CHAPTER-1&2

WATER TREATMENT AND ITS ANALYSIS

LECTURE-1

1.Introduction to water
1 INTRODUCTION WATER

2.Sources of water

3.Impurties of water :-

Introduction-: water is base of life it is more essential for human being, animal plant, agriculture industry and
pharmacy

2.Sources of water

1. Surface water
2. Underground water
3. Sea water
4. Rain water
5. Re-cyclization Water.

3.Impurties of water :-

1. Physical Impurities .
2. Chemical Impurities .
3. Microbiological Impurities .

4.USE OF WATER

All life on Earth needs water to survive. We humans use water daily to drink, to keep clean, for bathing, showering and
brushing our teeth. We need water to keep our environment clean and we use it in our homes to wash our clothes,
dishes, cars, toilets and pets. There are different indoor and outdoor water uses in our homes. Let’s take a look at
some of them. Indoor Water Uses We use water daily for our indoor activities, to cook food, wash fruits and vegetables
in the kitchen. To flush the toilet, we also wash our hands in the hand basin with soap and water after using the toilet.
We use water for bathing and showering. Imagine using soap only with no water to rinse it with. We also use water to
wash our dishes, both by hand or by dishwasher, and for our laundry, we can’t wear dirty clothes to school can we my
friends? Let’s not forget what the doctor said. W need to drink at least six glasses of water per day for your bodies to
function well. We also use water to make tea, coffee and juice. Wow there are so many things we use water for in our
homes. Outdoor Water Uses Water can also be used for outdoor activities such as the watering of plants that give us
healthy fruits and vegetables in the garden. Watering the grass, washing our pets so that they don’t make us sick when
we play with them, washing our cars and for fun water activities such as swimming or even fishing.
LECTURE -2
2. Hardness & Type of Hardness
1. Hardness of water

2. type of hardness

Soap consuming capacity of the water is known as hardness of water.

Hardness in water is that property , “which prevents the lathering of soap”.

Examples of hardness:-

1.CaCO3 , 2.Ca(HCO3)2 , 3.MgCO3 , 4.Mg(HCO3)2 , 5.CaCl2 , 6. CaSO4 , 7. MgCl2 , 8. MgSO4 ,

9.FeSO4 , 10. Al2(SO4)3

2. type of hardness

There are two types of hardness:-

1. Temporary hardness
2. Permanent hardness

1.Temporary hardness

1. It is due to presence of dissolve of carbonate and bicarbonate of calcium , magnesium and

other heavy metals.
2. It is also called as primary hardness.
3. It is also known as carbonate, bicarbonate and alkaline hardness.
4. It can be removed by boiling the water.
Examples of temporary hardness:-
1. CaCO3 2. MgCO3 3. Mg(HCO3)2 4.Ca(HCO3)2

Boiling test:-

BOIL, 100oC

Ca(HCO3)2 -----------------→ CO2(gas) + CaCO3 (ppt)+ H2O (pH=7)

BOIL, 100oC

THEORITICAL :- Mg(HCO3)2 -----------------→ CO2(gas) + MgCO3 (ppt)+ H2O (pH=7)

BOIL, 100oC

PRACTICAL :- Mg(HCO3)2 -----------------→ 2 CO2(gas) + Mg(OH)2 (ppt)(pH=7.05)

2. Permanent hardness:-
1. It is due to presence of dissolve of chlorides and sulphides of calcium, magnesium, aluminium
and iron.
2. It is also called as secondary hardness.
3. Permanent hardness is also known as non-carbonate or non-alkaline hardness.
Examples of secondary hardness:-
1. CaCl2, 2. CaSO4, 3. MgCl2, 4. MgSO4 , 5.FeSO4, 6. Al2(SO4)3

LECTURE -3
3. Hardness removing method
1.Soap solution method.

2.EDTA method.

1-.Soap Solution Method:-

A sample of hard water , when treated with soap does not produce lather , but on other hand ,
forms insoluble white scum or precipitate , which does not possess any detergent action. It is due
to formation of insoluble soaps of calcium and magnesium.

➢ 2 C17H35COONa (aq.) + CaCO3 (aq.) → (C17H35COO)2Ca (s) + Na2CO3 (aq.) Sodium Sterate
Calcium Calcium Sterate
(Soap) Carbonate (Complex)

➢ 2 C17H35COONa (aq.) + MgCO3 (aq.) → (C17H35COO)2Mg (s) + Na2CO3 (aq.) Sodium Sterate
Magnesium Magnesium Sterate
(Soap) Carbonate (Complex)

➢ 2 C17H35COONa (aq.) + Ca(HCO3)2 (aq.) → (C17H35COO)2Ca (s) +2NaHCO3 (aq.) Sodium

Sterate Calcium Calcium Sterate
(Soap) Bicarbonate (Complex)

➢ 2 C17H35COONa (aq.) +Mg(HCO3)2 (aq.) → (C17H35COO)2Mg (s) + Na2CO3 (aq.) Sodium

