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ABSTRACT
This experiment was carried out to determine the amount of dissolve oxygen (DO) in
the water sample. The water sample taken from UiTM Shah Alam Lake. The method use in
this experiment is Azide Modification of Winkler method and the water sample been titrated
with sodium thiosulphate to determine the amount of dissolve oxygen in the water sample.
Through observation, we know that the water sample contained the oxygen by having colour
of orange-brown with precipitate when added with Manganese Sulphate Powder Pillow with
Alkali Iodide Azide Reagent Powder Pillow and it have a colour of yellow when added with
sulfamic acid powder. As a result from the experiments, the water sample for 300 mL and 60
mL of BOD bottles contain 5.6 mg/L and 2.4 mg/L of dissolve oxygen respectively. Those
amount should be in the range of 2-10 mg/L as stated in Table 1 in our procedure in which
not in the range of Malaysia Standard of Water Quality. Therefore, the water sample cannot
be used for drinking and not suitable for daily activities. The water sample also polluted for
aquatic life.
2. INTRODUCTION
1
Dissolved oxygen can refer to the level of free, non-compound oxygen present in
water. The amount of dissolved oxygen present in water or wastewater is essential for most
forms of life. Dissolved oxygen is a good indicator of water quality. 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.
Oxygen dissolves into water by means of the atmosphere and plants. The level of DO
in water is dependent on many physical, chemical, and biochemical factors which are
aeration, wind, velocity of water flow, algae, temperature, atmospheric pressure, organic
compounds, salt content, bacteria, and animals. [Robert G, Wetzel (et al), 2000, pp 73, 84].
For lake or river, the primary source of oxygen for a body of water is from microscopic algae
or submerged plants. In the presence of sunlight, these plants produce oxygen via
photosynthesis. A dissolved oxygen level that is too high or too low can harm aquatic life and
affect water quality.
3. AIMS
1. Determine the dissolve oxygen (DO) level in the series lake water sample.
2. Identify whether the amount of dissolve oxygen (DO) in the water sample comply
with the Malaysia Standard of Water Quality or not.
3. Study and understand Azide Modification of Winkler method.
4. Determine the lake water sample is polluted or not for aquatic habitat.
5. Able to understand the chemical reaction takes place in Winkler method.
4. THEORY
First devised in 1889, the Winkler method is considered the "gold standard" for
measuring the concentration of dissolved oxygen in a sample of water. Through a series of
chemical reactions, the oxygen (O2) combines with iodine to form a golden yellow chemical.
Therefore each oxygen molecule is associated with an iodine molecule, and we can measure
oxygen by measuring the iodine. In the titration process, titration cartridge is use. The
titration cartridge is set to minimum 1.0 mL volume for each drop so the volume of sodium
thiosulfate added to neutralize the solution can be calculated more easily.
Once the water sample is collected, it is important to "fix" the sample immediately.
Phytoplankton, bacteria, and other organisms in the sample can quickly change the oxygen
content of the sample through photosynthesis and respiration. In the first test, 300 mL of
BOD bottle is used while 60 mL BOD bottle for second test. The first step of the Winkler
method is the addition of manganese (II) sulphate (a source of manganese ions) to the sample,
quickly followed by the addition of iodide-azide reagent powder (a source of iodine). In the
presence of the strong base, each oxygen atom binds with a manganese ion to form a white
precipitate Mn (OH )2 . Dissolved oxygen will oxidize manganese (II) ions. Alkali-iodide
azide also composed of Na N 3 that is an alkali azide compound that will eliminated the
4
nitrile interference that can interfere the reaction of reducing or oxidizing substances in this
test
2 MnSO4(s) + O2 (aq) 2MnO(OH)2 (s)
(Equation 4.1)
This reaction creates a pale precipitate that will eventually sink to the bottom of the
sample container. If oxygen is present inside the water, the Mn(OH)2 will react further to
OH
form an orange - brown precipitate, manganic oxide (MnO( 2 ) but if the oxygen is not
present inside the water sample, the colour of the white precipitate will remain unchanged.
[Ruth F. Weiner, (2003) pp84]
4Mn(OH)2 (s) + O2 (aq) + 2 H2O 4Mn(OH)3 (s)
(Equation 4.2)
Sulfuric or sulfamic acid is added to the solution to reduce the pH and dissolve the
precipitate. When this occurs, free iodine is produced at a rate of one iodine molecule per
manganese ion. This produces one iodine molecule for each oxygen molecule in the sample.
The Mn(SO4)2 formed by the acid converts the iodide ions into iodine ( I 2 ), that had give
the orange colour to the sample, itself being reduced back to manganese(II) ions in an acidic
medium. At this point, the sample is "fixed" (all the oxygen converted to iodine) and can be
set aside for several hours before final analysis.
