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NRP : 03211840000015
2020
CHAPTER 1
INTRODUCTION
Iron is one of the unwanted molecules in water. Bitter and metallic characteristic taste
are common characteristic of the presence of iron in water. It also oxidized precipitate that
can turn Fe into non soluble form. The oxidation process occurs while the water that
containing significant quantities of iron appears clear when drawn and change quickly upon
exposure to air. It involves the conversion of ferroin ion to ferric ion. Not only that, when tap
water that contains iron directly contacted with another thing, it may leave reddish stain. The
emerge of iron in tap water occurs from corrosion of pipe and dissolution process of iron
stones in nature. Besides impacted taste and odor, the emerge of iron can also lead to turbidity
of water. It is caused by iron bacteria growth leading of the clogging of pipes. Since the
parameter is turbidity, so we can measure the amount of iron by its absorbance level, using
spectrophotometer (Adebayo, et al., 2011).
Iron and manganese are primarily nuisance chemicals with characteristic staining
properties, although high levels can impart a bittersweet or metallic taste to drinking water.
The drinking water standard for iron is 0.3 milligrams per liter (mg/l), and the standard for
manganese is 0.05 mg/l. Typical values of dissolved iron and manganese in groundwater are
less than 10.0 mg/l and 2.0 mg/l, respectively (Lemley, et al., 2005).
Manganese is considered to be the 12th most abundant element in the biosphere. Its
concentration in earth crust reaches as high as 0.098%. It is widely distributed in soil, water,
sediment and biological materials. Manganese has cumulative properties. Various methods
for the determination of manganese with chromogenic organic reagents have been reported.
The reagents suggested for determination of manganese include: toluidine blue, Mordant
brown 33, phenoxazine, eosin (Rustamov & Abbasova G. G., 2014).
Among the various methods of volumetric analysis, precipitation titrations are based on
the formation of compounds of limited solubility. In particular, titrimetric methods based on
the use of silver nitrate as precipitating reagent are termed as argentometric titrations. The
endpoint of the titration is observed using potassium chromate as an indicator, which gives
brown-red silver chromate precipitate when all chloride ions have reacted with the silver
ions. Mohr’s method remains one of the oldest titration methods and is still used in many
laboratories. During the titration, the precipitation of silver chloride occurs
Ag2+ + Cl– = AgCl
and the endpoint of this titration is observed by the appearance of silver chromate
2Ag+ + CrO4 2– = Ag2CrO4
as the new equilibrium solid phase, when all chloride ions have reacted with the silver
ions. Mohr’s method remains one of the oldest titration methods and is still used in many
laboratories. This challenge examines the slight difference that exists between the observed
endpoint and the actual chemical equivalence in titration along with the magnitude of errors
that this discrepancy may cause (Meija, et al., 2016).
Manganese concentration in water is primarily controlled by pH and redox
conditions, where solubility increases under acidic as well as under anaerobic conditions. In
neutral conditions, the redox potential has a stronger influence on manganese mobility than
pH. The concentration of manganese under aerobic conditions - typical of shallow aquifers
and surface water - is generally low and as a rule do not reach detection limits. The reason is
that in aerobic conditions, manganese is found in its stable oxidized form, generally as MnO2,
which is highly insoluble. Spectrophotometric methods play an important role in manganese
determination for several decades. Aromatic amines, azo dyes, oximes, porphyrins and other
reagents have been used for the colorimetric determination of manganese. The measurement
is generally fulfilled applying the light absorption by permanganate or utilizing a relatively
large scale of reagents, for example formaldoxime and PAN. Manganese can be determined
by spectrophotometry with previous oxidation of Mn(II) in a strong basic medium, using 3,
3 ′ , 5.5 ′ -tertramethylbenzidine as a chromogenic reagent (Nadaska, et al., 2012)
Chlorinity is one of the most fundamental quantities associated with water quality,
and it is directly related to the salinity of sea water and often used to determine the salinity.
In recent years, physical methods of determining salinity, such as coulometry, measurements
of conductivity, refractive index, or density, have become more popular because of their
speed. Nevertheless, chemical measurements of chlorinity still remains an important and
independent method of characterizing water quality. Various chemical methods have been
reported for chlorinity determination: the gravimetric method with AgCl precipitates, various
volumetric precipitation titrations with silver (I) or mercury (II) ions, and a recent
spectroscopic method utilizing the Raman scattering band of OH stretching of water. The
analytical methods recommended in the Standard Method for the Examination of Water and
Waste Water and the Official and Standardized Method of Analysis are: (1) argentometric
titration with silver nitrate using potassium chromate indicator, (2) titration with mercuric
nitrate using s-diphenylcarbazone indicator, and (3) potentiometric titration using a glass and
a silver-silver chloride electrode (Hong, et al., 2010).
