Water
Water
Water
WATER
Textile industrySpecification
-
2)
LaundriesSpecification-
3)
BeveragesSpecification-
Neutralization occurs.
4)
5)
6)
Loss of heat.
Paper Industry -
Specification-
HARDNESS OF WATER
Those water which does not produce lather with soap are termed as hard water. On the other hand
soft water readily produce a lot of lather when mixed with a little of soap. The hard water causes boiler
troubles like scale formation etc. the hardness is mostly due to the presence of bivalent metallic ions
which react with soap and form precipitates. Some major bivalent cations are Mg++, Ca++ and Fe++. Some
important anions are HCO-3, NO-3, SO4-- etc.
Example :-
A reaction of soap (Sodium stearate) with calcium chloride and Magnesium sulphate is as
follows-
Hardness
Hardness
The water are commercially classified on the basis of degree of hardness as followsHardness
0-70 mg/litre
Soft water
70-150 mg/litre
150-300 mg/litre
Hard water
Types of Hardness
HARDNESS
Temporary Hardness -
Permanent Hardness2
(i)
heavy metals.
(ii) Salts which are responsible for temporary (ii) Salts which are responsible for
hardness are Ca(HCO3)2 and Mg(HCO3)2
are
into
decomposed
insoluble
and
carbonates
or
boiling of water.
hydroxides, which precipitate and settle down (iv) It is also known as non carbonate or
at the bottom of the vessel.
Mg(OH ) 2
B+2CO + CO A
2
Molar mass
Chemical equivalent
Multiplication
factor
for
162
81
100/162
Mg(HCO3)2
146
73
100/146
CaSO4
136
68
100/136
MgSO4
120
60
100/120
CaCl2
111
55.5
100/111
MgCl2
95
47.5
100/95
CaCO3
100
50
100/100
MgCO3
84
42
100/84
3
CO2
44
22
100/44
Mg(NO3)2
148
74
100/148
HCO-3
61
61
100/122
OH-
17
17
100/34
CO2-3
60
30
100/60
NaAlO2
82
82
100/164
Al2(SO4)3
342
57
100/114
FeSo4.7H2O
278
139
100/278
100/2
UNIT OF HARDNESSUNIT
(A)
(A)
(B)
(C)
(D)
Parts per Million (ppm) It is defined as the number of parts of CaCO3 equivalent hardness per
106 parts of water.
(B)
Milligrams per litre (Mg/L) It is defined as the number of milligrams of CaCO3 persent in one
litre of water.
(C)
Degree Clark (oCl) - It is defined as the parts of CaCO3 equivalent hardness per 70,000 parts of
water.
Or
It is the number of grains of CaCO3 equivalent hardness for a gallon of water.
(D)
Degree French) (oFr) It is defined as the parts of CaCO3 equivalent hardness per 105 parts of
water.
1 ppm = 1 Mg/L
0.1 oFr
= 0.07 oCl
1 mg/l = 1 ppm
0.1 oFr
= 0.07 oCl
1 oCl = 1.43oFr
14.3 ppm
= 14.3 mg/L
10 Mg/L
= 0.7 oCl
1 Fr = 10 ppm
Hence ;
= Massof CaSO 4 in Mg / L
= 500mg / L
50 O
L
M
80 P
N
Q
= 312.5 Mg/L =
Ex. (2) How many grams of MgCO3 dissolved per litre gives 90 ppm of hardness.
Solution-
L
chemical eq. of CaCO O
M
Nchemical eq.of MgCO P
Q
3
75.6 Mg/L
42 O
L
M
N50 P
Q
= 75.6 ppm
Ans.
-3
9.50 gm
CaSO4
13.60 gm
Ca(HCO3)2
16.20 gm
Solution:MgCl2 =
CaSO4
24+71
40+32+64
40+2(1+12+48)
40+12+48
= 95
= 126
= 162
= 100
95 gm of MgCl2
9.50gm of MgCl 2 =
Ca(HCO3)2
CaCO3
100 gm CaCO3
100
9.5
95
10 gm of CaCO3.