Mn(SO4)2 + 2 I (aq) Mn2+ (aq) + I2 (aq) + 2 SO42 (aq)
(Equation 4.3)
Then, by referring table 1, a sample of desired volume of the solution is taken and
poured into a graduated cylinder.
Range
(mg/L D.O)
Sample
Volume
Titration
cartridge
(NNa2S2O3)
Catalog
Number
Digit Number
1-5
200
0.200
22675-01
0.01
2-10
100
0.200
22675-01
0.02
>10
200
0.200
14401-01
0.1
Table 1
(Equation 4.4)
We can determine how much iodine was in the solution from the amount of
thiosulfate added. Furthermore, because each iodine molecule was produced by the reaction
of a single oxygen atom, the amount of thiosulfate added also tells us how much oxygen was
in the sample. 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 it by the digit multiplier given at a sample volume.
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.
The concentration of dissolve oxygen in the sample calculated using this formula ;
Concentration of dissolve oxygen = Digit required digit multiplier
= mg/L dissolved oxygen
(Equation 4.5)
The water quality test had being carried out so many times before this. For example,
physicochemical analysis on water quality status of Bertam River in Cameron Highlands,
Malaysia had conducted by Wan Mohd Afiq. The result obtained as follow;
Parameter
Dry
Wet
Range Mean (SD)
Range
Mean (SD)
pH
6.50 - 7.76 6.54 (0.15)
6.92 - 7.54
7.26 (1.21)
Temperature (C)
15.37 - 19.41 18.19 (0.91) 15.29 - 17.62
15.95 (2.65)
-1
Conductivity (Scm )
38 - 80 58.33 (9.19)
25 - 324 107.67 (17.94)
Dissolved Oxygen (mgL-1)
4.61 - 8.18 6.31 (1.87)
6.06 - 7.32
7.03 (0.08)
-1
Dissolved Solids (mgL )
28 - 52 43.33 (7.31)
65 - 72
68 (11.33)
Salinity (ppt)
0.01 - 0.02 0.01 (0.002)
0.02 - 0.03
0.02 (0.021)
Table 2 The physical characteristics of Bertam River water along different seasonal period
From the data taken, the mean concentration of dissolved oxygen in Bertam River was
obtained slightly high during wet rather than in dry season. During dry season the
concentration of oxygen is 6.31 mg/L while wet seasin give 7.03 mg/L concentration of
oxygen. The threshold range for Malaysian River is 3 - 5 mg/L. [Gasim M.B, et al (2006), pp
72].
5. APPARATUS
Using 300mL BOD Bottle (Test 1)
1.
2.
3.
4.
5.
6.
No
Materials
.
1.
2.
3.
4.
5.
6.
Distilled water
Table 5.1: List of Materials Used in test 1.
No
.
Materials
1.
2.
3.
4.
6. PROCEDURE
(Azide Modification of Winkler Method)
Using a 300 mL BOD bottle
1. Water sample is collected in a clean 300 mL BOD bottle.
2. One Manganese sulphate powder pillow and one alkaline iodide-azide reagent powder
pillow are added into the bottle.
3. The stopper immediately inserted so air is not trapped in the bottle. The bottle is
inverted several times to mix.
4. Wait until the floc in the solution is settled. The bottle inverted again several times
and wait until the floc has settled.
5. The stopper is remove and the content of one sulfuric acid powder pillow is added.
The stopper is replace without trapping air in the bottle and invert the prepared sample
several times to mix.
6. Select a sample volume and sodium thiosulfate titration cartridge corresponding to the
expected dissolved oxygen (D.O.) concentration.
7. Clean delivery tube inserted into the titration cartridge to the titrator body.
8. The delivery knob is turned to eject a few drops of titrant. Reset counter to zero and
wipe the tip.
9. Graduated cylinder is used to measure the sample volume. The sample is transferred
into 250 mL Erlenmeyer.
10. Delivery tube tip is placed into the solution and swirled the flask while titrating with
sodium thiosulfate to a pale yellow color.
11. I mL droppers of starch indicator solution is added and swirled to mix.
10
11
Observation
Conclusion
Orange-brown precipitate
present
Oxygen is
present
Yellow-gold solution
Oxygen is
present
200
0.200 N
Digit required
560
560 0.01
= 5.6
Table 7.2: Determine the dissolve oxygen using 300 ml BOD bottle.
