UNIT- I: Natural Sources and their Chemistry

Water Technology
1.1 Introduction
Water exists in three states: solid, liquid and gaseous. The important sources of water
are (i) rain water, (ii) ground water and (iii) sea water. Rain water carries all the
washed out minerals, salts and organic matter from the earth’s surface and it reaches to
water bodies such as ponds, lakes and rivers. Also, these impurities seep into
underground and are stored as ground water. Sea water is highly alkaline due to the
presence of dissolved salts.
The natural water contains numerous organisms and dissolved gases (ex:
oxygen), which is essential for aquatic organisms. The pure water is one which
is free from organisms. Water is required mainly for drinking and cooking, also for
industry, agriculture and many other activities. Pollution of water implies that it
contains a lot of inorganic and organic substances introduced by human activities,
which change its quality, not suitable for any purposes and also harmful for living
organisms. Any alteration in physical, chemical or biological properties of water, as
well as the addition of any foreign substance makes it unfit for health and which
decreases the utility of water, is known as water pollution. The major impurities
present in the water bodies are described below
1.1.1 Impurities:
1) Water takes up the impurities when it comes in contact with soil or ground
Water becomes impure when it comes in contact with sewage or industrial
waste.
2) Organic impurities in water are generally introduced by decomposition of
plants and animals.
1.1.2 Nature of impurities in water:
1) Dissolved gases: The water mainly contains carbon dioxide and oxygen. If
water contains ammonia, hydrogen sulphides and oxides of sulphur gives bad
smell and taste to water.
2) Suspended impurities: These are insoluble impurities, which can be removed
by filtration or settling. There are two types Clay, silica, oxides of iron are
 inorganic impurities. Wood and disintegrated part of dead animals are organic
impurities.
3) Microscopic matter: These consists mainly bacteria and other microorganisms
(algae and fungi). Generally responsible for water borne diseases
4) Dissolved mineral salts: These are the soluble impurities in water includes
carbonates, bicarbonates chlorides and sulphides of calcium and magnesium.
Oxides if iron lead etc.
5) Organic matter: It includes vegetable and animal matters i.e., decay plants and
animals.
6) colloidal impurities: They consisting of proteins, amino acids, ferric
hydroxides, clay and lumic acid etc.,

1.2 Potable water

Water of sufficient quality to serve as drinking water or water that is safe for
human consumption is called potable water.
The following are characteristics of potable water
 It should be sparking clear, soft, pleasant in taste, perfectly cool and odourless
 Its turbidity level should not exceed 10 ppm
 Its alkalinity should not be high (pH = 8.0)
 The total dissolved solids should not exceed 500 ppm
 It should be free from heavy metals such as lead, arsenic, cadmium, chromium
and manganese salts
 It should be free from dissolved gases such as hydrogen sulphide
 It should be free from disease producing micro-organisms.
1.3 Water analysis
1.3.1 Dissolved oxygen
Oxygen is poorly soluble in water. The solubility of water depends on the
concentration of the salts and temperature. Dissolved oxygen is consumed by aquatic
animals for their respiration. Aerobic bacteria consume the DO for the oxidation of
biodegradable matter.
 Dissolved oxygen in environment
1.3.1.1 Determination of dissolved oxygen (DO) by Winkler’s method
DO in water is determined by winkers method. This method is based on the
indirect iodometric titration. Manganese sulphate reacts with alkaline azide solution to
give manganese hydroxide. Manganese hydroxide reacts with DO to give basic
manganese hydroxide and precipitated. Precipitation is dissolved by addition of con
H2SO4 and nascent oxygen is liberated. Nascent oxygen oxides potassium iodide to
iodine. The liberated iodine is titrated against standard Na2S2O4
MnSO4 + 2KOH Mn(OH)2 + K2SO4

Mn(OH)2 + 1/2O2 [MnO(OH)2]

