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Hardness of water: Water which does not produce lather with soap solution
readily, but forms a white curd, is called hard water.
Units of Hardness:
1
1mg/L = 1 mg of CaCO3 eq. hardness of 1 L of water.
But 1 L of water weighs = 1kg =1000g =1000 X 1000 mg= 106 mg.
It is a complexometric method.
or MY2-
Where M= Ca or Mg.
2
10. When EBT is added to hard water buffered to a pH of about 10 by employing
NH4OH+NH4Cl buffer, a wine-red unstable complex is formed.
pH=10
M2+ + EBT ---------- [M-EBT] complex
titration
[M-EBT] complex + EDTA -------- [M-EDTA] complex + EBT
(Wine-red) (Blue)
However, when nearly all M2+ ions have formed [M-EDTA] complex, then next
drop of EDTA added displaces the EBT indicator from [M-EBT] complex and wine-red
colour changes to blue colour (due to EBT). Thus, at equivalent point,
3. Standardization of EDTA solution: Rinse and fill the burette with EDTA
solution. Pipette out 50mL of standard hard water in a conical flask. Add 10-15 mL of
buffer solution and 4 to 5 drops indicator. Titrate with EDTA solution, till wine-red
colour changes to clear blue. Let volume used be V1 mL.
Calculations:
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=> 50 X 1 mg of CaCO3 = V1 mL of EDTA
= V2 X 50 / V1 mg of CaCO3 eq
= 1000 V2 / V1 ppm
= V3 X 50 / V1 mg of CaCO3 eq
ALKALINITY
On the other hand titration of the water sample against a standard acid to
methyl orange indicator endpoint marks the completion of i), ii) & iii).
Hence the amount of acid used after the phenolphthalein end point
corresponds to one half of normal carbonate + all the bicarbonates; while the total
acid used represents the total alkalinity ( due to OH- , CO32- and HCO3- ions).
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ii) CO32- only or
iii) HCO3- only or
iv) OH- & CO32- together or
v) CO32- & HCO3- together
Thus, OH- & HCO3- ions cannot exist together in water. On the basis of same
reasoning, all the three ions (OH- , CO32- and HCO3-) cannot exist together.
Procedure: pipette out 100ml water sample in a clean conical flask. Add to it 2 to 3
drops of a phenolphthalein indicator. Run N/50 HCl from a burette, till the pink colour
is disappeared. Then to the same solution, add 2 to 3 drops of methyl orange ,
continue the titration, till the color changes yellow to orange pink.
i) When P=0, both OH- & CO32- ions are absent, and alkalinity in that case
due to HCO3- only.
ii) When P=½M, only CO32- ion is present, since half of carbonate
neutralization reaction i.e. [CO32- ] + [H+] [HCO3-] takes place with
phenolphthalein indicator; while complete carbonate neutralization
reaction i.e. [HCO3-] + [H+] H2O + CO2 occurs when methyl orange
indicator used. Thus, alkalinity due to CO32- = 2P.
iii) When P=M, only OH- is present, because neither CO32- nor HCO3- is
present, thus alkalinity due to OH- = M.
iv) When P > ½M, in this case, besides CO32- , OH- ions are also present. Now
half of CO32- equal to M-P; so alkalinity due to complete CO32- =2(M-P)
Therefore alkalinity due to OH- = M - 2(M-P) = 2P – M.
v) When P < ½ M, ;in this case, besides CO 32- , HCO3- ions are also present
now alkalinity due to CO32- = 2P.
Alkalinity due to HCO3- = (M-2P).
P=0 0 0 M
P=½M 0 2P 0
P=M M 0 0
P<½M 0 2P M-2P
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Ion exchange resin: Ion exchange resins are insoluble, cross linked, long chain
organic polymers with a microporous structure. The ion exchange property of these
polymers is due to mainly the functional groups attached to them. These functional
groups may be acidic or basic. Based on functional groups the resins may be
classified as: a) Cation exchange resins b) Anion exchange resins.
ii) Anion exchange resins (R’OH-): They are styrene-di vinyl benzene or
amino-formaldehyde copolymers, which contain amino or quaternary
ammonium or quaternary phosphonium or tertiary sulphonium groups as
an integral part of the resin matrix. These, after treatment with dil.NaOH
solution, become capable to exchange their OH- ion with the anions in
water.