Using 60 mL BOD Bottle
Reagent
Observation
Conclusion
Orange-brown
Oxygen is
present
20
0.200 N
Digit required
24
24
0.1
= 2.4
12
9. DISCUSSION
In the Winkler method, 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 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 dissolved oxygen is made to react with Iodide ion to yield Iodine which will
be titrated afterwards with thiosulfate. DO presented in the sample rapidly oxidizes an
equivalent amount of dispersed divalent manganese hydroxide precipitate to hydroxides of
higher oxidation states. In the presence of iodide ion and upon acidification, the oxidized
manganese reverts to the divalent state, with the liberation of iodide equivalent to the original
DO content in the sample.
First of all, the water sample poured in BOD Bottle 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. The
manganeous sulphate and alkaline iodide azide are added and its reacted by observing the
changes that a white precipitate Mn (OH )2 had formed.
Mn(OH )2
2++2 OH
(s) (White precipitate)
Mn
Mn (OH )2 (s) + O2 2Mn (OH )2 (s) (orange-brown precipitate)
2+
+
I2 + 3 H 2 O
The white precipitate that is Mn (OH )2 2 then had turned into an orange-brown
precipitate due to the present of oxygen inside the water. (Ruth F. Weiner, 2003) pp 84).
Then, the bottle nverted a few times in order to makes it mix with each other and react. Then,
the sulfamic powder pillow is added, and its dissolves the manganese oxide in that makes the
13
precipitate loses and forms iodine ( I 2 ), that had give the yellow-gold colour to the water
sample without precipitate due to the oxygen present.
Iodine is a strong oxidizing agent and it useful for titrating strong reducing agent such
as dissolved oxygen. In the other hand, iodine is the weak reducing agent and as basis to
determine the amount of dissolve oxygen in the water sample. In this experiment, to
determine the amount of oxygen dissolved is done by determining the I 2 produced which is
equivalent to the dissolved oxygen using the titration with thiosulfate.
By referring to the table one given, we had selected a 200mL of sample volume, then
transferred the water sample into Erlenmeyer flask by a graduated cylinder and a 0.200
titration cartridge with a catalog number 22675-1 and digit multiplier of 0.01. 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.
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. From this we know that the available quantity of Mn (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 Mn (OH )4 . So, the titration
of sodium thiosulphate solution measures a quantity of iodine directly related to the original
dissolved oxygen concentration. The titration continued 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 the water sample need to titrate until the solution becomes
colourless.
14
For the first test, the volume of sodium thiosulfate recorded is 0.56 mL and multiply
with digit multiplier 0.01. The concentration of dissolve oxygen is 5.6 mg/L. Its
concentration is not in the range of 1-5 (mg/L) from table 1. Thus the result is not valid. The
second trial should be carry out to take 100 mL of sample to get more accurate concentration
of dissolve oxygen in the range of 2-10 (mg/L).
Next, the 60mL of water sample is used to determine the amount of oxygen dissolve.
The step is the same as the first test, but oxygen powder pillow 1 and 2 are inserted 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. The amount of dissolved oxygen can be determined
by multiply the volume of sodium thiosulfate required with the digit multiplier which is 0.1.
The concentration of dissolve oxygen is 2.4 mg/L which it is valid as the range for the 60mL
of sample is not exceed 10 mg/L.
The difference of DO in both sample because of the presence of heavy metal in 60mL
of water sample. For example of heavy metal are Zn, Cu, Pb, and Cr. The difference reagents
used in test1 and 2 could also contribute in the difference in concentration of dissolve oxygen
in the tests even the water sample taken from the same sources.
Compared to the result obtained from Bertam river, results in test 1 was indicated that
the concentration of dissolved oxygen in Shah Alam lake water not much differ from Bertam
river (4.61 - 8.18) mgL-1 as recorded by Wan Mohd Afiq et al. But for test 2, the result was a
bit differ. This could be because of the different weather condition between this two places
that have a difference temperature. Bertam which close to Cameron highland has a low
temperature and was considered having cool climate, with temperatures no higher than 25C
during day time than hot dry condition in shah alam.
15
10. CONCLUSION
By
technique
this
experiment,
we
had
known
that
there
is
three
sampling
techniques are
Azide-Winkler Method, Probe and Meter Method, and QA/QC considerations. However in
this experiment, Azide-Winkler Method is used 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 5.60 mg/L oxygen dissolved and in the
second test, we have 2.4 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 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, used is to makes the nitrogen ion dont 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.
16
From the experiment, the lake water from Seksyen 7, Shah Alam is not drinkable.
This is because the dissolved oxygen in the water is extremely low. The drinking quality
water standard in Malaysia stated that in a drinking water, the dissolved oxygen in should be
more than 7. (National Water Quality Standard for Malaysia, WEPA) .So the water sample
are really not drinkable as it can affect the human health.
