Engineering Chemistry

Dr. Bhavna Mukesh Vyas

27-11-2024 © Bhavna M. Vyas 1

Unit 1: Dissolved Mineral Matter in Water
Most Important dissolved mineral matter in water

from Industrial application point of view): Hardness & Alkalinity

Hardness: Defined as soap consuming capacity of a water sample (mainly due to the
presence of Ca & Mg ions)

What are Soaps?

Soaps are sodium salts of long chain fatty acids such as oleic acid, palmitic and stearic acid

Ca & Mg ions react with sodium salts of long chain fatty acids present in the soap to form
insoluble scums of calcium and magnesium soaps which do not possess any detergent value

(does not produce lather or foam)

2𝐶17 𝐻35 𝐶𝑂𝑂𝑁𝑎 + 𝐶𝑎𝐶𝑙2 → 𝐶17 𝐻35 𝐶𝑂𝑂 2 𝐶𝑎 + 2𝑁𝑎𝐶𝑙
27-11-2024 © Bhavna M. Vyas 2
Water hardness is classified by the U.S. Department of
Interior and the Water Quality Association as follows:

Classification mg/l or ppm

• Soft 0 - 17.1
• Slightly hard 17.1 - 60
• Moderately hard 60 - 120
• Hard 120 - 180
• Very hard 180 & over

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 S.No. Drinking water
IS 10500 : 2012
Parameters
Maximum
Permissible Limit
Limit
1 Odor Agreeable Agreeable
2 Taste Agreeable Agreeable
3 No
pH 6.5 to 8.5
relaxation
4 TDS (mg/l) 500 2000
5 Hardness (as CaCO3) (mg/l) 200 600
6 Alkalinity (as CaCO3) (mg/l) 200 600
7 No
Nitrate (mg/l) 45
relaxation
8 Sulfate (mg/l) 200 400
9 Fluoride (mg/l) 1 1.5
10 Chloride (mg/l) 250 1000
11 Turbidity (NTU) 5 10
12 Arsenic (mg/l) 0.01 0.05
13 Copper (mg/l) 0.05 1.5
14 No
Cadmium (mg/l) 0.003
relaxation
15 No
Chromium (mg/l) 0.05
relaxation
16 No
Lead (mg/l) 0.01
relaxation
17 No
Iron (mg/l) 0.3
relaxation
18 Zinc (mg/l) 5 15
19 Fecal Coliform (cfu) 0 0
20 E. Coli (cfu) 0 0

27-11-2024 © Bhavna M. Vyas 4

 Unit 1: Hardness of Water
Hard Water: Does not produce lather with soap solution, forms precipitate

Soft water: Lathers easily with soap solution

Types of Hardness:

1. Temporary Hardness (Carbonate Hardness or Alkaline Hardness)

Due to the presence of dissolved impurities in water like bicarbonates of Ca, Mg, Fe, Al,
Mn that can be removed from water by merely boiling followed by filtration.

When natural water is boiled, the soluble bicarbonate ions present get decomposed and
form insoluble carbonates or hydroxides.
𝐶𝑎 𝐻𝐶𝑂 3 → 𝐶𝑎𝐶𝑂3 + 𝐻2 𝑂 + 𝐶𝑂2
𝑀𝑔 𝐻𝐶𝑂 3 → 𝑀𝑔 𝑂𝐻 2 + 2𝐶𝑂2

Thus, temporary hardness causing impurities can be easily removed by boiling and filtration
27-11-2024 © Bhavna M. Vyas 5
 Unit 1: Hardness of Water
Hard Water: Does not produce lather with soap solution, forms precipitate

Soft water: Lathers easily with soap solution

Types of Hardness:

1. Temporary Hardness (Carbonate Hardness or Alkaline Hardness)

Due to the presence of dissolved impurities in water like bicarbonates of Ca, Mg, Fe, Al,
Mn that can be removed from water by merely boiling followed by filtration.