136 gm of CaSO4 =
13.6gm of CaSO 4
100 gm of CaCO3
100
13.6 = 10gm CaCO 3
136
16.2 gm of CA ( HCO 3 ) 2
100
16.2 = 10gm CaCO 3
162
(ii)
Ex. (4) Calculate temporary hardness and total hardness of sample of water containing Mg(HCO3)2 = 7.3
Mg/L, Ca(HCO3)2 = 16.2 Mg/L, MgCl2 = 9.5 Mg/L, CaSO4 = 13.6 Mg/L
Solution:-
L
M
N
(5 + 10) Mg/L
15 Mg/L
L
M
N
O
P
Q
100
100
+ 13.6
Mg / L
95
136
20 Mg/L
Total Hardness
O
P
Q
100
100
+ 16.2
Mg / L
146
162
SOFTENING METHODS
B) Zeolite Process
C) Ion-exchange process
Water Softening :Removal of hardness of water whether temporary or permanent hardness is done through the
process called softening of water. It is very essential process since hard water is unsuitable for domestic
as well as industrial purposes, In steam generation hard water creates number of problems like scale and
sludge formation, priming and foaming etc.
Hardness can be removed by two methods
(1) External Treatment
(2) Internal Treatment
Raw water and calculated amount of chemicals (lime + soda + coagulant) are fed on top into the
inner vertical circular chamber, fitted with a vertical rotating shaft varying a number of paddles.
As the raw water and chemicals flow down, there is a vigorous stirring and continuous mixing, so
softening of water takes place.
The heavy sludge settles down in the outer chamber by the time and softened water reaches up.
The softened water then passes through a filtering media to ensure complete removal of sludge.
Filtered soft water finally flows out continuously through the outlet at the top.
7
Sludge settings at the bottom of the outer chamber are drawn of occasionally.
Reaction Tank The tank has three separate inlets and third for superheated steam. After
their entry they are mixed. The reaction starts and get completed in the reaction tank.
(b)
Conical Sedimentation Tank from reaction tank the reactants come in this tank and the
sludge settles down.
Sand filter It has layer of lime and coarse sand, which works as filter and makes its
(c)
Processing (i)
(ii)
(iii)
Some dissolved gases like CO2 also driven out of the water.
(iv)
(v)
The softening capacity of hot process is many times higher than that of the cold process.
(ii)
(iii)
Due to alkaline nature of treated water, pathogenic bacterias in water are reduced.
(iv)
(v)
For efficient and economical softening, careful operation and skilled supervision is required.
(ii)
(iii)
This can remove hardness only upto 15 ppm, which is not good for boilers.
Reaction
Hardness
Need
B
CaSO + Na CO CaCO B
+ Na SO
MgCl + Ca (OH ) Mg(OH ) B
+ CaCl
S
S
and MgSO4
Ca(HCO3)2
(Temp.
L+S
Ca)
Mg(HCO3)2
2L
(Temp. Mg)
HCO3- (NaHCO3)
Dissolved CO2
CO 2 + Ca (OH ) 2 CaCO 3 + H 2 O
Free acids H+
HCl and H2SO4
H2SO4
L-S
L+S
L+S
Coagulant FeSO4
CaSO 4 + Na 2 CO 3
Al2(SO4)3
B+CaSO
CaCO B
+ Na SO
L+S
NaAlO2
L+S
-L
= 2 10, Y = 2 6.
Zeolite is hydrated sodium alumino silicate, capable of exchanging reversibly its sodium ions
for hardness producing ions in water. Zeolites are also known as permutits. Zeolites are of two types.
(i)
Natural Zeolites
(ii)
Synthetic zeoliets.
(i)
(ii)
Natrolite
Thomsonite
Synthetic Zeolite They are porous are posses gel structure. Such zeolile passes higher exchange
capacity than natural zeolite but they are less durable.
PROCESS :- Hard water is percolated at a specific rate through a bed of zeolite, kept in a cylinder.
Hardness causing ions (Ca2+, Mg2+ etc) are retained by the zeolite as CaZe and MgZe, while
outgoing water contains sodium salts.
Caze
( Exhausted zeolite )
+ 2 NaCl
( Brine )
Na ze
2
(Re claimed zeolite )
+ CaCl 2
( washings)
The washings are led to drain and the regenerated zeolite bed thus obtained us used again for
softening purpose.