Sterate Magnesium Magnesium Sterate
(Soap) Bicarbonate (Complex)

➢ 2 C17H35COONa (aq.) + CaCl2 (aq.) → (C17H35COO)2Ca (s) + 2 NaCl (aq.) Sodium Sterate
Calcium Calcium Sterate
(Soap) Chloride (Complex)

➢ 2 C17H35COONa (aq.) + MgCl2 (aq.) → (C17H35COO)2Mg (s) + 2 NaCl (aq.) Sodium Sterate
Magnesium Magnesium Sterate
(Soap) Chloride (Complex)

➢ 2 C17H35COONa (aq.) + CaSO4 (aq.) → (C17H35COO)2Ca (s) + Na2SO4 (aq.) Sodium Sterate
Calcium Calcium Sterate
(Soap) Sulphate (Complex)

➢ 2 C17H35COONa (aq.) + MgSO4 (aq.) → (C17H35COO)2Mg (s) + Na2SO4 (aq.) Sodium Sterate
Magnesium Magnesium Sterate
(Soap) Sulphate (Complex)

➢ 2 C17H35COONa (aq.) + FeSO4 (aq.) → (C17H35COO)2Fe (s) + Na2SO4 (aq.) Sodium Sterate
Ferrous Iron Sterate
(Soap) Sulphate (Complex)

➢ 6 C17H35COONa (aq.) + Al2(SO4)3 (aq.) → 2(C17H35COO)3Al (s) + 3 Na2SO4 (aq.) Sodium

➢ Sterate Aluminium Aluminium Sterate
(Soap) Sulphate (Complex)

LECTURE-4
4.Determination of Hardness.(EDTA Method)

1. EDTA / Complex-o-metric Method :-

Purposes:-
1. To determine the concentrations of Ca2+(aq) and Mg2+(aq) ions in a commercial sample of bottled
mineral water.
2. To compare experimental results with the concentrations of the metal ions claimed by the
manufacturer.

Introduction:-
The ions involved in water hardness, i.e. Ca2+(aq) and Mg2+(aq), can be determined by titration with a
chelating agent, ethylenediaminetetraacetic acid (EDTA), usually in the form of disodium salt (H2Y2-).
The titration reaction is:

Ca2+(aq) + H2Y2-(aq) ⎯⎯→ CaY2-(aq) + 2H+(aq)

Erio-chrome Black T is commonly used as indicator for the above titration. At pH 10, Ca 2+(aq) ion first
complexes with the indicator as CaIn+(aq) which is wine red. As the stronger ligand EDTA is added, the
CaIn+(aq) complex is replaced by the CaY2-(aq) complex which is blue. The end point of titration is
indicated by a sharp colour change from wine red to blue.
Titration using Erio-chrome Black T as indicator determines total hardness due to Ca 2+(aq) and
Mg2+(aq) ions. Hardness due to Ca2+(aq) ion is determined by a separate titration at a higher pH, by
adding NaOH solution to precipitate Mg(OH)2(s), using hydroxynaphthol blue as indicator.

Materials and Apparatus :-

1. 50% w/v NaOH solution (50 g in 100 cm 3 solution)

2. Erio-chrome Black T indicator
3. pH 10 NH3-NH4Cl buffer, hydroxynaphthol blue indicator, 0.01 M EDTA (disodium salt)
4. Commercial sample of bottled mineral water, apparatus required for titration, 5 cm 3 measuring
cylinder.

Reactions Involved:-

1. Ca/Mg + EBT --------→ Ca-EBT / Mg-EBT

Blue Black Wine Red Colour

2. Ca-EBT / Mg-EBT + EDTA ------→ Ca-EDTA /Mg-EDTA + EBT

Wine Red Colour Blue Black

Experimental Procedures
Part A: Determination of total hardness:-
1. Pipette 50 cm3 mineral water into a conical flask.
2. Add 2 cm3 buffer solution followed by 3 drops of Erio-chrome Black T indicator solution.
3. Titrate with 0.01 M EDTA until the solution turns from wine red to sky blue with no hint of red (save
the solution for colour comparison).
4. Repeat the titration to obtain two concordant results.

Part B: Determination of concentration of Ca2+(aq) ions :-

1. Pipette 50 cm3 of mineral water into a conical flask.

2. Add 30 drops of 50% w/v NaOH solution, swirl the solution and wait for a couple of minutes to
completely precipitate the magnesium ions as Mg(OH)2(s).
3. Add a pinch of hydroxynaphthol blue (exact amount to be decided by the intensity of the resulting
coloured solution) and titrate with 0.01 M EDTA until it changes to sky blue (save the solution for colour
comparison).
4. Repeat the titration to obtain two concordant results.