When natural water is boiled, the soluble bicarbonate ions present get decomposed and
form insoluble carbonates or hydroxides.
𝐶𝑎 𝐻𝐶𝑂 3 → 𝐶𝑎𝐶𝑂3 + 𝐻2 𝑂 + 𝐶𝑂2
𝑀𝑔 𝐻𝐶𝑂 3 → 𝑀𝑔 𝑂𝐻 2 + 2𝐶𝑂2

Thus, temporary hardness causing impurities can be easily removed by boiling and filtration
27-11-2024 © Bhavna M. Vyas 6
 Unit 1: Hardness of Water
Types of Hardness:

2. Permanent Hardness (Non-Carbonate Hardness or Non-Alkaline Hardness)

Due to the presence of dissolved impurities in water like chlorides, sulphates and nitrates
of Ca, Mg, Fe, Al, Mn etc.

These salts cannot be removed by merely boiling, needs special water softening methods
to remove permanent hardness of water.

Temporary and permanent hardness together called as total hardness of water.

Total Hardness = Temporary Hardness + Permanent Hardness

27-11-2024 © Bhavna M. Vyas 7

 Unit 1: Hardness of Water
Degree of Hardness:

• Total hardness present in water is because of different salts of calcium and

magnesium with different molecular weights.

• Hence, hardness of water is conveniently expressed in terms of calcium

carbonate equivalence.

• The weights of different salts causing hardness are converted to weight

equivalent to that of calcium carbonate.

• If a water sample contains 2 or more salt their quantities are converted to

calcium carbonate equivalence and the sum will give total hardness in
terms of calcium carbonate equivalence.
27-11-2024 © Bhavna M. Vyas 8
 Unit 1: Hardness of Water
Degree of Hardness:

• Degree of hardness is defined as the number of parts by weight of calcium

carbonate hardness per particular number of parts of water, depending
upon the unit employed.

• Though the hardness does not always arise due to calcium carbonate in
water, it is a standard practice to express it in terms of equivalents of
CaCO3. WHY ?????

• Calcium carbonate is selected for expression of degree of hardness because:

• its molecular weight is exactly 100 which makes calculation convenient

• it is the most insoluble salt that can be precipitated out of water

27-11-2024 © Bhavna M. Vyas 9
 Unit 1: Hardness of Water
Degree of Hardness:

The CaCO3 equivalent for any dissolved salt in water can be calculated as:

𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑂3

CaCO3 equivalent of any salt = Weight of salt present (mg/l) ×
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑙𝑡

𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑂3

CaCO3 equivalent of bivalent salt = Weight of salt present (mg/l) ×
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑙𝑡

27-11-2024 © Bhavna M. Vyas 10

 Unit 1: Hardness of Water
Units of Hardness:

1. Parts per Million (ppm): It is the number of equivalent parts of CaCO3

present per million parts (106) parts of water by weight

2. Milligram per liter (mg/l): It is the number of mg of CaCO 3 dissolved in 1

litre of water.

3. Degree Clarke (0Cl): It is the number of equivalent parts of CaCO3 present

per 70,000 parts of water or 1 gallon of water

4. Degree French (0Fr): It is the number of equivalent parts of CaCO 3 present

per 105 parts of water 1 mg/l = 1 ppm (Prove)

27-11-2024 © Bhavna M. Vyas 11

 Numericals: Hardness of Water

27-11-2024 © Bhavna M. Vyas 12

27-11-2024 © Bhavna M. Vyas 13
 Unit 1: Chemical analysis of water
Determination of Hardness of Water by EDTA Method:

The hardness of water can be determined by complexometric titration.

Complexometric titrations involve formation of a soluble complex between a metal

ion and a complexing agent.

Metal ion is called the central atom and the complexing agent is called the
ligand. The ligands can be unidentate, bidentate or polydentate having one, two and
more than two donor atoms respectively which can form stable complexes.

The polydentate ligands form stable complexes with wide variety of metals as these
ligands form ring structures called chelates.

EDTA is used as complexing agent in determination of hardness of water

27-11-2024 © Bhavna M. Vyas 14
 Unit 1: Chemical analysis of water
Determination of Hardness of Water by EDTA Method:

Ethylene Diamine Tetra Acetic acid (EDTA) is one of the notable ligands used as
complexing reagent.

EDTA has six potential sites (hexadentate) for bonding a metal ion, the two amino
groups and four carboxy group. When EDTA is dissolved in water, it forms zwitterion
(an ion with a positive and a negative electrical charge at different locations within a
molecule). The various EDTA species are abbreviated as H4Y, H3Y-, H2Y2-, HY3- and
Y4-. EDTA forms stable complexes (chelates) with the metal ions.

