some of the oxygen formed by photosynthesis during the daylight
hours is lost at night when the algae consume oxygen as part of their metabolic processes.
When algae die, the degradation of their biomass also consumes oxygen.

Temperature has a significant impact on the solubility of oxygen in water. Increasing

the temperature will normally decrease the DO concentration in water. It is important to
distinguish between oxygen solubility, which is the maximum DO concentration at
equilibrium, and the actual concentration of DO, which is generally not the equilibrium
concentration and is limited by the rate at which oxygen dissolves. Water saturated with
oxygen at 25oC contains 8.4 mg/L.

Therefore, in this experiment, we will determine the amount of dissolve oxygen in

water by using a selected procedure that is Azide Winkler Method. Here, we had checked the
dissolve oxygen in the sample and it must be comply with Malaysian Standard of Water
Quality.
Theory

Winkler test is used in this experiment in order to measure the concentration of

dissolved oxygen (DO) in a water sample. In this method, excess manganese (II) sulphate
will react with the alkali-iodide azide reagent that is an iodide ion (I- ) and potassium
hydroxide ion (OH-) ion in water to form a white precipitate Mn(OH)2. Alkali-iodide azide
also composed of NaN3 that is an alkali azide compound that will eliminated the nitrile
interference that can interfere the reaction of reducing or oxidizing substances in this test.

MnSO4+2KOH Mn(OH)2+K2SO4 (1)

If oxygen is present inside the water, the Mn(OH)2 will react further to form an
orange- brown precipitate, manganic oxide (MnO(OH)2) but if the oxygen is not present
inside the water sample, the colour of the white precipitate will remain unchanged.
[ CITATION Rut03 \l 1033 ]pg84)
2Mn(OH)2 + O2 2MnO(OH) (2)

Sulfamic acid powder pillow, H3NSO3 is added, which dissolves the manganic oxide
and in together with the potassium iodide, KI added earlier, forms iodine (I2), that had give
the orange colour to the sample:
2Mn(OH)2 + 4H3NSO3 2Mn(SO4)2 + 6 H2O (3)
2Mn(SO4)2 + 4KI 2MnSO4 + 2K2SO4 + 2I2- (4)
Then, by referring table 1, a sample of volume of the solution is taken and poured into
a graduated cylinder.

Range
Sample volume Titration Cartridge, Catalog Digit
(mg/L
(mL) N (Na2S2O3) Number Multiplier
D.O)
1-5 200 0.200 22675-01 0.01

2-10 100 0.200 22675-01 0.02

>10 200 0.200 14401-01 0.10

The quantity of iodine is measured by titrating with sodium thiosulfate (Na2S2O3)

until the orange colour from I2 becomes pale yellow as yellow plastic straw.

4 Na2S2O3+ 2I2 2Na2S4O6+ 4NaI (5)

Starch is added near the end of the titration to measure if there is any unreacted iodine,I2 in
the solution as the starch will give a dark blue colour in the presence of I2 and gives a more
obvious colour of endpoint for the test. Then, it is titrated again with sodium thiosulphate
solution until the colour of the solution becomes colourless

The available quantity of MnO(OH)2 formed in the first step is directly proportional to
the dissolved oxygen, and the amount of iodine formed in the second step is directly
proportional to the MnO(OH)4. So, the titration of sodium thiosulphate solution measures a
quantity of iodine directly related to the original dissolved oxygen concentration. Therefore,
by calculating the amounts of sodium thiosulphate used by recording the digits at the body of
the mechanical titrator and multiply its by the digit multiplier given at a sample volume we
had used like in the table 1.
In test 2, we used oxygen powder pillow 1 and 2 to trap the oxygen that gives the
yellow colour of oxygen and then inserted oxygen powder pillow 3 to dissolve any precipitate
and titrate it with sodium thiosulphate as in test 1.

Digits required X Digit Multiplier = ____mg/L Dissolved Oxygen (6)

Here, we obtained the amount of dissolved oxygen in the sample of water that we had
used in this experiment.