Calculation:
1. From the results in Part A, determine the total concentration of Ca 2+(aq) and Mg2+(aq) ions in the
mineral water sample in mol dm-3.
2. From the results in Part B, determine the concentration of Ca 2+(aq) ions in the mineral water sample
in mg dm-3, or ppm.
3. Hence, calculate the concentration of Mg 2+(aq) ions in the mineral water sample in mg dm -3 or ppm.
Compare with the corresponding values displayed on the label of the bottle.

Results:-
Part A: Determination of total hardness
Average volume of 0.01 M EDTA used/cm3 :-

Part B: Determination of concentration of Ca2+(aq) ions

Average volume of 0.01 M EDTA used/cm3 :-

Safety:-
1. Avoid skin contact with chemicals.
2. Clothing contaminated with NaOH solution should be carefully removed.
3. Spillage adhering to skin should be immediately washed with plenty of water.

LECTURE-5
5. Unites and degree of hardness
1. degree of hardness
2. unites of hardness
Degree of Hardness:-

Hardness of water is conventionally expressed in terms of equivalent amount of CaCo3, the reason for
taking CaCo3..

1. Easily calculated.
2. Easily reporting in hardness of water.
3. It is insoluble in water.
4. It molecular weight is exact 100.

Degree of Hardness= Molecular weight of X Equivalent Amount of

Producing substance CaCO 3

Equivalent amount of producing substance

OR

Degree of Hardness= Quantity weight of X Molecular weight of

Producing substance CaCO 3

Molecular weight of producing substance

2.units of hardness

Types of unites:- four type of this

1. PPM (parts per million) 106

2. Mg/L (106)
3. French 0Fr (105)
4. Clark 0Cl (70,000)

There are four types of units:-

1. PPM (parts per million) 106 parts per water

2. Milligram per litre (Mg/L)106 parts per water.

3.French (105) parts of water

4.Clark (70,000) parts of water

1. PPM (parts per million) :- It is defined as the number of parts of equivalent hardness
present on 106 parts of water is called (PPM).
2. Mg/L :- It is defines as the number of milligrams of equivalent CaCO 3 hardness of
water present in 106 parts of water is called Mg/L.
3. French :- It is defined as number of parts of CaCO3 equivalent hardness of water
present on 105 parts of water is called French.
4. Clark :- It is defined as number of part of CaCO3 of equivalent hardness of water
present on 70,000 parts of water is called Clark.
Relation:-
PPM = Mg\L = oFr = oCl
106 = 106 = 105 = 70,000
100 = 100 = 10 = 7

1 PPM = 1Mg/L = 0.1oFr =0.07oCl

LECTURE-6

6 .Water softening Method

5.Softening of water by Lime Soda Method
1. internal method
2. external method

3.Internal Methods :-

➢ Colloidal treatment.
➢ Calgon Method.
➢ Carbonate conditioning.
➢ Phosphate conditioning.

2. External Methods :-

➢ Lime Soda Method.

➢ Zeolite Method.
➢ Ion Exchange Method.

Internal Methods:-

1.Colloidal Method:-

In order to minimize scale formation certain colloidal conditioning agents / chemicals are added
in abnormal water / hard water / impure water .
Ex:- Agar-Agar , Tanin Lignin
The scale forming substance to form loose precipitate , it is easily removed by filteration method
.
Water + Agar-agar → Precipitate of CaCO3 , MgCO3 , Mg(OH)2 , CaSO4.

2.Calgon Method:-

Calgon is Sodium Hexa –meta phosphate → Na2[Na4(PO3)6].

In this process scale forming substances are converted into highly soluble complexes which do
not easily precipitate under normal condition.
Calgon is entered for this method , it reacts with calcium cation to form insoluble complexes or
precipitate.
It is easily removed by blow down or filteration process.

Na2[Na4(PO3)6] + Water → 2Na+ + [Na4(PO3)6]2-

[Na4(PO3)6]2- + 2Ca+ → 4Na+ + [Ca2(PO3)6].

3. Carbonate Conditioning:-

In this process the sludge forming substances are converted into highly soluble complexes which
are not easily removed by filteration method.
Carbonate is added in water , it reacts with calcium cation to form insoluble solid calcium
carbonate . It is easily removed by filteration method.

Ca2+ + CO32- → CaCO3

4.Phosphate Conditioning:-

In high pressure boiler scales formation is minimized by adding sodium triphosphate (Na 3PO4)
. It reacts with calcium , magnesium cations to form insoluble precipitate . It is removed by
filteration method .

3 Cacl2 + 2 Na3PO4 → Ca3(PO4)2 + 6 NaCl

2.External Methods:-

1. Lime – Soda Method :-

The basic principle of this process is to chemically convert all the soluble hardness causing
impurities into soluble precipitate , which may be removed by filtration method .

There are two types of Lime – Soda process:-

2. Cold lime – soda process :-

These are further divided into two types:-

(1) Intermittent type.

(2) Continuous cold lime soda process.

ii) Hot lime – soda process.
**Difference between Cold lime - soda and Hot lime - soda process ?