Because of limited solubility of EDTA, the disodium salt Na2H2Y is used for
analytical work (high state of purity as the dihydrate)
27-11-2024 © Bhavna M. Vyas 16
 Structure of EDTA & Ca-EDTA Chelate
https://www.toppr.com

27-11-2024 © Bhavna M. Vyas 17

 Unit 1: Chemical analysis of water
Principle of EDTA Method:

• EDTA forms stable complexes (chelates) with the hardness causing metal (Ca or
Mg) ions.

• Hard water titrated against Na2EDTA in a complexometric titration.

• Eriochrome Black-T (EBT) indicator is used in complexometric titration. EBT is

pH sensitive indicator and effective in alkaline condition (about pH 10).

• Ammoniacal Buffer solution (NH4OH+NH4Cl) is used to maintain pH of about 10

during a complexometric titration.

• EDTA a complexometric titration works as follows:

27-11-2024 © Bhavna M. Vyas 18

 Unit 1: Chemical analysis of water
Principle of EDTA Method:

• EDTA solutions are used as Titrant in complexometric titration.

• Indicator EBT, which is a blue-coloured dye, forms an unstable & soluble wine-red color
complex with Ca and Mg ions in hard water at a pH of 9 to 10.

• When unstable wine-red color complex is treated with EDTA solution, EDTA being more
sensitive replaces Ca2+ and Mg2+ ions from the unstable indicator complex to form a stable
complex, with the result, indicator is set free giving its original blue color.
• [Mg2+ / Ca2+ - EBT] + EDTA → [Mg2+ / Ca2+ - EDTA] + EBT
(Wine-red) (Colourless) (Blue)
• Thus, in EDTA complexometric titration using EBT indicator, the end point is wine-red
turns blue

• Thus, the amount of EDTA consumed in titration corresponds to the hardness of water.
27-11-2024 © Bhavna M. Vyas 19
 Unit 1: Chemical analysis of water
Reactions:
Ca2+ / Mg2+ + EBT → Ca2+- EBT / Mg2+ - EBT
Colourless Wine Red Unstable Complex

Ca2+/Mg2+ + EDTA → Ca2+ - EDTA /Mg2+ - EDTA

Colourless Stable Complex

[Mg2+ / Ca2+ - EBT] + EDTA → [Mg2+ / Ca2+ - EDTA] + EBT

Wine Red Complex Colourless Stable Complex Blue
HIn2- + M 2+ ® MIn- + H +
EBT +Ca2+ / Mg 2+ ®Ca - EBT / Mg - EBT
MIn- + H 2Y 2- ® MY 2- + HIn 2- + H +
Ca / Mg + EDTA ® éëCa - EDTA / Mg - EDTAùû
2+ 2+

27-11-2024 © Bhavna M. Vyas 20

 Unit 1: Chemical analysis of water
Procedure to find Total Hardness of Water Volumetrically:

1. Standardisation of EDTA:

• Prepare standard ZnSO4 solution (of exact M1 molarity)

• Fill the burette with EDTA solution (of approximate M2 molarity)

• Pipette out V1 ml of standard ZnSO4 solution in a conical flask

• Add one-third test tube of ammoniacal buffer solution and few drops of EBT indicator

• Wine red coloured solution is then titrated against EDTA solution from burette till colour
changes to blue.

• Note down the end point as V2 ml (EDTA consumed)

(Standardisation: To get the Exact molarity of EDTA solution using primary standard substance )
27-11-2024 © Bhavna M. Vyas 21
 Unit 1: Chemical analysis of water
Procedure to find Total Hardness of Water Volumetrically:

2. Estimation of total hardness of water:

• Fill the burette with EDTA solution

• Pipette out V ml of hard water in a conical flask

• Add one-third test tube of ammoniacal buffer solution and few drops of EBT indicator

• Wine red coloured solution is then titrated against EDTA solution from burette till colour
changes to blue.

• Note down the end point as ‘Y’ ml (volume of EDTA consumed)

27-11-2024 © Bhavna M. Vyas 22

 Unit 1: Chemical analysis of water
Procedure to find Total Hardness of Water Volumetrically:

3. Calculations to find total hardness of water:

• For standardisation of EDTA: Using, M1V1= M2V2 (ZnSO4 vs EDTA)

Exact Molarity of EDTA can be found out.