[MnO(OH)2] + H2SO4 MnSO4 + 2H2O + [O]

[O] + H2SO4 + 2KI I2 + H2O + K2SO4

I2 + Na2S2O4 2NaI + Na2S4O6

Procedure:
150 cm3 of waste water is taken in a BOD bottle; add 2ml of MnSO4 and 2 ml of alkaline
KI to the reagent bottle containing a known volume of water. Obtained Basic manganese
hydroxide Precipitation is dissolved using con H2SO4. Take a 50 cm3 of the above reaction
mixture into 250 cm3 conical flask. Add 4-5 drop of starch indicator and titrate the liberated
iodine against standard sodium thiosulphate, till the colour changes from blue to colour less.
Observation and calculation
Normality of Na2S2O4 solution= N1
Volume of Na2S2O3(Sodium thiosulphate) solution =V1 cm3
Volume of water take for titration=V2 cm3
N1 x V 1
Normality of the dissolved N2= V2

V 1 x N1 x 8
Water of dissolved oxygen per liter of water = V2 g
V 1 x N1 x 8
X 1000 ppm
= V2

Note:
 The azide destroys the oxides of nitrogen due to this reason alkali is mixed with azide
 The oxygen carrier in winklers method is basic manganic oxide MnO(OH)2
 Starch is an adsorption indicator which is made of amyose and amylopectin.

1.4 Biological Oxygen Demand( BOD)

Definition: “ The amount of oxygen required in milligrams for the biological oxidation by the
microorganism to bring about oxidation of biological compounds present in 1 dm3 waste water
over a period of 5 days at 20oC.”

The biodegradable impurities present in the waste water are oxidizes by aerobic bacteria,
using dissolved oxygen. Biodegradable matter such as carbohydrates, proteins, oils and facts
utilized by aerobic bacteria’s as source of energy.

Characteristics of BOD
 It is expressed in parts per million (ppm) or mg/dm3.
 Larger the concentration of decomposable organic matter, greater is the BOD and
 consequently more is the nuisance value.
 Strictly aerobic conditions are required.
 Determination is slow and time consuming.
Some of the possible reaction during BOD estimation
CH3COO- + 2O2 CO2 + HCO3- + H2O

S2- + 2O2 SO42-

NH3 + 2O2 NO-3 + H+ + H2O

1.4.1 Winkler’s method BOD measurement:

In this method BOD is determined by measuring the dissolved oxygen contents before
and after 5 days incubation by indirect iodometric method.
Principle:
A known volume of sewage sample is diluted with known volume of dilution water
(containing micro organism). A mixed group of organism should be present. This solution is
divided in to two equal parts in BOD bottle. The DO of sample (D1) at day1 and the DO of the
sample after incubation after 5 days (D2) were determined and then BOD is calculated.
Procedure:
Preparation of dilution water: 1 dm3 of distilled water thoroughly aerated by bubbling
compressed air about a day. 1cm 3 of phosphate buffer, 1cm3 of MgSO4, 1 cm3 of CaCl2, 1cm3 of
FeCl3 are added and mixed well and 2 cm3 of sludge is added.

Note: 25 ml of waste water is diluted to 1000 ml, and divided in two BOD bottles (500 ml each)
Blank titration:
DO content of the one bottle determined immediately (Add 2ml of MnSO 4 and 2 ml of
alkaline KI to the reagent bottle containing a known volume of water. Obtained Basic manganese
hydroxide Precipitation is dissolved by the addition of 2 ml con H 2SO4 leading to give dark
yellow color. Take a 50 cm3 of the above reaction mixture into 250 cm 3 conical flask. Add 4-5
drop of starch indicator and titrate the liberated iodine against standard sodium thiosulphate, till
the colour changes from blue to colour less)
Sample titration:
 The second bottle is incubated for 5 days at 20oC, after 5 days unconsumed DO is
determined as above procedure and it is found to be D2.