LIMITATION:(i)
Water with turbidity should not be used as pores of zeolite get clogged.
(ii)
(iii)
Water containing Fe2+ and Mn2+ ions should be avoided because Fe2+ will form their zeolite
which cant be easily regenerated.
10
(iv)
(v)
ADVANTAGES
(i)
(ii)
(iii)
(iv)
It is quite clean.
(v)
ZEOLITE PROCESS
(i)
Water
with
zero
is (i)
produced.
(ii)
(ii)
(iii)
Plant is compact and occupies less (iv) Plant occupies more space.
space.
(v)
(vi)
limitations.
(vi) There
may
be
problem
after
precipitation.
like
salt,
coagulation, filtration.
involves
all
problems
11
45
50
g
58.5 of CaCO3 equivalent hardness.
This much hardness may be deemed to be present in 1000 litres of water sample.
Hardness of the water sample.
= 45
50 1,000
Mg / L
58.5 1,000
38.46 ppm
Ans.
Ex. (2) An exhausted zeolite softener was regenerated by passing 150 litres of NaCl solution, having a
strength of 150 g/l of NaCl. How many litres of hard water sample, having hardness of 600 ppm can be
softened, using softener ?
Solution150 litres of NaCl solution contains
150 X 150 g
= 22,500
22,500 g NaCl
50
g of CaCO 3 eq. hardness
58.5
Given that 1 litre of hard water contains 600 ppm hardness = 600 mg of CaCO3 = 0.6 g of CaCO3.
The amount of hard water that can be softened by this softener
=
22,500 50
0.6 58.5
32,051 litres.
Ex. (3) The hardness of 100000 litres of a sample of water was completely removed by passing it through
a zeolite softener. The softener then required 400 litres of sodium chloride solution containing 100 g/litre
of NaCl for regeneration. Calculate the hardness of the water sample.
Solution
400 L of NaCl solution
=
= 40,000
= 40,000 g NaCl
50
g CaCO 3 eq.
58.5
34,188
100,000
341.9 mg
Ion exchange resins are insoluble cross-linked, long chain organic polymers with a micro-porous
structure and the functional groups attached to the chains are responsible for the ion-exchanging
properties.
Resins containing acidic functional groups (-COOH, -SO3H etc) are capable of exchanging their
H+ ions with other cations.
Resins containing basic functional groups (-NH2) are capable of exchanging their anion with other
anion.
(i)
Cation exchange resins (RH+) - are mainly styrene divinyl benzene copolymers, which on
sulphonation or carboxylation become capable to exchange their hydrogen ions with the cations
in the water.
(ii)
Anion exchange resins (R OH-) are styrene divinyl benzene or amine formaldehyde
copolymers, which contain amino groups as an integral part of the resin. These after treatment
with dil NaOH solution become capable to exchange their OH- anions with other anions of water.
PROCESS :- The hard water is passed first through cation exchange column, which removes all the
cations like Ca2+, Mg2+ etc. from it, and equivalent amount of H+ ions are released from this column to
water. Thus;
2RH + Ca2+ R2Ca
+ H+
Advantages :(i)
(ii)
It produces water of very low hardness (~2ppm). So it is very good for treating water for use
in high pressure boiler.
Disadvantages :(i)
(ii)
BOILER TROUBLE
A proper quality of water for use in boilers is very important. If impure water is made use of as boiler
feed water, then following boiler problems may occurs.
(i)
(i)
(ii)
(iii)
Caustic embrittlement.
(iv)
progressively. When their concentrations reach saturation point, they are thrown out of water in the form
of precipitates on the inner walls of the boiler.
If Precipitate
Sludge :(1)
(2)
(3)
Sledges are formed by substances which have greater solubility in hot water than in cold water.
Ex. MgCO3, MgCl2, MgSO4, etc.
(4)
It is formed at colder portions of the boiler and collects in areas, where flow rate is slow.
Sludge is poor conductors of heat, so they tend to waste a portion of heat and thus decrease boiler
efficiency.
14
(2)
It sludge are formed along with scale, then sludge gets entrapped in the scale and both get
deposited as scale.
