Water Chemistry
Water Chemistry
Water Chemistry
Water
Introduction
The pure water is composed of two parts of hydrogen and one part of oxygen by volume and
dissolves many substances. These dissolved salts are the impurities in water. Water is a very
good solvent. So it is called as universal solvent.
Soft water: - The water which can give lather with soap easily is called as soft water.
(Soluble salt)
Hard water
Temporary hardness:- The hardness that can be removed simply by boiling is called the
temporary hardness. It is due to the presence of boiling. On boiling Ca(Hco 3)2, Mg(Hco3)2 are
precipitated as insoluble salts. Which can remove through filtration?
39
Permanent Hardness:- Permanent hardness cannot be removed by boiling . It is due to CaCl 2,
3+ 3+
CaSO4, MgCl2, MgSO4 and nitrates in H2O. These salts cannot remove this hardness. Fe , Al
& Mn2+ also cause hardness in water.
Units of Hardness:-
(1) Parts per million (ppm):- It is the number of parts of equivalents of CaCO3 hardness causing
salt present in one million parts(106 parts ) of water.
(2).Miligram per litre(mg/l):-It is the number of milligrams of equivalentof CaCO 3 per litre
of hard water. E.g.:- 1mg/li means 1 mg of equivalent caco 3 present in litre of hardwater.
(4)Degree French (o Fr):- It is a French unit. The number of parts of caco 3 equivalent hardness
causing substance in 105 parts of water.
Principle:- The ca 2+ &Mg2+ ions present in water are responsible for hardness. These icons
form selectable complexes with the indicator (EBT) and these metal icons forms stable
complexes with EDTA. This fact is used to estimate the hardness of water sample.
The metal ions ca 2+ & Mg2+ react with the EBT indicator and forms a stable complex at PH-10.
PH 9-10
40
Whenever we are adding EDTA solution to the wine- red color (M-In) solution, the metal ions
form more stable complex with EDTA. When all the metal ions in the sample complexed with
EDTA, further addition of EDTA liberates the free indicator solution at PH-10 which in blue
color indicates the end point of the titration
A known volume of water sample is taken in a beaker and boiled for half an hour, after cooling it
is filtered and the filtrate titrated against EDTA by adding EBT indicator & PH-10 buffer
solution. Here the volume of EDTA consumed v 2ml gives us the permanent hardness of water.
41
Determination of Hardness of Water by Winkler
The determination of dissolved oxygen is to bring about the oxidization of potassium iodide with
the dissolved oxygen present in the water sample after adding MnSO4, KOH and KI. The basic
manganic oxide formed acts as an oxygen carrier to enable the dissolved oxygen in the molecular
form to take part in the reaction. The liberated iodine is titrated against standard hypo Solution
using starch indicator.
2Mn (OH) 2 + O2 )2
Starch + I2
Experimental Procedure:
Take the standard flask with 200 ml of water to that add 2ml of MnSO 4 and 2ml of KI + KOH
(alkali potassium iodide).Light brown precipitate forms, to this add 2ml of conc.H 2SO4
precipitation dissolved into brown colour. Take 100 ml of solution which is in the standard flask
and pour it into conical flask. To the conical flask add 1 2ml of starch needed immediately
colour changed to blue. Then titrate the solution with hypo solution until the solution becomes
colourless. Note down the readings and repeat it. Amount of dissolved oxygen content is
obtained in mg/ lit (or) ppm.
FORMULAE:
42
Effects of hardness: - (1) Hard water is harmful for drinking due to the presence of excess of
(2)Hard water used in boilers forms scales & sludge and results in corrosion, priming caustic
embrittlement of the boilers.
(3)Hard water used does not give lather with soap, so it sticks to clothes and body.
(5)Hard water is not suitable for laboratory analysis, because hardness producing icons interfere
in various reactions.
3.2 Boiler Troubles: - Continues use of hard water in boilers causes boiler troubles that are
1. Priming: -
and high velocities of steam, the water droplets moves out with steam from the boiler. This
process of wet steam generation is caused by (i) The presence of large amount of dissolved
solids.(ii)High stream velocities (iii) sudden boiling (iv) improper designing of boilers (v)
sudden increase in stream production rate and (vi) The high levels of water in boilers.
2. Foaming: - Formation of stable bubbles at the surface of water in the boiler is calling
foaming. More foaming will cause more priming. It results with the formation of wet steam that
harms the boiler cylinder and turbine blades. Foaming is due to the presence of oil drops, grease
and some suspended solids.
(1)Adding antifoaming chemicals like castor oil. The excess of castor oil addition can cause
foaming.
(3) Replacing the water concentrated with impurities with fresh water.
43
3. Scale &sludge formation:- The water in boiler is continuously heated causes the increase in
the concentration of dissolved and suspended solids. These are precipitated and slowly
precipitate on the inner walls of the boiler plate. This precipitation takes place in two ways.