CHAPTER II
WORK SCHEME
25 ml of water sample
1 ml concentrated HCl
0.5 ml Hydroxylamine
1 ml Phenanthroline Monohydrate
Result
25 ml of sample
AgNO3 solution
25 ml of sample
Pour into 100 ml Erlenmeyer Flask
1/35,45 N AgNO3
Result
CHAPTER III
DISCUSSION
Add 1mL
Phenanthroline Works as specific reagent
Monohydrate solution for measuring Fe(II) in
into each Erlenmeyer water.
flask
Fe
Absorbance mg/L
y x
0.025 0.1
0.03 0.15
0.05 0.25
0.1 0.5
0.165 0.8
0.2 1
0.25 1.2
Table 3.1 Calibration Data of Fe
Fe Absorbation Curve
0.3
0.25
y = 0.2045x + 0.0003
0.25
0.2
0.2
Absorbance
0.165
0.15
0.1
0.1
0.05
0.05 0.03
0.025
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Concentration
From the curve above, we can plot the absorbance result into the curve and calculate
the amount of iron dissolved in the water sample by:
So, from this calculation we know that the amount of iron contained in the outlet
sample is -0.98mg/L and -1.9mg/L. As the result, we take the average level absorbance
which is -1.44 mg/L. A negative concentration value indicates that the sample was
analyzed but that the concentration was below the determination limits of the analytical
method. Concentrations below this lower determination limit are too small to be detected
by the method. Systematic effects can also give rise to negative results. For example,
over-correcting of interference effects is sometimes encountered in the determination of
elements by atomic spectrometry and is one cause of the problem. Another common
cause is lack of fit at the low end in an estimated calibration function (Analytical
Methods Committee, 2001). The other possibilities are the cuvette hit the wall of
spectrophotometer, or the blank solution contaminated with Fe since the distilled water
is produced from the pipe which may contain iron from corrosion. The other interference
is that might be have high level of salinity so it forms colloidal substances and will affect
the turbidity that is read by spectrophotometer. Since there are no changes in color after
the addition of reacting agents, we assume that the water sample has low concentration
of Fe2+ ion (under zero). This result does qualify the standard of Indonesia Public Health
Ministry Regulation 492/Menkes/per/IV/2010, which states that concentration of iron in
water must be below 0.3 mg/L.
3.4.1 Manganese Analysis by Spectrophotometry Method
Iron and manganese are common metallic elements found in nature. Manganese
forms a black residue. The drinking water standard for manganese is 0.05 mg/l. Typical
values of dissolved iron and manganese in groundwater are less than 10.0 mg/l and 2.0
mg/l, respectively (Lemley, et al., 2005) Manganese is considered to be the 12th most
abundant element in the biosphere. Its concentration in earth crust reaches as high as
0.098%. Various methods for the determination of manganese with chromogenic
organic reagents have been reported. The reagents suggested for determination of
manganese include: toluidine blue, Mordant brown 33, phenoxazine, eosin (Rustamov
& Abbasova G. G., 2014).
The first step is to add three drops of concentrated nitric acid to 25 mL of sample
in Erlenmeyer flask. Nitric acid is steamy, clear and colorless. Adding it causes no
change to the sample. The purpose of adding HNO3 is to create acidic condition in the
sample, dissolve manganese and get rid of Cl- ions and other interfering substances.
Next, is doing titration with AgNO3 as titrant. It helps to bind the unwanted Cl- ion in
water sample. Volume of AgNO3 needed to titrate the sample is 8 mL This titration is
done to get rid of pollutant or interfering substances by binding Cl - and Ag+, forming
AgCl which forms the white sediments. After titration, the sample contains sediments at
the bottom and becomes viscous and turbid.
Then, the solution is heated until it boils. But before it boils, we should add
K2S2O8 crystal into the solution. It is aim to oxidize manganese ions of low valency into
manganese oxide and potassium permanganate. The persulfate method is suited for
routine determinations of manganese because pretreatment of samples is not needed to
overcome chloride interference. Ammonium persulfate is commonly used as the
oxidizing agent. The oxidation of manganese in lower valences to permanganate by
persulfate requires the presence of Ag+ as a catalyst. The reaction involved in the
oxidation may be represented as follows:
2Mn2+ + 5S2O82- + 8H2O → 2MnO4- + 10SO42- + 16H+
(Sawyer, et al., 2003)
After sample boils, no color change is observed. This indicates that there is low
manganese present and the experiment is stopped.
3.4.2 Chloride Analysis by Mohr’s Argentometric Method
The most used methods for the determination of chloride concentration in water
include Mohr method, consisting in titration of chloride with a solution of silver nitrate
in excess, detectable in presence of potassium chromate as indicator (Jacoban &
Macoveanu, 2015). Chlorinity is one of the most fundamental quantities associated with
water quality, and it is directly related to the salinity of sea water and often used to
determine the salinity. Various chemical methods have been reported for chlorinity
determination: the gravimetric method with AgCl precipitates, various volumetric
precipitation titrations with silver (I) or mercury (II) ions, and a recent spectroscopic
method (Hong, et al., 2010).