Dissolve oxygen water in the water is 2.4 in 60 mL water sample. So it can be
concluded that the water sample is not suitable aquatic life population to survive. Thus, the
Shah Alam lake water is polluted.
11. RECOMMENDATIONS
Instead of using manganese sulphate powder and alkaline iodide-azide powder, why
do not we used it in solution state. It might faster the reaction and the molecules fully react to
each other. In addition, the powder in pillow are difficult to cut and pour in the BOD bottle
which contains the sample. Then, there is also some powder stuck in the pillow and take time
to take it out. This also can interrupt the concentration of oxygen in the sample. That means
the volume of titration and range also change.
Then, store the solution for a few days or weeks to get more accurate result. This is
because the reaction can be fully done. This experiment are done for ensure that the water can
be drink or not. So if the result are not correct it will affect our health.
Other than that, 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.
17
18
WATER
QUALITY
QUALITY
Parameter
DRINKING
STANDARDS
Maximum
Acceptable
Group
Acceptable Value
Value
(mg/litre (unless
(mg/litre
otherwise stated))
(unless
otherwise
stated))
0 in 100 ml
0 in 100 m
5 NTU
15 TCU
6.5 - 9.0
0.2 - 5.0
Not Less Than
Total Coliform
E.coli
Turbidity
Color
pH
Free Residual Chlorine
1
1
1
1
1
1
Combined Chlorine
Temperature
Clostridium perfringens
1.0
-
Absent
(including spores)
19
Coliform bacteria
Colony count 22
Conductivity
Enterococci
Odour
Taste
Oxidisability
1500
1000
Chloride
250
250
Ammonia
1.5
1.5
Nitrat
10
10
Ferum/Iron
1.0
0.3
Fluoride
1.5
0.4 - 0.6
Hardness
500
500
Aluminium
0.2
Manganese
0.2
0.1
10
1.0
1.0
Nitrite
Mercury
0.001
0.001
Cadmium
0.003
0.003
Arsenic
0.01
0.01
Cyanide
0.07
0.07
Plumbum/Lead
0.05
0.01
Chromium
0.05
0.05
Cuprum/Copper
1.0
1.0
20
Zinc
Natrium/Sodium
200
200
Sulphate
250
250
Selenium
0.01
0.01
Argentum
0.05
0.05
Magnesium
150
150
Mineral Oil
0.3
0.3
Chloroform
0.2
Bromoform
0.1
Dibromoklorometana
0.1
Bromodiklorometana
0.06
Fenol/Phenol
0.002
0.002
Antimony
0.005
Nickel
0.02
Dibromoacetonitrile
0.1
Dichloroacetic acid
0.05
Dichloroacetonitrile
0.09
Trichloroacetic acid
0.1
Trichloroacetonitrile
0.001
Trihalomethanes - Total
1.00
Aldrin / Dealdrin
0.00003
0.00003
DDT
0.002
0.002
0.00003
0.00003
Methoxychlor
0.02
0.02
Lindane
0.002
0.002
Chlordane
0.0002
0.0002
Endosulfan
0.03
0.03
21
Hexachlorobenzena
0.001
0.001
1,2-dichloroethane
0.03
2,4,5-T
0.009
2,4,6-trichlorophenol
0.2
2,4-D
0.03
0.03
2,4-DB
0.09
2,4-dichlorophenol
0.09
Acrylamide
0.0005
Alachlor
0.02
Aldicarb
0.01
Benzene
0.01
Carbofuran
0.007
MCPA
0.002
Pendimethalin
0.02
Pentachlorophenol
0.009
Permethrin
0.02
Pesticides
Pesticides - Total
0.02
Vinyl chloride
0.005
Gross alpha ()
0.1Bq/l
0.1Bq/l
Gross beta ()
1.0 Bq/l
1.0 Bq/l
Tritium
Polycyclic aromatic
hydrocarbons
Propanil
Tetrachloroethene and
Trichloroethene
22
Class
pH
I
>7
II
6-7
III
5-6
IV
5
V
<5
DO
>7
5-7
3-5
1-3
<1
BOD
<1
1-3
3-6
6 - 12
> 12
COD
< 10
10 - 25
25 - 50
50 - 100
> 100
TSS
< 25
25 - 50
50 - 150
150 - 300
> 300
NH3-N
< 0.1
0.1 - 0.3
0.3 - 0.9
0.9 - 2.7
> 2.7
WQI
> 92.7
76.5 - 92.7
51.9 - 76.6
31.0 - 51.9
< 31.0
Status
Clean
Slightly Polluted
Slightly Polluted
Polluted
Polluted
USES
23
Class I
Class IIA
Class IIB
Class III
Class IV
Class V
24