Objectives

1. To learn the specific sampling technique in

determining dissolved oxygen concentration in a
sample of water.
2. To understand the chemical principle of water for
dissolves oxygen measurement.
3. To determined the dissolved oxygen that contained in
a water sample
Apparatus and Material

Apparatus

I) 300mL BOD Bottle

1. Bottle, with stopper, BOD, 300-mL

2. Clippers, for opening pillows
3. Cylinder, graduated, 250-mL
4. Digital Titrator
5. Flask, Erlenmeyer, 250-mL
6. Delivery tubes
Material

1. Alkaline Iodide-Azide Powder Pillows 50/pkg 107266

2. Manganous Sulfate Powder Pillows 50/pkg 107166
3. Sodium Thiosulfate Titration Cartridge, 0.2000 N each 2267501
4. Starch Indicator Solution
5. Sulfamic Acid Powder Pillows

II) 60mL BOD Bottle

Apparatus

1. Bottle, with stopper, BOD, 60-mL

2. Clippers, for opening pillows
3. Digital Titrator
4. Flask, Erlenmeyer
5. Polypropylene Beaker
6. Delivery tubes
Material
1. Dissolved Oxygen 1 Reagent Powder Pillows
2. Dissolved Oxygen 2 Reagent Powder Pillows
3. Dissolved Oxygen 3 Reagent Powder Pillows
4. Sodium Thiosulfate Titration Cartridge, 0.2000 N each
 5. Procedure :-

i) Azide Modification of Winkler Method

a) Using a 300mL BOD Bottle.

1. Water sample is collected in a 300 mL BOD bottle.

2. Sample is allowed to overflow the bottle for 2-3 minutes to ensure that air bubble is
not trapped.
3. Stopper is inserted immediately and inverts several times to mix so that air is not
trapped in the bottle. (Flocculent precipitate formed, H will be orange, brown if
oxygen is present or white if oxygen is absent.)
4. Wait until the flocculent in the solution had settled. The bottle is inverted again for
several times and waits until the flocculent settled again.
5. The stopper is removed and contents of 1 sulfamic acid powder are added into the
solution. The stopper is replaced without trapping air in the bottle and the bottle is
inverted several times for it’s to mix.
6. A sample volume of sodium thiosulphate titration cartridge is selected corresponding
to the expected dissolved oxygen (D.O) concentration from table 1.
7. A clean delivery tube is inserted into the titration cartridge. The cartridge is attached
to the titrator body.
8. Delivery knob is turned to eject a few drops of titrant. The counter is reset to zero and
the tip is wiped.
9. A graduated cylinder is used to measure the sample volume from table 1. The sample
is transferred into a 250mL Erlenmeyer flask.
10. The delivery tube tip is placed into the solution and the flask is swirl while titrating
with sodium thiosulphate to a pale yellow colour.
11. Two 1 mL drop of starch indicator is added into the solution and swirl to mix. (note a
dark blue colour will develop)
12. The titration is continued to a colourless end point and the number of the digits
required is recorded.
13. The value of Dissolved Oxygen in water is calculated by the formula:

Digits required X Digit Multiplier = ____mg/L Dissolved Oxygen

a) Using a 60mL BOD Bottle.

1. A water sample is collected in a clean 60mL glass-stoppered BOD bottle.

(Note: Allowed the sample to overflow the bottle for 2-3minutes to ensure air bubbles
are not trapped)

(Note: If samples cannot be analysed immediately see sampling and storage following
these steps.

(Note: This procedure is followed when using the 60mL glass-stoppered BOD bottle
supplied with DREL Portable laboratories.

2. The contents of one dissolved oxygen 1 reagent powder pillow and one dissolved
oxygen 2 reagent powder pillows is added.
3. The stopper is inserted immediately so air is not trapped in the bottle. The bottle is
inverted several times in order for it to mix.
4. Wait until the flocculent in the solution has settled and the top half of the solution is
clear. The bottle is inverted again for several times and waits until the flocculent has
settled.
(Note: Results are not affected if the flocculent does not settle or if some of the
reagent powder does not dissolve.)
5. The stopper is removed and the contents of one dissolved oxygen 3 powder pillow are
added. The stopper is replaced without trapping air in the bottle and it is inverted for
several times to mix.
(Note: The flocculent will dissolve and leave the yellow colour of Oxygen if present)
6. 20mL of the prepared sample is accurately measured and transfer into the 250mL
Erlenmeyer flask.
7. A clean straight-stem delivery tube is attached to a 0.2000N sodium thiosulphate
titration cartridge. The cartridge is twisted onto the titrator body.
8. The delivery tube is flushed by turning the delivery knob to eject a few drops of
titrant. The counter is reset to zero and the tip is wiped.
9. The prepared solution is titrated with 0.2000N Sodium Thiosulphate until the sample
changes from yellow to colourless. The number of digits is recorded.
10. The amount of dissolved oxygen in the water sample is calculated

Digits required X Digit Multiplier = _____mg/L Dissolved Oxygen

Result:-
(I) To Determine the Amount of Dissolved Oxygen in the Water Sample.
300 mL BOD bottle.