• Calculation of total hardness of water: EDTA forms 1 : 1 complex with Ca and Mg ions
• 1 mole of EDTA = 1 mole of CaCO3
• 1000 ml of 1 M EDTA = 100 g of CaCO3
• 1 ml 1 M EDTA = 100 mg of CaCO3
• ‘CBR’ ml M2 EDTA = 100 x ‘CBR’ x M2 mg of CaCO3
• V ml water sample contains = ….. mg of CaCO3

100∗Volume of EDTA consumed(ml)∗Molarity of EDTA∗1000

𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 = Volume of water sample (ml)
𝑝𝑝𝑚
27-11-2024 © Bhavna M. Vyas 23
27-11-2024 © Bhavna M. Vyas 24
 Numericals

1. 250 mL of a water sample on EDTA titration with Eriochrome Black –T consumed 13 mL

of 0.022 N EDTA till end point is reached. Calculate the hardness of water.

2. (Hardness = 114.4 ppm)

3. 100 mL of a sample of water required 15 mL of 0.01 M EDTA for titration using

Eriochrome Black –T as indicator. In another experiment, 100 mL of the same sample was
boiled to remove the temporary hardness, the precipitate was removed and the cold
solution required 8 mL of 0.01 M EDTA using Eriochrome Black –T as indicator. Calculate
the total hardness, permanent hardness and temporary hardness in mg/L of CaCO3
equivalent.

4. (Total Hardness = 150 ppm, PH=80 ppm & TH=70ppm)

27-11-2024 © Bhavna M. Vyas 25

 Numericals

3. 100 mL of the hard water sample required 35 mL of the same EDTA

solution on titration. After boiling 100 mL of this water, cooling, filtering and
then titration required 10 mL of EDTA solution. Calculate the temporary and
permanent hardness of water.

(Total hardness = 350 ppm, Permanent Hardness = 100 ppm, Temporary

Hardness = 250 ppm )

27-11-2024 © Bhavna M. Vyas 26

 Alkalinity of water
Alkalinity is a measure of the ability of water to neutralize the acids

• The alkalinity of water is normally due to the presence of

bicarbonates, carbonates and hydroxides of sodium, potassium,
calcium and magnesium.

• Some of the salts, which cause alkalinity, also cause hardness, but
not all. (However, the presence of other bases such as borates,
silicates, phosphates can also contribute to the total alkalinity,
though to a small extent)
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 Alkalinity of water
Classification of Alkalinity: Alkalinity based on the anions
present in the water is classified as:

1. Caustic Alkalinity (due to Hydroxide and Carbonate ions)

2. Bicarbonate Alkalinity (due to Bi-carbonate ions)

Alkalinity of a water sample due to different ions can be

determined by neutralization titration using a standard acid
and making selective use of indicators. The indicators used are
Phenolphthalein and Methyl orange.
27-11-2024 © Bhavna M. Vyas 28
 Alkalinity of water
Reactions: The determination is based on following reactions

i. OH- + H+ ⇢ H2O
ii. CO3- - + H+ ⇢ HCO3-
iii. HCO3- + H+ ⇢ H2CO3

➢ Reaction 1 and 2 corresponds to Phenolphthalein (P) end point i.e.

complete neutralization of OH- and half neutralization of CO3- -
➢ Reaction 1 to 3 corresponds to Methyl Orange (M) end point i.e.
complete neutralization of OH- , CO3- - and HCO3- ions.

27-11-2024 © Bhavna M. Vyas 29

 Alkalinity of water
Alkalinity may be due to presence of following combinations:

1) Alkalinity due to HCO3- only

2) Alkalinity due to, CO3- - only

3) Alkalinity due to, OH- , only

4) Alkalinity due to, CO3- - and HCO3- ions

5) Alkalinity due to, OH- and CO3- -

The possibility of OH– and HCO3– together is ruled out, they combine instantaneously
to form CO3- - ions, thus all ions cannot exist together.

Thus, on the basis of Phenolphthalein alkalinity and methyl orange alkalinity, the
alkalinity in water due to different ions ©can
27-11-2024
be calculated.
Bhavna M. Vyas 31
 Alkalinity of water
Procedure:
• Pipette out 100 mL of the water sample in a clean titration flask.

• Add 2–3 drops of phenolphthalein indicator.

• Run in N/50 H2SO4 or HCl (from a burette), till the pink color is just
discharged. This is the first end point.