(1)The precipitation in the form of soft loose and slimy deposits (sludge)
(2)The precipitation in the form of hard deposits, which are sticky on the walls of boilers (scale)
Sludge: The muddy solid at the bottom of the boiler (or) the loose, slimy and soft deposits in the
boiler are called sludge.
Causes of the sludge:- The sludge is caused by MgCO3, MgCl2,CaCl2 which have more
solubility in hot water.
Disadvantages of sludges: - 1. sludges are bad conductors of heat and results in wastage of heat
and fuel.
2. Sludges entrapped in the scale get deposited as scale causes more loss of efficiency of boiler.
3. Excessive sludge formation leads to setting of sludge in slow circulation. Areas such as pipe
connections leading to chocking (or) blockage of the pipes.
Prevention of sludge formation: - (1) By using soft water which is free from dissolved salts like
, MgCO3, MgCl2, CaCl2&MtgSO4.
Scale: - Scales are hard sticky deposits on the inner walls of boiler. The scales are very difficult
to remove.
Reason of Scale:- (1) Due to the decomposition of Ca(HCO 3)2 at high temperature & pressure
present in boiler, It forms caco3 insoluble salt settles as ppt in the boiler.
(2) CaSO4 present in water in highly solute in cold water and less soluble in hot water. So the
CaSO4 in boiler water is precipitates out as hard scale, whenever the temp of boiler increases.
(3) Hydrolysis of MgCl2:- The dissolved mgcl2 present in water is precipitates as Mg (OH) 2 at
high temperature, deposits as scale.
(4)Sio2 present in water deposits as calcium silicate or magnesium Silicate. The deposits are very
hard.
44
Disadvantages of Scale: - (1) As the scale is hardly sticky on the walls of the boiler and it is
very bad conductor of heat. So there is loss of heat and fuel.
2. Due to the scale formation we have to heat the boiler to high temperatures this causes the
weakening of boiler material.
4) Due to uneven heat there may be developing of cracks in Scale. Whenever the water passes
through this crack comes to contact with boiler plate and generates sudden steam and high
pressure results explosion of boiler.
Removal of Scales:-
(2) By giving thermal shocks done by heating to higher temperature and suddenly cooling.
(3)The CaCO3 scale is removed by the washing with 5-10% HCl Solution and CaSO 4 scale in
removed washing with EDTA solution.
4. Caustic embrittlement:- The Na2 CO3 present in water hydrolysed to NaOH at high
pressures in boilers.
The NaOH formed concentrates after long use. It causes inter-granular cracks on the boiler walls,
especially at the stress points. The concentrated alkali is dissolved iron as sodium ferrote in
cracks and cause brittlement of boiler.
The formation of cracks in boilers due to NaOH is called caustic embrittlement. The created
concentration cell is explained
45
Iron at bends concentrated Diluted Iron at plane surface
2) By adding tannin or lignin to boiler water which block the hair cracks and pits in boiler.
3) By adding sodium sulphate to soften the water and this also blocks the hair cracks present on
the surface of the boiler plate.
Lime-soda Ion-exchange
1. Process process
zeolite
Process
46
Na2 Ze + Ca2+ CaZe + 2 Na+
Naturally occurring Zeolite is Natolite Na2 O.Al2 O3.SiO2.2H2 O.The Synthetic Zeolites are also
prepared with the help of feldspar &China clay on heating.
Process:-The apparatus is made of cylindrical metallic vessel several beds are made inside it
where zeolite salt is kept. Raw water is poured inside the apparatus through inlet that passes
through beds and thus chemical ion exchange reactions are takes place. After the use of this
process for a certain time, Zeolite is exhausted .i.e all Na+ ions are replaced by ca2+/mg2+ and
therefore this will not be used for soften the water.
Exhausted Zeolite on washing with cold water, CaC 2 & MgCl2 can be removed and regenerated
zeolite is this ready to be reused.
Zeolite softener
47
The process can be made automatic & continuous. (6) This process is very cheap since
regenerated permutit is used again.
Disadvantages:-1) In zeolite process 2Na+ ions replaces by ca2+/mg2+ icons. The soft water
obtained by this process has excess of Na+ ions.
2) If the hard water containing acid destroys the zeolite bed.
3) The turbidity (or) suspended particles present in water will block the pores of zeolite.
4) Bicarbonate & carbonate ions present in water are converted as sodium salts resulting the
alkalinity of water.
(5) The coloured ions like Mn2+ &Fe2+ cannot be removed by this process.
cation exchange resins:- The resins containing acidic functional groups such as -COOH,-SO 3H
etc. are capable of exchanging their H+ ions with other cations are cation exchange resins ,
+
represented as RH
Anion exchange resins:- The resins containing amino or quaternary ammonium or quaternary
exchanging their oH- ions with other anions. These are called as Anion exchanging resins
-
represented as R OH
Process: The hard water is passed first through cation exchange column. It removes all the
cation (ca2+ & Mg2+) and equivalent amount of H+ icons are released from this column.