S.No. COLD LIME – SODA PROCESS HOT LIME – SODA PROCESS

1. Its temperature is around 25-40 oC . Its temperature is around 90-100 oC .

2. Cold lime – soda process is a slow process. Hot lime – soda process is a fast process.

It requires Sodium Aluminate (NaAlO2). It does not requires Sodium Aluminate

3. (NaAlO2).
In cold lime – soda process filteration is
difficult. In hot lime – soda process filteration is easy.
4.
In cold lime – soda process dissolved gases In hot lime – soda process dissolved gases
are not removed. are removed.
5.
Its residual hardness is about Its residual hardness is about
50-60 ppm. 15-30 ppm.
6.
After this process , low water softening After this process , high water softening
capacity is found. capacity is found.
7.
LECTURE-7

7.Alkalinity of Hard water :-

Titration of acid base

Titration of carbonate and bicarbonate

Alkalinity is a measure of the capacity of water or any solution to neutralize or “buffer” acids. This
measure of acid-neutralizing capacity is important in figuring out how “buffered” the water is against
sudden changes in pH.

Alkalinity should not be confused with pH. pH is a measure of the hydrogen ion (H+) concentration, and
the pH scale shows the intensity of the acidic or basic character of a solution at a given temperature.
The reason alkalinity is sometime confused with pH is because the term alkaline is used to describe pH
conditions greater than 7 (basic).

The most important compounds in water that determine alkalinity include the carbonate (CO 32-) and
bicarbonate (HCO3-) ions. Carbonate ions are able to react with and neutralize 2 hydrogen ions (H+)
and the bicarbonate ions are able to neutralize H+ or hydroxide ions (OH-) present in water. The ability
to resist changes in pH by neutralizing acids or bases is called buffering.

Alkalinity is important to aquatic organisms because it protects them against rapid changes in pH.
Alkalinity is especially important in areas where acid rain is a problem

Three Types of Alkalinity

Alkalinities are classified according to the endpoint of titration with strong acid:1

(1a) M alkalinity = Alk = total alkalinity (endpoint: CO2 EP)

(1b) P alkalinity = carbonate alkalinity (endpoint: HCO3- EP)

(1c) caustic alkalinity (endpoint: CO3-2 EP)

Here, “M” refers to the pH indicator methylorange (endpoint 4.2 to 4.5); “P” refers to the
pH indicator phenolphthalein (endpoint 8.2 to 8.3).2 “M alkalinity” is what we usually call
“alkalinity” or “general alkalinity” or “total alkalinity”.

For a simple carbonate system (i.e. a pure CO2 solution with a background electrolyte, but
without any other weak acids or bases) alkalinities are defined by:3

(2a) M alkalinity = ( [OH-] – [H+] ) + [HCO3-] + 2 [CO3-2]

(2b) P alkalinity = ( [OH-] – [H+] ) + [CO3-2] – [H2CO3*]

(2c) caustic alkalinity = ( [OH-] – [H+] ) – [HCO3-] – 2 [H2CO3*] = 2P – M

From these three alkalinities it is sufficient to measure M and P alkalinity only; the caustic
alkalinity is then given by 2P – M.

Once M alkalinity and P alkalinity is known we are able to calculate the total amount of
dissolved inorganic carbon:

(3) M–P = [H2CO3*] + [HCO3-] + [CO3-2] = DIC

The equations above are restricted to carbonate systems without other weak acids or
bases. The formula for the general case is given here, which is used in standard
hydrochemistry programs (including aqion). The calculated M and P alkalinities are then
displayed in output tables and simple overviews.

Alkalinity Relationships (Approximations)

Things become simpler at pH > 4.2, i.e. above the M-alkalinity titration endpoint. In this pH
range (which is typical for natural waters), the two species H 2CO3* and H+ almost vanish
and Eqs. (2a) and (2b) reduce to:

(4a) M alkalinity ≈ [OH-] + [HCO3-] + 2 [CO3-2]

(4b) P alkalinity ≈ [OH-] + [CO3-2]

Five special cases are obtained after inserting the following five conditions into Eqs.(4a)
and (4b):

(5a) [OH-] = 0 , [CO3-2] = 0 ⇒ [HCO3-] = M and P=0

(5b) [OH-] = 0 ⇒ [HCO3-] = M – 2P and P = [CO3-2]

(5c) [OH-] = 0 , [HCO3-] = 0 ⇒ [CO3-2] = M/2 and P = [CO3-2]

(5d) [HCO3-] = 0 ⇒ [CO3-2] = M – P and [OH-] = 2P – M

(5e) [HCO3-] = 0 , [CO3-2] = 0 ⇒ [OH-] = M and P=M

These results can be rearranged into the following table where 5a corresponds to column
P = 0, 5b to column P < M/2, 5c to column P = M/2, 5d to column P > M/2, and 5e to column
P = M:

P=0 P < M/2 P = M/2 P > M/2 P=M

[OH-] 0 0 0 2P–M M

2 · [CO3-2] 0 2P M 2(M–P) 0
P=0 P < M/2 P = M/2 P > M/2 P=M

[HCO3-] M M–2P 0 0 0

[OH-] + 2 [CO3-2] + [HCO3-] M M M M M

he bottom row represents the sum in each column. According to Eq.(4a) the sum of the
first column embodies the M alkalinity. This equality is fulfilled across the whole table.