Process: It consists of two tanks. Cation resins and anion resins are kept in the 1st
and 2nd tank respectively. The hard water first is passed first through cation
exchange column, which removes all the cations like Ca 2+, Mg2+ etc. from it, and
equivalent amount of H+ ions are released from this column to water.
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2 RH+ + Ca2+ R2Ca2+ + 2 H+
2 RH+ + Mg2+ R2Mg2+ + 2 H+
After cation exchange column, the hard water is passed through anion
exchange column, which removes all the anions like SO42-, Cl-, etc. present in the
water and equivalent amount of OH- ions are released from this column to water.
The H+ and OH- ions released from both the column get combined to produce
water molecule.
H+ + OH- H2O
Thus, water coming out from the ion exchanger is free from cations as well as
anions. Ion free water is known as deionized or demineralized water.
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R2Mg2+ + 2 H+ 2 RH+ + Mg2+ (washings)
The column is washed with deionized water and washings which contain Ca 2+,
2+
Mg , SO42- , Cl- ions is passed to sink or drain.
• It produces water of very low hardness (2ppm), so it is very good for treating
water for use in high pressure boilers.
Disadvantages:
• If water contains turbidity, then the out put of the process is reduced. The
turbidity must be below 10ppm. If it is more it has to be removed first by
coagulation and filtration.
Thus, in reverse osmosis process methods pure water is separated from its
contaminants, rather than removing contaminants from the water.
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The membrane consists of very thin film of cellulose acetate, affixed to either
side of a perforated tube. However, more recently superior membranes made of
polymethacrylate and polyamide polymers have come into use.
Advantages:
• Reverse osmosis process is a distinct advantage of removing ionic as well as
non ionic, colloidal and high molecular weight organic matter.
• It removes colloidal silica, which is not removed by demineralization.
• The maintenance cost is almost entirely on the replacement of the semi
permeable membrane.
• The life time of membrane is quite high, about 2years.
• The membrane can be replaced within a few minutes, there providing
uninterrupted water supply.
• Due to low capital cost, simplicity, low operating cost and high reliability, the
reverse osmosis is gaining ground at present for converting sea water into
drinking water and for obtaining water for very high pressure boilers.
Textile industry needs frequent dying of clothes, and the water used by this industry
should be soft and free from organic matter. If hard water used uniform dying is not
possible. Because hard water decrease the solubility of acidic dyes. Basic dyes even
precipitate out in such hard water. Organic matter imparts foul smell. If the matter
contains Fe, Mn, color or turbidity it causes uneven dyeing and leaves stains on
fabrics. Hence, water should be free from these impurities.
Laundries require soft water, free from color, Mn and Fe. Because hardness increases
consumption of soaps. Salt of Fe and Mn impart grey or yellow shade to the fabric.
Boilers require water of zero hardness otherwise efficient heat transfer is prevented
by scale formation. Untreated water can also lead to corrosion of boiler material,
some times even explosion can also occur.
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Paper industry requires water free from SiO2, turbidity, alkalinity and hardness. SiO2
produces cracks in the paper. Turbidity, Fe & Mn affects the brightness and color of
the paper. Alkalinity consumes alum and increase the cost of paper. Hardness
increases the ash content of the paper.
Beverages require water which should not be alkaline as it destroys or modifies the
taste as it tends to neutralize the fruit acid.
Sugar industry If hard water is used in sugar refining it results in the formation of
deliquescent sugar. More over, these impurities cause difficulty in the crystallization
of sugar.
Cooking water used should be free from dissolved salts producing hardness. Fuel
requirement is high if hard water is used. More over, more time is required for
cooking. Also if hard water is used for making tea or coffee, it imparts unpleasant
taste and muddy-looking extract.
Dairies and pharmaceutical industries require ultra pure water which should be
colorless, taste less, odorless and free from pathogenic organism.