R 2Mg2+
After this the hard water is passed through anion exchange column, which removes all the anions
like SO42-,Cl-,CO32- etc and release equal amount of OH- from this column.
The output water is also called as de -ionised water after this the ion exchanges get exhausted.
The cation exchanges are activated by mineral acid (HCl) and anion exchanges are activated by
dil NaOH solution.
Advantages:-The process can be used to soften highly acidic or alkaline wate. (2) It produces
water of very low hardness. So it is very good for treating for use in high pressure boilers.
Disadvantages:- The equipment is costly and common expensive chemicals required. (2) It water
contains turbidity, and then output of this process is reduced. The turbidity must be below 10
ppm.
49
Internal treatment: - In this method raw water in treated inside the boiler. This is a process
of adding suitable chemical to residue scale &sludge formation. It is mainly based on solubility.
This is a corrective method. This method is also called conditioning method.
Conditioning of water:-
1) Carbonate conditioning:- In low pressure boilers scale formation can be avoided by treating
the boiler water with Naco3. Where CaSO4 is converted into CaCO3.
CaSO4 is precipitated as loose sludge in the boiler which can be scrapped off.
2) Calgon conditioning: - calgon means calcium gone i.e the removal of ca 2+. Sodium hexa-
meta phosphate is called calgon. It reacts with calcium ion and forms a water solute compound.
Converted to scale which on drying converted to scale reduces the efficiency of the boiler.
At higher temperature NaPO3 is converted to Na2P2O4 that also reacts Ca2+ to foam loose sludge
of Cap2 O7.removed by blowing air.
Trisodium phosphate is used when the alkalinity of boiler water is 9.5 to 10.5 at that PH Ca gets
precipitated.
If alkalinity is too high NaH2pO4 (acidic) is used and Na2HPO4 is used if sufficiently of alkaline.
(4). Treatment with Sodium Aluminate: - when boiler water heated with Sodium aluminate it
gets hydrolyses to give NaOH and gelatinous precipitate of Al (OH) 3.
The NaOH formed react with MgCl2 to form Mg (OH) 2 . These two precipitates entrap
colloidal impurities like oil drops, sand and make them settle down.
50
Disadvantages of hard water in domestic and Industrially In Domestic use:-
Washing:-
Hard water, when used for washing purposes, does not producing lather freely with soap.
As a result cleaning quality of soap is decreased and a lot of it is wasted.
Hard water reacts with soap it produces sticky precitates of calcium & Mg soaps. These are
insoluble formations.
(a) Bathing:-
Hard water does not produce lather freely with soap solution, but produces sticky scum on the
bath-tub and body. Thus, the cleaning quality of soap is depressed and a lot of it is wasted.
(b) Cooking:-
The boiling point of water is increased because of presence of salts. Hence more fuel and time
are required for cooking.
(c) Drinking:-
Hard water causes bad effects on our digestive system. Moreover, the possibility of forming
calcium oxalate crystals in urinary tracks is increased.
Industrial use:-
(a) Textile industry:- Hard water causes wastage of soap. Precipitates of calcium and magnesium
soaps adhere to the fabrics and cause problem.
(b) Sugar Industry:- Water containing sulphates, nitrates, alkali carbonates etc. if used in sugar
refining, causes difficulties in the crystallization of sugar. Moreover, the sugar so produced may
be de-liquiscent.
(c) Dyeing industry:- The dissolved salts in hard water may reacts with costly dyes forming
precipitates.
(d) Paper Industry:- Calcium, magnesium, iron salts in water may affect the quality of paper.
(e) Pharmaceutical Industry:-Hard water may cause some undesirable products while preparation
of pharmaceutical products.
(f) Concrete making:- water containing chlorides and sulphates, if used for concrete making,
affects the hydration of cement and the final strength of the hardened concrete.
(g) Laundry:- Hard water, if used in laundry, causes much of the soap used in washing to go as
waste iron salts may even causes coloration of the cloths.
Steam generation purpose boilers are used in Industries. If the hard water is fed directly
to the boilers, there arise many troubles such as:
(a) Scale & Sludge formation:- The hardness of water fed to the many causes scale & sludge
formation.
(b) Corrosion:- Hard water may cause caustic embrittlement which is a type of boiler corrosion.
51
(c) Priming & Foaming:- Hard water used in boiler cause priming and foaming which results in the
formation of wet steam
(d) Caustic embrittlement
= 28.7+90.1=118.8ppm
Permanent Hardness=CaCl2+MgSO4
= 64+40 = 104ppm
= 118.8+104=222.8ppm
(2) One liter of water from khammam Dist in A.P showed the following analysis.