The table above is often used by water-treatment professionals to estimate the content of
HCO3- and CO3-2 from measured M and P alkalinities. In contrast to these approximations,
modern hydrochemistry programs provide the complete/exact carbonate speciation based
on thermodynamic data – for the whole pH range and for any aqueous solution.

Two remarks:

1. In the equations above, [HCO3-] represents the free hydrogen carbonate HCO3- plus all
hydrogen-carbonate complexes such as CaHCO3+. Similarly, [CO3-2] represents
the free carbonate CO3-2 plus all carbonate complexes such as CaCO3.

2. The quantities in square brackets are given in molar units such as mol/L or mmol/L.
Thus, the quantity “2 · [CO3-2]” in the first column of the table stands for carbonate in eq/L
or meq/L (which is the same as val/L or mval/L).

Example no 2.
ALKALINITY Alkalinity is classified as Depending up on the anions that are responsible for the alkalinity of water, there
are three types of alkalinity: 1. Hydroxide alkalinity – due to hydroxide ions 2. Carbonate alkalinity - due to carbonate
ions 3. Bicarbonate alkalinity - due to bicarbonate ions The alkalinity due hydroxide and carbonate can be detected by
Phenolphthalein indicator and so they are collectively called as Phenolphthalein Alkalinity , represented by P. The
alkalinity due hydroxide, carbonate and bicarbonate can be detected by Methyl orange indicator and so it is called as
in Methyl orange Alkalinity, represented by M. 1.Determination of Phenolphthalein Alkalinity ,P : 100 ml of given water
sample is taken in the conical flask , a few drops of Phenolphthalein indicated are added and titrated against N/50
H2SO4 ; let the titre value when the solution becomes colourless, be V1. 2.Determination of Methylorange Alkalinity
,M : The in the same solution a few drops of Methylorange indicator are added and titrated against the same acid until
the colour changes from yellow to red ; let the titre

So, M = V1 + X = V2

(a)Calculation of P: Volume of the acid = V1 cc Normality of the acid , N1 = 1/50 Volume of water , V2 = 100 cc Normality
of water N2 = V1 X 1/50 X 1/ 100 P in terms of CaCO3 = N2 x equivalent of CaCO3 X 1000 mg of CaCO3 = V1 X 1/50 X
1/ 100 X 50 X 1000 mg of CaCO3 = 10 V1 P = 10 V1 ppm (a)Calculation of M: Volume of the acid = V2 cc Normality of
the acid, N2 = 1/50 Volume of water, V1 = 100 cc Normality of water N1 = V2 X 1/50 X 1/ 100 M in terms of CaCO3 =
N1 x equivalent of CaCO3 X 1000 mg of CaCO3 = V2 X 1/50 X 1/ 100 X 50 X 1000 mg of CaCO3 = 10 V2 M = 10 V2 ppm
ALKALINITY HYDROXIDE CARBONATE BICARBONATE P= 0 0 0 M P = 1/2 M 0 2P 0 P = M M or P 0 0 P < 1/2 M 0 2P M -
2P P > 1/2 M 2P - M 2(M - P ) 0
LECTURE-8

8.Zeolite process (water softening)

Introduction

Reaction

apparatus

the Permutit Process, the permutit is placed in a suitable container and hard water allowed to
percolate through. The whole of the hardness is thereby removed. The sodium permutit is thus
gradually converted into the calcium or magnesium salt. Thus:

Reactions involved in Zeolite process:-

CaCO3 + Na2Ze ----→ CaZe + Na2CO3

MgCO3 + Na2Ze ----→ MgZe + Na2CO3
Ca(HCO3)2 + Na2Ze ----→ CaZe + 2 NaHCO3
Mg(HCO3)2 + Na2Ze ----→ MgZe + 2 NaHCO3
CaCl2 + Na2Ze ----→ CaZe + 2NaCl
MgCl2 + Na2Ze ----→ MgZe + 2NaCl
CaSO4 + Na2Ze ----→ CaZe + Na2SO4
MgSO4 + Na2Ze ----→ MgZe + Na2SO4
FeSO4 + Na2Ze ----→ FeZe + Na2SO4
Al2(SO4)3 + 3Na2Ze ----→ Al2Ze3 + 3 Na2SO4

Regeneration Process :-

The regeneration of the permutit is effected by soaking with a 10 per cent, solution of sodium
chloride, whereby sodium permutit is regenerated and soluble calcium and magnesium
chlorides pass into solution and are washed away.

CaPm + 2NaCl = CaCl2 + Na2Pm

and
MgPm + 2NaCl = MgCl2 + Na2Pm.