• Let the volume of acid used until phenolphthalein end point = V 1 mL.

• Then to the same solution, add 2 to 3 drops of methyl orange. Continue

titration, till the yellow colour changes to orange/red. This is the second
end point.

• Let volume of acid used to methyl

27-11-2024 orange
© Bhavna M. Vyas end point = V2 mL. 32
 Alkalinity of water
OBSERVATIONS:
Volume of water sample (unknown alkalinity) selected = _ ml
For Phenolphthalein end point
• Burette: HCl solution of _________N
• Indicator: Phenolphthalein
• End point: Pink turns colourless
• Volume of titrant (HCl) consumed, V1 = ______ml
For Methyl orange end point
• Burette: HCl solution of _________N
• Indicator: Methyl Orange
• End point: Yellow turns orange/red
• Volume of titrant (HCl) consumed, V2 = ______ml
27-11-2024 © Bhavna M. Vyas 33
 Alkalinity of water
CALCULATIONS:

50 × 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 (𝑚𝑙) × 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝑎𝑐𝑖𝑑 × 1000

𝑃ℎ𝑒𝑛𝑜𝑙𝑝ℎ𝑡ℎ𝑎𝑙𝑒𝑖𝑛 𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑃 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒(𝑚𝑙)

50×𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 (𝑉2)×𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝑎𝑐𝑖𝑑×1000

𝑀𝑒𝑡ℎ𝑦𝑙 𝑂𝑟𝑎𝑛𝑔𝑒 𝐴𝑙𝑘𝑎𝑙𝑖𝑛𝑖𝑡𝑦 𝑀 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒

From the measurement of Phenolphthalein alkalinity and methyl orange

alkalinity, it is possible to calculate the magnitude of various forms of
alkalinity present in water sample,
27-11-2024 © Bhavna M. Vyas 34
 Alkalinity of water
Sr. No. Alkalinity OH- (ppm) CO32- (ppm) HCO3- (ppm)

1 P=0 NIL NIL M

2 P= M
1 NIL 2P NIL
2

3 P<
1
M NIL 2P (M- 2P)
2

4 P> M
1 (2P – M) 2 (M-P) NIL
2

5 P=M P=M NIL NIL

27-11-2024 © Bhavna M. Vyas 35

 Alkalinity of water
(i) When P = 0, both OH– and CO32– are absent and alkalinity in that case is
due to HCO3– alone.

(ii) When P = M neither CO32– nor HCO3– ions are present, only OH– ions are
present, Thus alkalinity due to OH– = P = M.

(iii) When P = 1/2 M or V1 = V2/2, only CO32– is present,

since half of carbonate neutralisation (ie CO32– + H+ → HCO3– ) takes place

with phenolphthalein, while complete carbonate neutralisation (CO 32– + H+ →
HCO3– ; HCO3– + H+ → H2O + CO2) occurs when methyl orange indicator is
used. Thus, alkalinity due to CO32– = 2P.

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 Alkalinity of water
(iv) When P>1/2 M or V1>V2/2 In this case, besides CO32– , OH– ions are also
present.

Now half of CO32– (i.e., HCO3– + H+ → H2O + CO2 ) is equal to (M – P), so

alkalinity due to complete CO32– = 2(M–P) and

alkalinity due to OH– = M–2(M–P) = (2P–M).

(v) When P<1/2 M or V1<V2/2, in this case, besides CO32– , HCO3– ions are
also present, now alkalinity due to CO32– = 2P and alkalinity due to HCO3– =
(M – 2P).
27-11-2024 © Bhavna M. Vyas 37
 Numericals on Alkalinity of water
1. 50 mL of a sample of water required 5 mL of N/50 H2SO4 using methyl orange as
indicator but did not give any coloration with phenolphthalein. What type of alkalinity is
present? Express the same in ppm. (P=0, Only HCO3-)

2. 200 mL of water sample on titration with N/50 H2SO4 using phenolphthalein as indicator
gave the end point when 10 mL of acid were run down. Another lot of 200 mL of the
sample also required 10 mL of the acid to obtain methyl orange end point. What type of
alkalinity is present in the sample and what is its magnitude? (P=M/2, Only CO3--)

3. 500 mL of a water sample on titration with N/50 H2SO4 gave a titre value of 29 mL to
phenolphthalein end point and another 500 mL sample on titration with same acid gave a
titre value of 58 mL to methyl orange end point. Calculate the alkalinity of the water
sample in terms of CaCO3 and comment on the type of alkalinity present.

