Water and its treatment

Prepared
By
Dr. Biswajit Saha
 Water and its treatment

Importance of water (H2O)

Without of water non existence of living organism (animals, plants,
microorganism etc).

Although water is natures most abundant compound but only 1% of

the worlds water resources are available for ready use.

D2O called heavy water and it uses in nuclear reactor

Different uses of water demand different specifications

Textile industry, Laundries, Boilers, paper industry, Bevarages,
Sugar industry, cooking, dairies and pharmaceutical Industries.
 Sources of water

1.Surface water- rivers, lakes, ponds, reservoirs, etc.

2.Underground water wells and springs
3.Rain water
4. Sea water

Impurities in water

Suspended impurities
inorganic (clay, sand) organic (oil, plant, and animal
matter)
Colloidal impurities- finely divided silica and clay
Dissolved impurities salts and gases
Microorganisms bacteria, fungi and algae
 Surface water
River water dissolved minerals
Cl-, SO42-, HCO3- of Na+, Mg2+, Ca2+ and Fe2+

suspended impurities- Organic matter, sand, rock

composition is NOT constant depends on the contact with soil.

Lake water: High in organic and less in minerals.

Rain water pure form dissolved organic and inorganic particles and
dissolved industrial gases CO2, NO2, SO2 etc

Underground water- free from organic impurities due to filtering

action of the soil but large amount of dissolved salt.

Sea water very impure; too saline for industrial uses except cooling
 Hardness of water
Hardness in water is that characteristic, which prevents the
lathering of soap.

Why?????

Hardness of water due to the presence of salts of Ca, Mg, Al, Fe and Mn
dissolved in it and prevents the lathering of soap. Produces white precipitate.

For example, :

Soap Na or K salts of long chain fatty acids C17H35COOH

2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl

2C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

 Difference between hard and soft water
Hard Water
Does not produce lather with
soap
Contains Ca and Mg salts
Soap is wasted and cleaning
quality is depressed
Boiling point elevated, more time
and fuel for cooking
Soft Water
Produces lather easily with soap
Does not contain dissolved Ca
and Mg salts
Cleaning quality of soap not
depressed.
Less fuel and time required for
cooking
 Types of Hardness
Temporary Hardness

Permanent Hardness

Temporary Hardness : Caused by dissolved bicarbonates of

Ca and Mg
Temporary hardness can be removed by boiling of water
Ca(HCO3)2 CaCO3 + H2O + CO2
Mg(HCO3)2 Mg(OH)2 + 2 CO2

Also known as alkaline or carbonate hardness

Determined by titration with HCl using methyl orange as indicator

 Permanent Hardness
Permanent Hardness dissolved Cl- and SO42- of Ca, Mg, Fe
and Al etc. i.e. CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2(SO4)3
Cannot be destroyed on boiling the water but can be removed by
Lime-soda process, Zeolite Process, Ion-exchange process

Also known as non-carbonate or non alkaline hardness.

Total hardness = alkaline hardness+ non alkaline hardness

What is carbonate and non-carbonate hardness???

 Hard Water

Advantages Disadvantages
Tastes better Produces scum with soap.
Ca in water helps produce strong Boiler feed water should be
teeth and bones. free from hardness or even
explosions can occur.
Hard water coats lead pipes with
layer of insoluble CaCO3,
preventing any poisonous lead
dissolving in drinking water.
 Degree of Hardness
Hardness is expressed as equivalent amount (equivalents) of CaCO3

Reason: Molar mass is exactly 100, and is the most insoluble

salt that can be precipitated in water treatment.

Equivalents of CaCO3 = ( mass of hardness producing substance in

mg/L)x100 / (eq.wt of substanc ex 2)

Hardness= Mass of a substance (mg/L) x 50 / E

E=eq.wt of substance

A water sample contains 204 mg/L of CaSO4, Calculate the hardness in terms of
CaCO3 equivalent. M.wt of CaSO4 =136.
(Ans. 176.47 ppm):
Units of hardness:
1. Perts per million (ppm): 1 parts of CaCO3 equivalents in hardness in
106 parts of water.
2. Milligrams per litre (mg/L): the no. of mg of CaCO3 equivalents in
hardness in one Liter of water.