Reagent Observation Conclusion

Manganous Sulphate Powder Orange-Brown with Oxygen is Present

Pillow + Alkaline Iodide Precipitate
Azide Powder Pillow
Sulfonic Acid Powder Yellow Colour Oxygen is Present

Digit Required : 317

Digit Multiplier 0.02

Range (mg/L) Dissolve Oxygen = Digit Required X Digit Multiplier

= 317 X 0.02
= 6.34 mg/L (In Range)

(II) 60 mL BOD bottle.

Reagent Observation Conclusion

(Dissolved Oxygen 1 + Dissolved Oxygen 2 + Orange-Brown Oxygen is Present

Dissolved Oxygen 3 ) Reagent Powder Pillow

Digit Required : 71
Digit Multiplier 0.1

Range (mg/L) Dissolve Oxygen = Digit Required X Digit Multiplier

= 71 X 0.1
= 7.1 mg/L (In Range)
Sample Calculation:

Digits required X Digit Multiplier = _____mg/L Dissolved Oxygen

(I) To Determine the Amount of Dissolved Oxygen in the Water Sample.

300 mL BOD bottle.

Digit Required : 317

Digit Multiplier 0.02

Range (mg/L) Dissolve Oxygen = Digit Required X Digit Multiplier

= 317 X 0.02
= 6.34 mg/L (In Range)

(III) 60 mL BOD bottle.

Digit Required : 71
Digit Multiplier 0.1

Range (mg/L) Dissolve Oxygen = Digit Required X Digit Multiplier

= 71 X 0.1
= 7.1 mg/L (In Range)
Discussion

In this experiment, we want to determined the amount of dissolved oxygen in the

water sample that we had taken in the pond at Dataran Cendikia. In this experiment, we used
Winkler Test and the main solution here is azide, so the method is known as Azide-Winkler
Test and the solution used is known as alkali-iodide azide solution. This is due to the role of
azide or NaN3 in becoming the inhibitor for the interference of nitrogen ion from interfering
the oxidation and reduction process that occurred in this experiment by the oxygen and
iodine. The solution used is according to the situation we are facing.

First of all, we had inserted the water sample until it overflow. This is to ensure there
is no air bubbles trapped and in order to get the accurate reading of the oxygen level that is
inside the water sample. If not, the reading will be altered as the air bubbles trapped also have
oxygen inside it. So it will not just be only the water sample oxygen reading.

We added manganeous sulphate and alkaline iodide azide, here we know that its
reacted by observing the changes that a white precipitate Mn(OH)2 had formed and we can
understand it by equation one

MnSO4+2KOH Mn(OH)2+K2SO4 (1)

The white precipitate that is Mn(OH)2 then had turned into an orange-brown
precipitate that is (MnO(OH)2) due to the present of oxygen inside the water. [ CITATION
Rut03 \l 1033 ]pg84) Here, we inverted the bottle a few times in order to makes it mix with
each other and react.

2Mn(OH)2 + O2 2MnO(OH)2 (2)

Then, the sulfamic powder pillow, H3NSO3 is added, and its dissolves the manganese
oxide in together with the, KI added earlier that makes the precipitate loses and forms iodine
(I2), that had give the orange colour to the water sample without precipitate due to the oxygen
present.
 By referring to the table one given, we had selected a 100mL of sample volume, then
transferred into Erlenmeyer flask by a graduated cylinder and a 0.200 titration cartridge with
a catalog number 22675-1 and digit multiplier of 0.02. The digital titrator need to be adjusted
first after inserting the cartridge. First of all, a few drops of titrant must be ejected from the
digital titrator in order to get rid of the air bubble because we want an accurate value of
dissolve oxygen in the water sample and if we had air bubble inside the cartridge of the
digital titrator this will make us having a systematic error.

The delivery tube must be placed inside the solution of sample in order to prevent any
air from the environment entering the sample while conducting this experiment. The flask is
swirl in order to mix the solution faster until it turn to pale yellow.

4 Na2S2O3+ 2I2 2Na2S4O6+ 4NaI (5)

Then, we add two 1mL droppers of starch indicator solution and swirl and here we
had observed that the solution had turned into a dark blue colour. This is due to the iodine
exist inside the solution. By the equation, we know that the available quantity of MnO(OH)2
formed in the first step is directly proportional to the dissolved oxygen, and the amount of
iodine formed in the second step is directly proportional to the MnO(OH)4. So, the titration of
sodium thiosulphate solution measures a quantity of iodine directly related to the original
dissolved oxygen concentration.