27-11-2024 © Bhavna M. Vyas 38

 Numericals on Alkalinity of water
• A sample of water was alkaline to both phenolphthalein and methyl orange. 100 mL of this
water sample required 30 mL of N/50 H2SO4 for phenolphthalein end point and another 20
mL for complete neutralisation. Determine the type and extent of alkalinity present.

• (P = 300 ppm, M = 500 ppm; Since P > M/2, OH– alkalinity = 100 ppm CO32–
alkalinity = 400 ppm )

• A water sample is alkaline to both phenolphthalein as well as methyl orange. 200 mL of

this water sample on titration with N/50 HCl required 9.4 mL of the acid to
phenolphthalein end point. When a few drops of methyl orange are added to the same
solution and titration is further continued, the yellow color of the solution just turned red
after addition of another 21 mL of the acid solution. Elucidate on the type and extent of
alkalinity present in the water sample.

• (P = 47 ppm, M = 152 ppm, P < M/2 , HCO3– alk. = 58 ppm & CO32– alk.= 94 ppm )
27-11-2024 © Bhavna M. Vys 39
 Unit 1: Water Softening Techniques
Water Softening:

Process of converting hard water into soft water. Softening methods are of 2 types:

1) Internal Treatment

2) External Treatment Process: Based on following Principle

1) Precipitation 2) Ion-exchange

a) Zeolite Method or Permutit Process

b) Demineralization or Deionization Method

c) Lime Soda Method (Hot/Cold)

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 Zeolite Method

• Zeolites are also known as permutit and in Greek it means ‘boiling stone’.
They occur naturally as hydrated alumino silicate minerals like
Na2O.Al2O3. x SiO2. y H2O

• where x = 2–10 and y is 2–6. They are capable of exchanging reversibly

sodium ions for hardness producing ions in water.

• 1. Natural Zeolites Non porous, amorphous and durable, for example,

Natrolite Na2O.Al2O3. 4SiO2. 2H2O

• 2. Synthetic Zeolites Porous with gel-like structure. They are prepared by

heating sodium carbonate (Na 2CO3), alumina (Al2O3) and silica (SiO2).

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 Zeolite Softener

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 Zeolite Method
• Process Hard water is percolated at a specified rate through a bed of zeolite
stacked in a cylindrical unit. The hardness causing elements (Ca2+, Mg2+
etc) are retained by zeolite as CaZe and MgZe, while the outgoing water
contains sodium salts.

• The chemical reactions involved are

Na2Ze + Ca(HCO3)2 → CaZe + 2 NaHCO3
Na2Ze + Mg(HCO3)2 → MgZe + 2NaHCO3
Na2Ze + CaCl2 (or CaSO4) → CaZe + 2NaCl (or Na2SO4)

Na2Ze + MgCl2 (or MgSO4) → MgZe + 2NaCl (or Na2SO4)

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 Zeolite Method
• After some time, all the sodium ions in zeolite are replaced by Ca and Mg ions
giving CaZe/ MgZe. Such a zeolite bed is unable to soften water further and is
said to be exhausted. It has to be regenerated to enable it to soften water again. It
may be noted that the water obtained by zeolite process is used mostly for
laundry purpose; it cannot be used in boilers.

• Regeneration

• When the zeolite bed is exhausted the supply of hard water is stopped and it is
regenerated by treating with a concentrated brine (10% NaCl) solution.

• CaZe (or MgZe) + 2NaCl → Na2Ze + CaCl2 (or MgCl2)

(exhausted zeolite) (Brine) Reclaimed (Washings)

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 Zeolite Method
• The washings (containing CaCl2, MgCl2, etc.) are led to drain and the regenerated
zeolite bed is used again for softening. (NaNO3, KCl, KNO3, etc. can also be used
for regeneration instead of NaCl, but NaCl is mostly used because of its low cost
and the products of regeneration process (CaCl2 or MgCl2, ) are highly soluble and
can be easily rinsed out of the zeolite bed).

• By knowing the amount of NaCl used for regeneration of the exhausted zeolite
bed, the hardness of the water sample can be calculated by using the formula.