Relation between them??????

1mg/L=1 ppm
3. Clarkes degree (oCl): the no. of mg of CaCO3 equivalents in
hardness in one gallon of water.
1 oCl = 1 part of CaCO3 per 70,000 parts of water.

4. Degree Frence (oFr): 1 oFr = 1 part of CaCO3 per 105 parts of

water.

Relation between them???????

1 ppm=0.1 oFr=0.07 oCl=1 mg /L ( home assessment )

A sample of water on analysis was found to contain the following impurities
Ca(HCO3)2=4 mg
(M. w.=162)
Mg(HCO3)2=6 mg
(M. w.=146) Calculate the temporary, permanent and
CaSO4= 8 mg total hardness of water in ppm???
(M. w.=136)
oFr, oCl ???
MgSO4=10 mg
(M. w.=120)
NaCl= 20 mg
(M.W=58
 Determination of hardness
STRUCTU
EDTA method: Complexometric titration, using standard EDTA
as titrant and EBT as an indicator
RE OF
EDTA: (Ethylene Diammine tetra acetic Acid)

Structure of EBT

It is also represented as H2Y2-

 Metal- EDTA complex:

EDTA being a chelating ligand react

with multivalent metal ions to form
stable complex, in alkaline medium
i.e. pH=8-10.
In hard water, bivalent cations like Ca
& Mg ions are present which form
complex with EDTA.
That`s why this method is used to
determine hardness in water.

Principle of EDTA titration

1:1 interaction of metal ions with EDTA leading to the formation
of stable complex is the basis of complexometric titrations
 Principle of Complexometric Titration:
The hard water is buffered to PH of nearly 10 using
NH4OH-NH4Cl buffer.
A few drops of EBT indicator solution are added and forms
week complex with metal ions, which is wine-red colour.

Ca2+/ Mg2+ + + EBT Ca/Mg-EBT

(blue) (red)

Slowly addition of standard EDTA solution, EDTA Combines

with free Ca2+, or Mg2+ ions to give very stable complex and
the solution becomes blue and the end point of the titration.

Ca2+ +/ Mg2+ + EDTA MG?Ca-EDTA + H+

Mg-EBT + EDTA Mg-EDTA + EBT
(red) (colorless) (colorless) (blue)
(stable complex)
The stability order of complex
CaY2- > MgY2- > MgIn- > CaIn-
1) Before EDTA was added (pH 10)
Mg2+ + + EBT Mg-EBT
(blue) (red)
2) Among titration
Ca2+ + EDTA Ca-EDTA + H+
Mg2+ + EDTA Mg-EDTA + H+
3) End point
Mg-EBT + EDTA Mg-EDTA + EBT
(red) (colorless) (colorless) (blue)
(stable complex)
Procedure for titration using EDTA
1. Standarization of EDTA solution
2. Determination of total hardness of water
3. Determination of permanent hardness of water
Total hardness = permanent + temporary

Calculation
Standard solution of hard water = 1 mg/mL of CaCO3
Volume of EDTA consumed for 50 mL of SHW=V1 mL
V1 mL of EDTA is used for= 50 mg of CaCO3
1 mL of EDTA is used for =50/ V1 mg of CaCO3
Total hardness
Volume of EDTA used for 50 mL of sample HW=V2 mL
V2 mL of EDTA consumes = 50/ V1 x V2 mg of CaCO3
Therefore 1000 mL of sample water= V2x 1000/V1mg of CaCO3
Numerical problem

1. A standard hard water contains 1.5 gm. of CaCO3 per Liter and
20 mL of this required 25 ml. of EDTA soln., while 100 mL. of
sample water required 18 mL of EDTA soln. The sample after
boiling required 12 mL EDTA soln. Calculate the temporary
hardness of the given sample of water, in terms of ppm.