(3)
(4)
Sludge deposited on pipe connection, plug opening so choking of pipes takes place.
(2)
SCALE :(1)
(2)
(3)
They are difficult to remove, even with the help of hammer and chisel.
(4)
Ca ( HCO 3 ) 2 Ca (OH ) 2 + Co 2
( So lub le )
This scale is soft and is the main cause of scale in lower pressure boiler. But in high pressure
boilers CaCO3 is soluble.
CaCO 3 + H 2 O Ca ( OH ) 2 + CO 2
( So lub le )
(2)
Deposition of CaSO4 The solubility of CaSO4 in water decreases with rise of temperature.
Temp.
15oC
230oC
320oC
Solubility
3,200 ppm
55 ppm
27 ppm.
Means CaSO4 is soluble in cold water but almost completely insoluble in super heated water.
(3)
B+2HCl A
Presence of silica (SiO2) Even present is small quantities deposits as MgSiO3 and CaSiO3. It
deposited in the inner walls of boiler and very difficult to remove.
15
Wastage of fuel Scales are poor conductor of from boiler to inside water is decreased. So
excessive or over heating is deeded, this causes increase in fuel consumption.
Thickness of Scale
0.325
0.625
1.25
2.5
12
Wastage of fuel
10%
15%
50%
80%
150%
(2)
Lowering of boiler safety The over heating of the boiler tube makes the boiler material softer
and weaker this causes distortion of boiler tube and make boiler unsafe.
(3)
Decrease in efficiency Scales sometimes deposited in the valves and condensers of the boiler
and choke them, this results in decrease in efficiency.
Prevention of Scale formationInternal treatment An internal treatment is accomplished by adding a proper chemical to the boiler
water. Some methods are(1)
Colloidal Conditioning In lower pressure boiler by adding organic substance like kerosene,
tannin, agar agar. Scale formation can be avoided. They get converted over the scale, so scale
will be non sticky and loose deposits, which can easily be removed by blow down operation.
(2)
Phosphate Conditioning In high pressure boilers by adding sodium phosphate scale formation
can be avoided. They formed non-adherent and easily removable, soft sludge of phosphate. Which
can easily removed by blow down operation.
3cacl2 + 2Na3SO4 Ca3(PO4)2 + 6NaCl
(i)
(ii)
(iii)
(3)
Carbonate Conditioning In lower pressure boiler scale formation can be avoided by adding
sodium carbonate.
CaSO4 + Na2CO CaCO3 + Na2SO4
CaCO3 is loose sludge which can be removed by blow down operation.
(4)
Calgon Conditioning By adding calgon (Sodium hexa meta phosphate (NaFO3)6 in boiler
water. It forms soluble complex with Ca+ ion.
Na 2 [ Na 4 ( PO4 ) 6 ] 2 Na + [ Na 4 P6O18 ]2
(5)
Treatment with sodium aluminate (NaAlO2) :- NaAlO2 gets hydrolysed yielding NaOH and a
gelatinous precipitate of aluminum hydroxide.
16
B+2NaCl
The ppt of Mg(OH)2 plus Al(OH)3 produced inside the boiler, entraps finely suspended and colloidal
impurities, including oil drops and silica.
(ii)
Boiler corrasion is deeay of boiler material by a chemical a Hack by its environment Main resons for
boiler corrasion are-
(a)
Dissolved Oxygen Water usually contains above 8 mL of dissolved oxygen per litre. Dissolved
oxygen in presence of high temperature, attacks boiler material2Fe + 2H2O + O2 2Fe(OH)2
4Fe(OH)2 + O2 2[Fe2O3 . 2H2O]
Rust.
By Mechanical de aeration Water spraying ina perforated plate fitted tower, heated from
sides and commeeted to veccum pump. High temperature low pressure and large expased surface
reduees the dissolved oxygen in water.
(iii)
CAUSTIC EMBRITTLEMENT
This type of boiler corrosion is caused because of use of high alkaline water in high pressure
boilers. When water is softened by lime and soda process and is ped into the boiler it may be likely that
some residual Na2CO3 is still present in the softened water. Na2CO3 decomposer to give NaOH and CO2,
and NaOH thus produced makes the boiler water caustic.