DISINFECTION OF WATER
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Advantages of chlorination:
Disadvantages:
Initially for lower doses of Cl 2 , there is no free residual chlorine since all
the added chlorine gets consumed for doing complete oxidation of reducing
substances present in water.
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After minima, the added chlorine is not used in any reaction. Thus, the
residual chlorine keeps increasing in proportion to added chlorine. Hence, for
effectively killing micro organisms, sufficient chlorine has to be added. Addition of
chlorine in such dosages is known as break-point or free residual chlorination.
De-chlorination: Over chlorination after the break point produces unpleasant taste
and odour in water. These objectionable qualities may be removed by filtering the
over-chlorinated water through a bed of molecular carbon. Alternatively, a small
percentage of activated carbon may be added directly to the water and after allowing
a short reaction period, it is then removed by filtration. Objectionable qualities
resulting from over-chlorination may also be remedied by the addition of a small
percentage of sulphur dioxide or sodium sulphate or sodium thiosulphate, etc.
O3 - O2 + [O]
nascent
The nascent oxygen is very powerful oxidizing agent and kills all the
bacteria as well as oxidizes the organic matter present in water.
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For carrying out the disinfection by ozone, ozone is injected into the water
and the two are allowed to come in contact in a sterilizing tank. The disinfected
water is removed from the top. The contact period is about 10-15 minutes and the
usual dose strength 2-3ppm.
Advantages: removes colour, odour and taste without giving residue, not harmful,
since it is unstable an decompose into oxygen.
BOILER TROUBLES
(Boiler Scales)
If the precipitation takes place in the form of loose and slimy precipitate, it
is called sludge. On the other hand, if the precipitated matter forms a hard, adhering
crust/coating on the inner walls of the boiler, it is called scale.
Sludge is a soft, loose and slimy precipitate formed within the boiler. Sludge
can easily be scrapped off with a wire brush. It is formed at comparatively cold
portions of the boiler and collects in areas of the system, where the flow rate is slow
or at bends. Sludges are formed by substances which have greater solubilities in hot
water than in cold water. E.g. MgCO3, MgCl2, CaCl2, MgSO4, etc.
Scales are hard deposits, which stick very firmly to the inner surfaces of
the boilers. Scales are difficult to remove, even with the help of hammer and chisel.
Scales are the main source of boiler troubles.
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MgCl2 + 2H2O Mg(OH)2 + 2HCl
Scale
Effects of scales:
• Scales have a low thermal conductivity, so the rate of heat transfer from
boiler to inside water is greatly decreased. In order to provide steady supply
of heat to water, excessive or over heating is done and this causes increase in
fuel consumption.
• The over-heating of the boiler tube makes the boiler material softer and
weaker and this causes distortion of boiler tube and makes the boiler unsafe
to bear the pressure of the steam, especially in high pressure boilers.
• Scales may some times deposit in the valves and condensers of the boilers
and choke them partially. This results in decrease in efficiency of the boiler.
• When thick scales crack, due to uneven expansion, the water comes suddenly
in contact with over-heated iron plates. This causes in formation of a large
amount of steam suddenly. So sudden high pressure is developed, which may
even cause explosion of the boiler.
Removal of scales:
• If they are loosely adhering, with the help of scraper or piece of wood or wire
brush.
• If they are brittle, by giving thermal shocks.
• If they are adherent hard, by dissolving them by adding them chemicals.
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Some important questions:
2 Name the salts responsible for the temporary and permanent hardness of
water sample.
4 Explain the principle behind the colour change from wine red to blue of the
indicator in the EDTA titration of hardness estimation of water.
9 What is the indicator used in EDTA method? What is the end point.?
15 Discuss briefly the role of cation and anion exchange resins in softening
water.
19 What are scales and sludges in boilers? What are their disadvantages caused
to boilers?
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20 How the carbonate and bicarbonate alkalinity is determined experimentally in
a water sample?
- - - - -2
21 Water sample contains OH , HCO3 & CO3 , Cl , SO4 . Which ion causes
alkalinity & why.
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