Hardness (H) = 50 × m× V1 ×103 /58.5×V

V = Total Volume of water softened in litres;

V1 = Total volume of NaCl used for regeneration and

M = amount of NaCL in g/L present in V1

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 Zeolite Method
• Advantages of Zeolite Process

• Hardness is removed almost completely, and the residual hardness is

about 10 ppm.

• The equipment is compact and occupies less space.

• It is a clean and rapid process. Sludge is not formed as the impurities are
not precipitated.

• It requires less skill for maintenance as well as operation.

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 Zeolite Method
Limitations and Disadvantages of Zeolite Process
• Turbid water cannot be used as turbidity clogs the pores of zeolite bed
making it inactive.
• Mn2+ and Fe2+ present must be removed first because these ions react with
zeolite bed to give manganese and iron zeolites which cannot be easily
regenerated.
• Mineral acids, if present in water, destroy the zeolite bed and hence they
must be neutralised with soda in advance.
• This method does not remove anions. The bicarbonates present in hard
water get converted into NaHCO3 which goes into soft water effluent. If this
water is used in boiler, NaHCO3 dissociates as NaOH and CO2. NaOH leads
to caustic embrittlement and CO2 makes the water acidic and corrosive.
• The treated water contains more sodium salts.
• Moreover, high cost of the plant and material also acts as limiting factor.

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 Numericals on Zeolite Method
• A zeolite softener was used to remove the hardness of 95,000 liters of hard
water completely. The softener required 475 liters of NaCl solution
containing 18 g/liter of NaCl for regeneration. Calculate the hardness of
hard water in ppm.

(Hardness (H) = 76.92 ppm)

• An exhausted zeolite softener was regenerated by 325 liters of NaCl

solution containing 60 g/liter of NaCl. How many liters of hard water of
hardness 250 mg/L can be softened by the zeolite softener.

(Total volume of hard water softened = 66666.67 liters)

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27-11-2024 © Bhavna M. Vyas 49
 Numericals on Zeolite Method
1. A zeolite softener was completely exhausted and was regenerated by passing 100 liters
of NaCl solution containing 120 g/liter of NaCl. How many liters of sample of water of
hardness 500 ppm can be softened by this softener.
[Ans 20512.8 liters]
2. A zeolite softener was completely exhausted after softening 145,000 liters of hard
water. To regenerate the zeolite softener 540 liters of NaCl solution containing 110 g/liter
of NaCl is required. Calculate the hardness of one liter water sample in ppm.
[Ans 350.13 ppm]
3. 200 liters of NaCl solution containing 85 g/liter of NaCl was required to regenerate a
completely exhausted zeolite softener. How many liters of hard water of hardness 600
ppm can be softened by the softener.
[Ans 24216.5 liters]
4. When a zeolite softener was completely exhausted it was regenerated by passing 200
liters of NaCl solution containing 120 g/liter of NaCl. How many liters of a sample of
water of hardness 550 mg/liter can be softened by the zeolite softener before regenerating
it again.
[Ans 37296.037 liters]
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 Unit 1: Purification of Water
Purification of Water: Performed by 2 processes

1. Membrane Process (RO & Electrodialysis)

2. Thermal Process (Distillation)

Membrane Process: Membranes are used in the water purification

Membranes act as barrier. Membranes blocks the different size molecules

Membranes are Organic, Inorganic and Biological (Kidney Tissues)

Types of Membranes:

Permeable Impermeable

Semi-permeable Selectively Permeable

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 Unit 1: Purification of Water
Key differences in Membranes:

• Permeable Membrane: Membrane which allows passage of all materials through it

• Impermeable Membrane: Membrane which does not allow the passage of materials through
it.

• Semi-permeable membrane: Membrane which allows some materials (certain molecules or

ions) to pass through it by diffusion or facilitated diffusion while blocking the passage of
other molecules.

• Selectively Permeable: A membrane that is selectively permeable, i.e., being permeable to

only certain molecules or ions and not to all molecules or ions.