When water is very hard it is sometimes partially softened by a preliminary treatment with
lime and soda. In some cases the permutit plant fed with such treated waters has ceased to
work satisfactorily after a number of years, the permutit becoming contaminated with chalk.

Sodium permutit is gradually attacked by dissolved carbon dioxide and more rapidly by
mineral acids. Waters therefore containing acids in solution are filtered through limestone or
marble before reaching the permutit.

In this connection it may be mentioned that a manganese permutit filter has been invented for
the removal of ferrous salts, which become oxidised in some manner, possibly in part through
catalysis, but also through reduction of the manganese permutit, which requires periodic
revivifying by treatment with a solution of permanganate of lime.
The following analyses of water before and after softening by permutit are interesting. The
data are expressed as parts per million (mg. per litre):

Before Softening After Softening

Silica 15 11
Iron oxide and alumina Trace trace
Lime 98 nil
Magnesia 10 4
CO2 - bound 81 121
CO2 - free or half bound 111 78
SO3 28 28
Cl 34 36
KOH, NaOH 58 234
Total hardness 11.2 0.6
Permanent hardness 0.9 nil

The water after Permutit Process is beautifully softened, but is rendered more corrosive towards iron
and steel
LECTURE-9

9.Ion Exchange Method:-

Apparatus

Introduction

Reaction

Working

Demineralisation

For many applications, all ions in the water must be removed. In particular, when water is heated to
produce steam, any impurity can precipitate and cause damage. As there are cations and anions in the
water, we must use two different types of resins: a cation exchanger and an anion exchanger. This
combined arrangement produces pure water, as presented in the general introduction.
Demineralisation is also called deionisation. The cation resin is used in the hydrogen form (H +) and
the anion resin in the hydroxyl form (OH–), so that the cation resin must be regenerated with an acid
and the anion resin with an alkali.

A de-gasifier is used to remove the carbon dioxide created after cation exchange when the water
contains a significant concentration of bicarbonate.
The cation resin is usually located before the anion resin: otherwise if the water contains any hardness,
it would precipitate in the alkaline environment created by the OH — form anion resin as Ca(OH)2 or
CaCO3, which have low solubility.

Layout SAC – (DEG) – SBA

Let us first consider a simple demineralisation system comprising a strong acid cation exchange resin
in the H+ form, a degasifier (optional) and a strong base anion exchange resin in the OH – form. The
first step is decationisation as shown above:

RSAC-H + Na+ RSAC-Na + H+

With calcium instead of sodium (also valid for magnesium and other divalent cations):

2 RSAC-H + Ca++ (RSAC)2-Ca + 2 H+

In the second step, all anions are removed with the strong base resin:

RSBA-OH + Cl– RSBA-Cl + OH–

The weak acids created after cation exchange, which are carbonic acid and silicic acid (H2CO3 and
H2SiO3) are removed in the same way:

RSBA-OH + HCO3– RSBA-HCO3– + OH–

And finally, the H+ ions created in the first step react with the OH– ions of the second step to produce
new molecules of water. This reaction is irreversible:

H+ + OH– H 2O

What happens to the water

1: Cation exchange removing all cations (as in decationisation) followed by degassing:

SAC (H) DEG

Raw water Decationised water Decat + degassed water

2: Anion exchange removing all anions (strong and weak acids):

SBA (OH)

Decat + degassed water Demineralised water

Demineralised water is completely free of ions, except a few residual traces of sodium and silica,
because the SAC and SBA resins have their lowest selectivity for these. With a simple demineralisation
line regenerated in reverse flow, the treated water has a conductivity of only about 1 µS/cm, and a silica
residual between 5 and 50 µg/L depending on the silica concentration in the feed and on regeneration
conditions.
Note that the pH value should not be used as a process control, as it is impossible to measure the pH of
a water with less than say 5 µS/cm conductivity.

Regeneration:-The SAC resin is regenerated with a strong acid, HCl or H 2SO4:

R-Na + H+ R-H + Na+

And the SBA resin is regenerated with a strong alkali, NaOH in 99 % of the cases:

RSBA-Cl + OH– RSBA-OH + Cl–

Layout WAC/SAC – DEG – WBA/SBA

Because weakly acidic and weakly basic resins offer a high operating capacity and are very easy to
regenerate, they are used in combination with strongly acidic and strongly basic resins in large plants.
The first step with the WAC resin is dealkalisation (removal of bicarbonate hardness), and the second
step with the SAC removes all the remaining cations. A WAC resin is used when both hardness and
alkalinity are present in large relative concentrations in the feed water.