2. 200 mL of hard water sample require 30 mL of 0.02 N of EDTA

with buffer and EBT indicator. Another 200 ml. of the sample is
boiled for about half an hour and filtering the ppt., the volume
of filtrate is made 200 mL by the addition of distilled water. 20
mL of this boiled water sample required 5 mL of 0.01 N EDTA
following the same procedure. Calculate the temporary and
permanent hardness of the sample.
Advantages of EDTA methods

The Advantages are

High accuracy
Convenience and easy to handle
More rapid procedure
 Alkalinity of water
Alkalinity is a measure of the ability of water to neutralize the acids
The Alkalinity of water is due to mainly the presence of, CO32-, OH-,
HCO3-
Alkalinity of water means the total content of those substances in it which
causes an increased hydroxide ion concentration [OH-] upon dissociation
or due to hydrolysis
i) Caustic alkalinity (due to OH- and CO32- ions)
ii. Bicarbonate alkalinity (due to HCO3- ions)

Combination
1) OH- + CO32- ALKALINITY
2) HCO3- + CO32- ALKALINITY
Questions
1. Causes of alkalinity in water ????
2. Why combination of OH- and HCO3- is not possible ???
Determination of Alkalinity

The alkalinity can be estimated by titration against standard acid,

using phenolpthalein (P) and methyl orange (M) as indicators

The determination is based on the following reaction:

i. [OH-] + [H+] H2O -P -M

ii. [CO32-] + [H+] [HCO3- ] -P -M
iii. [HCO3- ] + [H+] H2O + CO2 -M

P = OH- + CO32-
M = OH- + CO32- + HCO3-

Phenolpthalein
Methyl orange
 PROCEDURE:
Known volume of water sample + 1-2 drops of phenolphthalein.

Appearance of pink color

Titrate with std. Acid End point pink to colorless

Titrate with same sample with same

Std. acid by using methyl orange

INDICATOR. End point yellow orange to dark pink

The vol of acid consumed is noted.

 CALCULATIONS
FOR Phenolphthalein ALKALINITY:
N1V1 = N2V2
N1 = N2V2/ V1

Now the alkalinity in terms of CaCO3 per litter

PALK = N1 X 50 X 1000 ppm

FOR METHYLORANGE ALKALINITY:

N1V1 = N2V2

(AWS) (STD. ACID)

N1 = N2V2/ V1

Now the alkalinity in terms of CaCO3 per litter

MALK = N1 X 50 X 1000 ppm

Procedure of determination of alkalinity due to OH-,CO3-, HCO3-,
OH- and CO32- Combine, CO32- and HCO3- combine

Hydroxide Carbonate Bicarbonate

P = O, M=O O O O

P=O O O M

P=M P O O

P = 1/2M O 2P O

P >1/2M 2P - M 2(M - P) O

P <1/2 M O 2P M - 2P
RESULT: OH- (hydroxyl) ALKALINITY=--------ppm
2) CO32- (carbonate) ALKALINITY=-----------ppm
3) HCO3- (bicarbonate) ALKALINITY=-----------ppm

Drawbacks of using highly alkaline water

1. It may lead to caustic embrittlement

2. It may lead to deposition of precipitation and sludge in boiler tubes and
pipes.
Numerical problem
200 ml. of water sample required 25 ml. of N/50 H2SO4 during titration by
using phenolphthalein indicator and 26 ml. of acid by using methyl orange
indicator. Calculate the alkalinity of each type in terms of CaCO3
equivalent. ( Due to OH- 120 ppm and due to carbonate 10 ppm)

100 ml. of water sample required 4 ml. of N/50 H2SO4 for

neutralization phenolphthalein end point. Another 16 ml. of
same acid was needed for further titration to methyl orange
end point. Determine the type and amount of alkalinity.
(Ans. CO32-= 80 ppm, HCO31-= 120 ppm)