Na2CO3 + H2O 2NaOH + CO2
The NaOH containing water floues into the minute hair cracks always present in the inner side of
boiler by capillary action. Here water evaporates and the dissolved caustic soda concentration increases
progressively and attacks the surrounding boiler material and iron is dissolved as sodium ferrate. This
causes embrittlement of boiler walls more particularly stressed parts. Like bends, joints
rivets etc.
Embitterment arises due to setting up of a concetration cell, with the iron surrounded by dil NaOH
acts as a cathode while the iron surrounded by conc. NaOH acting as the Anode.
Iron at +
Concentrated
Dilute
Iron at
rivets, bends
NaOH
NaOH
Plane
Joints, etc.
Solution
Solution
surfaces.
(ii)
By adding tannin or lignin to boiler water, since these blocks the hair cracks.
(iii)
It has been observed that caustic cracking can be prevented, it Na2SO4 is added to boiler water so that
the ratioNa 2SO 4 concentration
NaOH concentration
(iv)
PRIMING When steam is generated rapidly in the boilers, some droplets of the liquid water are carried
along with the steam. This process is called wet steaming or priming.
Priming is caused by(i)
(ii)
(iii)
Sudden boiling.
(iv)
(v)
(ii)
Proper boiler design so that water level in boilers may be maintained at low level.
(iii)
FOAMING Foaming is the formation of small but stable bubbles above the surface of water, which do
not break easily.
18
Foam formation takes place when concentration of solids in the surface layer is different from that in the
mass of the liquid.
Foaming is caused by The presence of substances like oil (which greatly reduce the surface tension of
water.)
Foaming can be avoided By(i)
The addition of antifoaming agents which reduces the surface tension of water. Ex.- caster oil.
(ii)
Removing oil from boiler water by adding compound like sodium aluminate.
Determinate of Alkalinity-
Alkalinity of water means the total content of those substances in it, which causes an increased [OH]
upon dissociation.
Alkalinity of water may be due to presence of:
-
(i)
(ii)
These can be estimated separately by titration against standard acid, using phenolphthalein and
methyl orange as indicator. The determinations are based on following reaction.
(i) OH + H + H 2 O
P
(ii) CO 23 + H + [ HCO 3 ]
(iii)
HCO 3 + H + H 2 O + CO 2
The titration of the water sample against a standard acid up to phenolphthalein end point (P)
marks the completion of reaction, (i) and (ii) only this amount of acid
1
CO 23
2
M = OH , CO 23 and HCO 3
The possible combinations of ions causing alkalinity
(i)
water are-
(ii)
OH Only or (ii) CO2-3 only or (iii) HCO-3 only or (iv) OH- and CO2-3 together (v) CO2-3 and
HCO-3 together.
* The possiblility of OH- and HCO-3 ions together is ruled out because they combine instantaneously to
from CO2-3 ions.
OH + HCO 3 CO 32 + H 2 O
19
OH-
CO 2
3
HCO 3
P=0
Nil
Nil
P=M
Nil
Nil
P= M
Nil
2P
Nil
P> M
(2P-M)
2(M-P)
Nil
P<M
Nil
2P
[M-2P]
Nu. 100 ml of water sample, on titration with N/50 H2SO4 gave a litre value of 5.8 ml to [P] end point
and 11.6 ml to [M] end point. Calculate the alkalinity of the water sample in terms of CaCO3 and
comment on the type of alkalinity present.
Soln P = 5.8 ml, M = 11.6 ml
it means all alkalinity is due to CO--3 only.
Since P = M,
Further, the volume of N/50 H2SO4 eq. To Co2-3 present in 100 ml of water sample.
=
2P
2 X 5.8 =
Since 1 ml of 1N H2SO4
11.6 ml
=
50 mg of CaCO3
CO--3
11.6 mg of CaCO3
11/6 X (1000/100)
116 mg/L
116 ppm
Result = The alkalinity of water sample is 116 ppm which is only due to CO--3.
Nu. (2) A water saple is not alkaline to [P] However, 100 ml of the sample, on titration with N/50 HCl,
required 16.9 ml to obtain the end point, using [M] as indicatar, are tlu types and amount of alkalinity
present in the sample ?
20