Mg(HCO3)2=0.0256 gms, Ca(HCO3)2=0.0156 gms, NaCl=0.0167gms, CaSO 4=0.0065gms, and
MgSO4=0.0054gms. Calculate temporary, Permanent & total hardness.
52
S. No Constituent Amount Mg/l Mol. Wt. of salt Equivalent of
CaCO3 mg/l
1 CaSO4 6.5 136 =4.77
2 MgSO4 5.4 120 =4.5
3 Ca(HCO3)2 15.6 162 =9.6
4 Mg(HCO3)2 25.6 146 =17.5
5 NaCl 16.7 _ _
Temporary hardness=Mg(HC3)2+Ca(HCO3)2
= 17.5+9.6=27.1 ppm
Permanent hardness=CaSO4+MgSO4
=4.77+4.5=9.27 ppm
= 27.1+9.27=36.37 ppm
(3) Calculate the temporary & permanent hardness of 100 litre of water containing the following
impurities per litre MgCl2=19 mg, MgSO4=60 mg, NaCl=36.5 mg, CaCl 2=11.1 mg,
Ca(HCO3)2=32.4 mg & Mg(HCO3)2=7.3 mg
=5+20=25
53
Temporary hardness for 100ml = 25×100=2500 Mg/l
= 10+20+50=80 Mg/l
=25+80=105Mg/l
(4) A sample of hard water contains the following dissolved salts per liter
CO2=44Mg, Ca (HCO3)2=16.4Mg, Mg (HCO3)2=14.6 Mg
CaCl2=111 Mg, MgSO4=12 Mg, &CaSO4=13.6 Mg. Calculate the temporary &
=100+10+10=120 mg/l
=100+10+10=120 mg/l
Conversion of hardness:-
54
Temporary hardness = 120 mg/l, 120 ppm, 120*0.07 = 8.4 °cl
= 120*0.1= 12°french.
(5) Calculate the lime and soda needed for softening 50,000 litres of water containing the following
salts: CaSO4 = 136 mg/l, MgCl2=95mg/l, Mg(HCO3)2 = 73 mg/l, Ca(HCO3)2= 162 mg/l. given
that molar mass of Ca(HCO3)2 is 162 and that of MgCl 2 is 95.
= (100+2*50+100+100)
= * =296 mg/l
= * =212mg/l
3.4 Disinfection:- The process of destroying/killing the disease producing bacteria, micro
organisms, etc, from the water and making it safe are, is called Disinfection.
Disinfectants:- The chemicals or substances which are added to eater for killing the bacteria. The
disinfection of water can be carried out by following methods
55
(a) Boiling:- Water for 10 -15 min.boiled,all the disease producing bacteria are killed and water
become safe for use.
(b) Bleaching powder:-
It is used to purity the drinking water from micro organisms. The purification process is
achieved by dissolving 1 kg of bleaching powder in 1000 kilo litres of water. This dissolved
water solution is left undisturbed for many hours when bleaching powder is mixed with water,
the result of chemical reaction produces a powerful Germicide called Hypochlorous acid. The
presence of chlorine in the bleaching powder produces disinfection action, kills germs and
purifies the drinking water effectively.
CaOCl2+H2O Ca(OH)2+Cl2
H2O+Cl2 HCl+HOCl
(c) Chlorination:-
Chlorination is the process of purifying the drinking water by producing a powerful
Germicide like hypochlorous acid. When this chlorine is mixed with water it produces
Hypochlorous acid which kills the Germs present in water.
H2O+Cl2 HOCl+HCl
Chlorine is basic (means PH value is more than 7) disinfectant and is much effective over
the germs. Hence chlorine is widely used all over the world as a powerful disinfectant.
Chlorinator is an apparatus, which is used to purity the water by chlorination process.
(d) Ozonisation:-
Ozone is powerful disinfectant and is readily dissolved in water. Ozone being unstable
decomposes by giving nascent oxygen which is capable of destroying the Bacteria.This nascent
oxygen removes the colour and taste of water and oxidizes the organic matter present in water.
O3 O2+ [O]
-
56
Fig3.9 Breakpoint chiorination
3.5 Desalination
The removal of dissolve solids (NaCl) from water is known as desalination process. It can be
carried out by
57
This method is applicable mainly for the desalination of sea water. Sea water and pure
water are separated by a semi-permeable membrane made up of cellulose a cetate fitted on both
sides of a perforated tube. Inventions are in progress to search for better membrane.
Polymethylmethacrylate and polyamides have been proved to be better membranes.
The process is very easy. It is used to make pure water. It removes the ionic and non ionic
substances in the water. It also can remove suspended colloidal particles. The life of a membrane
is nearly 2 years and it should be replaced after this period. By this process, sea water is made to
fit for drinking water obtained after being treated by this process is used in boilers.
58