WBA resins remove only the strong acids after cation exchange. They are not capable of removing the
weak acids such as SiO2 and CO2. In the regenerated, free base form, they are not dissociated, so no
free OH– ions are available for neutral anion exchange. On the other hand, their basicity is enough to
adsorb the strong acids created after cation exchange:

RWBA + H+Cl– RWBA.HCl

In the last step, a SBA resin is thus required to remove the weak acids, as shown in the preceding section:

RSBA-OH + HCO3– RSBA-HCO3– + OH–

What happens to the water

1 & 2: Cation exchange beginning with the removal of temporary hardness (WAC, as in dealkalisation)
followed by the removal of all remaining cations (SAC):
WAC (H) SAC (H)

Raw water Decarbonated water Decationised water

3 & 4: Anion exchange begining after degassing with the removal of strong acids (WBA) followed by
the removal of weak acids (SBA):

WBA (FB) SBA (OH)

Decat + degassed water Partially demineralised Demineralised water

A full demineralisation line is shown below, with a cation exchange column (WAC/SAC), a degasifier,
an anion exchange column (WBA/SBA), and a polishing mixed bed unit. The use of a weakly acidic resin
and the degasifier column are conditioned by the presence of hardness and alkalinity in the feed water,
as explained in the previous sections.

ADVANTAGES OF ION-EXCHANGE SOFTENING

Compared with lime-soda ash softening, ion-exchange has certain advantages. It is compact and has a
low capital cost. The chemicals used are safer for the operator to handle and operation is much easier.
It can be almost totally automated. Because resins have the ability to remove all hardness from the
water, treated water must be blended with water that has been by-passed around the softener (or
adjustments made) to obtain a hardness level the operator needs to maintain.

Many systems have found ion-exchange to be the most cost effective way to produce quality water for
their customers. If zeolite units are used to soften surface water, it must be preceded by surface water
treatment.

• Variety of cost effective standard models.

• Improved aesthetics and rugged design.
• User friendly, low maintenance and easy to install.
• Simpler distribution and collection systems.
• Quick availability.
• Pre dispatch assembly check.
• The multiport valves are top mounted as well as side mounted with the necessary high pressure
rating PVC piping.
• Single valve operation as compared to the six valves in conventional filters
• Each operating step is clearly marked on the valve, thereby eliminating chances of error in the
operating sequence.
• Single valve assembly, with its simplified frontal Piping, simpler distribution collecting systems is
Very easy to install.
• Rust free
• Less power consumption
• Durable
• Economical
• High shelf life

LECTURE-10
10.Boiler Problems :-
Four types of problem

1. scales and sludge

2 carry over

3 caustic embitterment

4.boiler corrosion

Boiler require high quality water and high quantity water for their efficient operation . Generally
, the water is used in boiler for steam generation and distillation . If feed water is feed directly to
the boiler , there arise many problems.

**Difference between scales and sludge formation

S.NO. SCALES FORMATION SLUDGE FORMATION

1. Scales are hard deposites on inner wall Sludges are soft and loose precipitate on
of boiler. upper part of the boiler.

2. Scales are formed by calcium sulphate Sludges are formed by calcium

and magnesium hydro-oxide. chloride,magnesium chloride,calcium
carbonate magnesium carbonate,
magnesium sulphate.
Scales are generally formed at heated
3. portion of boiler. Sludges are generally formed at colder
portion of boiler.
Scales formation decreases the
4. efficiency of boiler. Sludge formation also decreases the
efficiency of boiler but less dangerous.

Scales are very difficult to remove. Sludge can be very easily removed.
5.
**Write a shote note on Caustic Embrittlement ?

Caustic embrittlement is the phenomena in which boiler material becomes brittle due to
presence of caustic materials.This type of boiler corrosion is caused by using highly alkaline
water in the boiler especially in the boiler which are operated at high pressure.
In Lime –soda process free Na2CO3 is usually present in small amount of water . It decomposes
to give sodium hydro-oxide and carbon dioxide.
Na2CO3 + H2O → 2NaOH + CO2
Potassium Carbon dioxide
hydro-oxide

This makes the water caustic . The sodium hydro-oxide containing

water runs into minute hair packs present in the inner side of boiler
. This causes the brittlement of the boiler parts , particular parts like
bends , joints , lids etc., leads to failure of boiler.

**Write a short note on Boiler Corrosion ?

Decay of boiler material by a chemical or electrochemical attack in
environmental condition.The corrosion in boiler is due to gases like
O2,CO2 and SO2.
1.Dissolved oxygen (DO):-
➢ Water contain usually 8 ppm around dissolved oxygen at room temperature.
➢ As water is heated , the dissolved oxygen is set free and te boiler starts corroding .
Dissolved oxygen reacts with iron of boiler , in the presence of water and under prevailing
high tempertaure to form ferric oxide(rust).

4Fe + 2H2O + O2 → 4Fe(OH)2

4Fe(OH)2 + O2 → 2[ Fe2O3.2H2O]
Ferrous Hydroxide Ferric Oxide(rust)

10.Boiler Troubles (Priming and foaming & caustic embrittlement

**Define Carry Over ?

The phenomena of carrying water along with impurities of steam is called carry over . Carry over
is due to priming and foaming.