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 Unit 1: Reverse Osmosis

Osmosis: Osmosis is the spontaneous net movement of solvent molecules through a

selectively permeable membrane into a region of higher solute concentration due to
difference in osmotic pressure, in the direction that tends to equalize the solute
concentrations on the two sides. Eg.: Roots of the plants absorbing water from the soil

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 Unit 1: Reverse Osmosis
Reverse Osmosis System:
• It is a water purification process
• It uses a partially permeable membrane to separate ions, unwanted molecules and larger
particles from contaminated or unfiltered water to obtain potable water.
• A semipermeable membrane has small pores that block contaminants but allow water
molecules to flow through, which consists of very thin films of cellulose acetate,
polymethacrylate, polyamides etc.
• Water flows from the more concentrated side (more contaminants) of the RO membrane to
the less concentrated side (fewer contaminants) to provide clean drinking water.
• The fresh water produced is called the permeate. The concentrated water left over is called
the waste or brine.
• In Reverse osmosis, pure water (solvent) is separated from it’s contaminates, rather than
removing contaminates from the water. For example, when pressure is applied to a volume
of saltwater during reverse osmosis, the salt is left behind and only clean water flows
through.
• https://www.youtube.com/watch?v=4RDA_B_dRQ0
27-11-2024 © Bhavna M. Vyas 54
https://www.youtube.com/watch?v=8bzYETuc3bY
Unit 1: Reverse Osmosis

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 Unit 1: Reverse Osmosis
Distinct Advantages:

• It removes ionic as well as nonionic, colloidal and high MW organic matter.

• It removes colloidal silica which is not removed by demineralisation

• Maintenance cost is almost entirely on the replacement of semi permeable

membrane

• Life of membrane is quite high almost 2 years

• Membranes can be replaced within few minutes

• Low capital cost low operating cost and high reliability

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 Unit 1: Electrodialysis
Electrodialysis:

• For more efficient separation usually ion selective membranes are employed

• An ion selective membrane has permeability for only one kind of ions with
specific charge

• Cation selective membrane is permeable to cation only because of presence of

charged fixed functional groups inside the membrane which rejects anions

• Similarly, anion selective membrane has positively charged fixed functional

groups which permeate anions only and rejects cations

• https://www.youtube.com/watch?v=wYkkLUckmg4
27-11-2024 © Bhavna M. Vyas 57
 Unit 1: Electrodialysis
Electrodialysis:

• Electro Dialysis (ED) is a membrane process, during which ions are transported through
semi permeable membrane, under the influence of an electric potential.

• By placing multiple membranes in a row, which alternately allow positively or negatively

charged ions to flow through, the ions can be removed from wastewater.

• It is a method in which ions (of the salts presents) are pulled out of the salty water by
passing direct current using electrodes and thin rigid plastic membranes (natural or
synthetic)
• When direct electric current is passed through saline water the cations move towards
negative pole (or cathode) while the anions start moving towards the positive pole (or
anode) through its membrane
• As a result, the concentration of brine decreases in the central compartment while it
increases in the side compartment
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 Unit 1: Electrodialysis
Ref:http://waterions.aceenvironment.com

https://www.youtube.com/watch?v=AFTWjU04yg4

27-11-2024 © Bhavna M. Vyas 59

 Unit 1: Electrodialysis
Electrodialysis Process:

• An Electro dialysis cell consist of large number of paired sets of rigid plastic
membranes.

• Saline water is passed under pressure of about 5 to 6 kg/sq.m between

membrane pairs and an electric field is applied perpendicular to the direction of
water flow.

• Fixed positive charges inside the membrane repel positively charged ions yet
permit negatively charged ions to pass through.

• Similarly, the fixed negative charged inside the other type of membrane repel
negatively charged ions yet permit cations to pass through

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 Unit 1: Electrodialysis
Electrodialysis:

• Water in one compartment of cell is deprived of its salt while the salt
concentration in adjacent compartment increases.

• Thus, we get alternate streams of pure water and concentrated brine.

• https://www.youtube.com/watch?v=eW5efz2LTOo

Advantages:

• Compact unit

• Economical cost of installation and operation

• Best suited if electricity is easily available

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 Unit 1: Electrodialysis
Limitations:

• Non-ionic matter cannot be removed

• Colloidal, silica cannot be removed

Applications of Electrodialysis:

• Used for conversion of sea water to potable water

• Desalination of boiler feed water for reuse

• Salt recovery from salt concentrated water

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 Design the Questions
Questions on RO & Electrodialysis:

1. Mention water purification processes

2. What is the principle of reverse osmosis?

3. How is sea water purified in reverse osmosis?

4. Explain desalination by reverse osmosis method

5. Explain electrodialysis for desalination of water with the help of a neat

diagram

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 Thank You

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