The first reagent used in chloride analysis is potassium dichromate and it is added as
much as 0.5 ml to 25 ml of outlet sample in Erlenmeyer flask. K 2Cr2O4 is yellow liquid,
has odor and at room temperature. After addition sample turns light yellow. K2Cr2O4 is
added as an oxidizing agent and as an indicator to the end-point of titration. Then, 1
spoonful spatula of zinc oxide in white, fine powder form, is added to the sample.
Addition of ZnO causes the sample to turn milky yellow with sediments. The purpose of
adding ZnO is as indicator to formation of sediments by bonding impurities that can
disturb chloride analysis. Lastly, the sample is titrated with 1/35.45 N of silver nitrate
until appearance of first red color. AgNO3 is clear and colorless liquid. After titration the
sample turns slightly red. Volume of AgNO3 used for titration until first reddish color
appears are 1.6 mL and 2 mL. So, the average is 1.8 mL to make first reddish stain color
is appeared. The purpose of this titration is to form precipitate in chloride from the
samples. The end point of the titration occurs when all the chloride ions are precipitated.
Then additional silver ions react with the chromate ions of the indicator, potassium
chromate, to form a red-brown precipitate of silver chromate. Then, the amount of
chloride dissolved in sample can be determined by this formula:
b x N x 35.45
Cl2 (mg/L) = 1000 x
mL sample
From this “Analysis of Iron, Manganese and Chloride” experiment, we can conclude that the
water sample from Gebang area has the following properties:
1. Iron content of -1.44 mg/L. This result qualified the standard of Indonesia Public Health
Ministry Regulation 492/Menkes/per/IV/2010, which states that concentration of iron in
water must be below 0.3 mg/L; The negative concentration may cause by human error,
high salinity in blank solution, or iron contamination in blank solution.
2. Does not contain any dissolved manganese ions due to absence of violet color in final
solution;
3. Concentration of dissolved chloride is 72 mg/L. This does fulfill the 250 mg/L standard
of Indonesia Public Health Ministry Regulation 492/Menkes/per/IV/2010.
CHAPTER V
QUESTIONS AND ANSWERS
1. Explain in what form iron can be analyze with Phenanthroline method and how it
works?
2. Explain the effect of iron in drinking water!
3. Explain the function of persulfate in Manganese analysis!
4. Explain the purpose of addition of Ag+ in Manganese analysis!
5. Explain the effect of Manganese in drinking water!
6. What is the effect of high concentration of chloride in drinking water?
7. Does the excessive addition of indicator into water affected the value of chloride
analysis in Mohr method?
ANSWERS:
1. Iron must be in the form Fe2+. To become that form, water solutions must be oxidized with
Hydroxylamine (Fe3+ to Fe2+) and Phenanthroline Monohydrate (complex ions to Fe2+),
besides that, iron is already expose to atmosphere so it will be oxidized automatically.
2. Effects of iron in drinking water:
• If iron drink by someone it will damage the transportation of the oxygen to blood, damage
the intestine, and iron will accumulate in the body because our body can excrete iron, so
it will make skin go black.
• Taste will be a little bitter
• Form sediments, pollute piping and plumbing (clog the pipe)
3. Persulfate oxidize the manganese contained in the sample, through this equation
2 Mn2+ + 5S2O82- → 2MnO4 - + 10 SO42- + 16 H +
4. To bind the Cl- ion, so after that the color of the solution becomes white
5. Effects:
• It will damage the lung. Manganese make our lungs weaker so it is difficult to breathe,
causes bronchitis and pneumonia,
• It will damage the brain permanently.
6. Chlorine will accumulate in our body and become carcinogenic.
7. If too much indicator is added into the sample, there will be no difference in the result,
because the amount of reagents will limit the reaction, so it will be the same.
REFERENCES
Adebayo, B., Ayejuyo, S., Okoro, H. & Ximba, B., 2011. Spectrophotometric Determination
of Iron (III) in Tap Water using 8-Hydoxyquinoline as a Chromogenic Reagent. African
Journal of Biotechnology, 10(71), pp. 16051-16057.
Analytical Methods Committee, 2001. AMC Technical Brief. In: AMC Analyst. s.l.:The
Royal Society of Chemistry, pp. 256-259.
Chemetrics, 2018. Iron (total, soluble, ferrous) - Phenanthroline Method, s.l.: s.n.
Hong, T.-K., Kim, M.-H. & Czae, M.-Z., 2010. Determination of Chlorinity of Water without
the Use of Chromate Indicator. International Journal of Analytical Chemistry.
Jacoban, C. & Macoveanu, M., 2015. A Comparison of Argentometric Titration and
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ATTACHMENT