Priming:- When steam is produced rapidly in the boilers , some droplets of the liquid water are
carried along with the steam .This process of “Wet Steam” formation is called priming.
Priming is caused by:-
➢ The presence of considerable quantities of dissolved solids (mainly due to suspended
impurities and dissolved impurities in water.)
➢ High steam velocities carry droplets of water into the stam pipe.
➢ Sudden boiling.
➢ Faulty design of boiler.

Foaming:- Foaming is the production of foam or bubbles in the boiler which donot break easily
. It is due to presence of oil and alkalis in boiler feed water .
Oil reduces the surface tension of water
Foaming can be avoided by adding sodium aluminate (NaAlO 2).
LECTURE-11

11.Numerical Lime Soda Method method

Calculate the amount of lime required for softening 50,000 liter of hard water containing CaCO3= 25 ppm,
MgCO3= 144, CaCl2= 111ppm, MgCl2= 95 ppm, Na2SO4= 15 ppm, Fe2O3= 25 ppm. Constituent
Multiplication factor CaCO3equivalent CaCO3= 25 MgCO3= 144 CaCl2= 111 MgCl2= 95 100/100 100/84
100/111 100/95 25 X 100 X 100 = 25.0 mg/L 144 X 100 X 84 = 171.43 mg/L 111 X 100 X 111 = 100.0 mg/L 95
X 100 X 95 = 100.0 mg/L Lime required for softening 50,000 L of water = 74/100 [CaCO3+ 2 x MgCO3+ MgCl2as
CaCO3eq] x Vol. of water = 74/100 [25.0 + 2 x 171.43 100]mg/L x 50,000 L = 74/100 [467.86 mg/L] x 50,000 L
= 1, 73,10,820 mg = (1.73, 10,820 x 106) kg = 17.311 kg2.Calculate the quantity of lime and soda required for
softening 50,000 liters of water containing the following salts per liter: Ca(HCO3) = 8.1mg ; Mg(HCO3)2= 7.5mg
; CaSO4= 13.6 mg; MgSO4= 12.0 mg; MgCl2= 2.0 mg; and NaCl = 4.7 mg. Ans 1.0134 kg (Lime) ; 0.9068
kg(Soda).3.A water sample contains the following impurities: Ca 2+= 20ppm. Mg 2+= 18 ppm, HCO3-= 183
ppm and SO42-= 24 ppm. Calculate the amount of lime and soda needed for softening. Ans. 166.5 ppm or
mg/L (Lime): Negative or nil (Soda). 4.Explain with chemical and the amount of lime and soda needed for
softening 1,00,000 liters of water containing the following :
LECTURE-12

12. Numerical Zeolite Method method

Numerical based on ZEOLITE Process : The hardness OF 100.000 lit of water was completely
removed by passing it through a zeolite softener.

he hardness OF 100.000 lit of water was completely removed by passing it through a zeolite softener. The
softener then required 40o lit of NaCl containing 100 gm /lit NaCl for regeneration Calculate hardness of
water

Total amount of NaCl required for regeneration = 100 x 103 x 400 = 4 x 107 58.5 gm of NaCl = 50
gm of CaCO3
4 x 107 mg NaCl = 4 x 107/58.5 X 50
CaCO3 equivalent of NaCl =3.419 X 107mg of CaCO3
Volume of water = 100,000 lit
Hardness of water =CaCO3 equivalent of NaCl /hardness
Hardness of water =3.419 X 107 /100,000
Hardness of water =3.419 X 102p

Numerical OF Alkalinity
Calculation of Bicarbonate, Carbonate and Hydroxide Alkalinity 1. remember, total alkalinity is the amount
of acid required to lower the pH of the solution to 4.5 2. can be divided into various species if inflection points
are known a. phenolphthalein alkalinity (hydroxide and ½ carbonate neutralized) occurs when sufficient acid
has been added to lower pH to 8.3 -- solution goes pink i. carbonate actually converted to bicarbonate (by pH
7) b. additional acid to reduce pH 8.3 to 4.5 neutralizes remaining ½ carbonate (already converted to
bicarbonate) and the bicarbonate -- solution turns orange (a) carbonate alkalinity is present when the
phenolphthalein alkalinity is not zero, but less than the total alkalinity (b) Hydroxide alkalinity is present if
the phenolphthalein alkalinity is more than half the total alkalinity (c) Bicarbonate alkalinity is present if the
phenolphthalein alkalinity is less than half the total alkalinity (d) Bicarbonate and Hydroxide alkalinities
cannot be present together (e) All hydroxide alkalinity is neutralized by pH 10.0 (f) all Carbonates are
converted to bicarbonates by pH 8.3 Group Result of Hydroxide Carbonate Bicarbonate Titration Alkalinity
Alkalinity Alkalinity A P = 0 0 0 T (initial pH < 8.3) B P = 0.5T 0 2P 0 C P = T T 0 0 D P < 0.5T 0 2P T-2P