We had to continued the titration until the colour become colourless because the
amount of sodium thiosulphate used is equal to amount of Iodine inside the solution and more
importantly it is equal to the amount of dissolve oxygen inside the solution. This is the reason
why we need to titrate until the solution becomes colourless.

Therefore, by calculating the amounts of sodium thiosulphate used by recording the

digits at the body of the mechanical titrator and multiply its by the digit multiplier given in
table 1, we will know the amount of oxygen dissolved inside the sample solution.
 In the second test, we used the 60mL of BOD bottle in order to determined the
dissolved oxygen in the water sample. The step is the same as the first test, but we had
inserted oxygen powder pillow 1 and 2 first into the sample in order to trap all the available
oxygen inside the water sample. The yellow colour of the solution that is allowed to settle
before adding oxygen powder pillow 3 is the oxygen colour that had been trapped by the
oxygen powder pillow 1 and 2. The third powder pillow is inserted to eliminate any particles
before the titration process.

Then, the titration is done like the first test by using sodium thiosulphate cartridge
with the digital titrator until the colour of the solution turn to colourless. By calculating the
amounts of sodium thiosulphate used by recording the digits at the body of the digital titrator
and multiply its by the digit multiplier given in table 1 that we had used, we will know the
amount of oxygen dissolved inside the sample solution.
Conclusion

By this experiment, we had known that there is three sampling technique in

determining dissolved oxygen concentration in a sample of water. The three techniques are
Azide-Winkler Method, Probe and Meter Method, and QA/QC considerations. However in
this experiment, we used Azide-Winkler Method as it is the most accurate method in
determining oxygen dissolved content in sample of water. Azide-Winkler Method is a
titration method by using sodium thiosulphate and the amount of oxygen dissolved is equal to
the amount of sodium thiosulphate used in this experiment.

After conducting this experiment, we measured that the oxygen colour is orange-
brown and the dissolved oxygen in 300mL BOD bottle that we used in the first test contain
6.34 mg/L oxygen dissolved and in the second test, we have 7.1 mg/L oxygen dissolved. We
had conduct this experiment with the same water sample and the first test is to measure the
dissolve oxygen accurately and the second test is to measure the oxygen content inside the
water sample roughly so the first test that we had done don’t have an exceeding value.

We also had understand the chemical principle of water for dissolved oxygen
measurement by the understanding the reaction between the reactant used and the water.
Overall, there is it is basically a redox reaction which uses the dissolved oxygen as a reagent.
The alkali azide, NaN3 used is to makes the nitrogen ion don’t interfere the reaction reduction
and oxidation reaction that proceed in this experiment. If alkali azide not exist, the nitrogen
ion contain inside water sample will interfere the reaction and this phenomenon is called as
interference.
Recommendation

We must swirl the bottle after mixing each drop of the sodium thiosulphate solution
during the titration process so that the reactant react faster. Place a white paper or other white
background as a base to the bottle so that we can observed the colour change better and this is
a vital step as the change of the yellow colour to colourless is the end point of this experiment
and we will know the dissolve oxygen concentration by calculating the sodium thiosulphate
solution that we had used in the titration process. As if we had added it excessively, we would
not get an accurate result.

If the water sample is collected on a cold day, it is very important to do the dissolved
oxygen test in an instant after collecting the water sample as the oxygen inside the water will
lowered when the day become warmth. First, we must put the first two chemicals that is
Dissolved Oxygen powder pillows one and two in order to entrapped all the oxygen inside
the water sample and then we can take it back to warmth to finish the test as the oxygen
dissolved inside the water sample will be unchanged as it is trapped inside the water sample
by the dissolved oxygen powder pillow.
References

Bibliography

1. Ruth F. Weiner, R. A. (2003). Environmental engineering. United States Of America:

Elsevier Science (USA).

2. http://pubs.acs.org/doi/abs/10.1021/i560097a014

3. http://en.wikipedia.org/wiki/Iodine

4. http://en.wikipedia.org/wiki/Iodine_clock_reaction

5. http://en.wikipedia.org/wiki/Manganese

6. v=onepage&q=MnSO4%20reaction%20in%20winkler&f=false

7. http://en.wikipedia.org/wiki/Sulfamic_acid

8. http://www.lamotte.com/pages/common/pdf/instruct/7414.pdf
Appendices