Observation and calculation

D1 is the DO of the sample in mg/ml at the start of the experiment
D2 is the DO of the sample in mg/ml after 5 days.
A is ml of the sample before dilution
B is ml of the sample after dilution
D1 −D2
= xB
BOD A mg of O2/ dm3
Importance of BOD:
BOD is most important in sewage treatment, as it indicates the amount of decomposable
organic matter in the sewage or extent of pollution or amount of dissolved oxygen. On the basics,
environments design the treatment.
Larger the concentration of decomposable organic matter, greater is the BOD and
consequently more is the nuisance value. Strictly aerobic conditions are required. Determination
of BOD is little slow and time consuming.

Problems:
20 ml of sewage sample was diluted to 600ml and equal volumes were filled in two BOD
bottle. Do in one bottle was determined immediately and 200ml of the solution required 4.2 ml
of N/40 Na2S2O3 solution. The second sample was incubated for 5 days and in DO determined;
200ml solution required 2.2 ml of N/40 Na2S2O3 solution. Calculate BOD of the solution.
Volume of sample before dilution, A =20 ml
Volume of the sample after dilution, B = 600ml
Volume of Na2S2O3 solution required for blank = 4.2ml(V1)
Volume of Na2S2O3 solution required for sample after 5 days= 2.2ml(V3)
Normality of Na2S2O3 solution= N/40=1/40=0.025 N
Volume of water sample taken =200ml.(V2)
V 1 x N1 x 8
g /dm−3
Water of dissolved oxygen per liter of water = V2
 4.2 X 0.025
X8
= 200
D1 =4.2X10-3g/dm-3 = 4.2 mg/dm-3
V 3 x N1 x 8
g /dm−3
Water of dissolved oxygen per liter of water= V2 =

2.2 X 0.025
X8
200
D2 =2.2X10-3 g/dm-3 =2.2 mg/dm-3
D1 −D2 4 . 2−2 .2
= xB mg/dm−3 X 600 =60 mg/dm− 3
Therefore= A = 20
1.5 Chemical oxygen demand:
Definition: “It is the amount of oxygen in milligrams required to complete oxidation of organic
and inorganic compounds present in one ldm3 of waste water by using strong oxidizing agent
such as K2Cr2O7.”

Principle
A known volume of waste water sample ifs refluxed with excess of K 2Cr2O7 solution in
sulphuric acid medium in the presence of Ag2SO4 and HgSO4. K2Cr2O7 acts as oxidizing agent in
acidic media which oxidizes all the oxadizable impurities present in waste water. The amount of
unreacted K2Cr2O7 is determined by titration with known strength FAS (Ferrous ammonium
sulfate). The amount of K2Cr2O7 consumed for the oxidation corresponds to COD of waste water.
In this titration Ferroin is used as indicator. This indicator is redox indicator which
contains Fe+2 ions. This indicator is red in colour. Oxidizing agents oxidizes the iron in the
indicator to +3 oxidation state which is in pale blue colour.
Procedure
 Pipette out 25 ml of waste water in to 250 ml conical flask and 1 ml and 1g of mercuric
sulphate and 1 g silver sulphate are added fallowed by the addition of 25ml of potassium
dichromate solution of known strength.
 The above mixture is refluxed for two hours and cools the mixture. Titrated the mixture
against standard FAS solution, till the colour changes from green to brown using Ferrion
as a indicator.
  Once again blank titration is carried out same procedure without waste water
Reaction involved
K2Cr 2O7 + 4H2SO 4 K2SO 4 + Cr 2(SO 4)3 + 4H2O + 3(O)

[2FeSO 4 +H2SO4 + (O) Fe2(SO 4)3 + H2O] x 3

K2Cr 2O 7 + 6FeSO 4 + 7H2SO 4 K2SO 4 +Cr 2(SO 4)3 + 3Fe(SO 4)3 + 7H2O

Let the volume of FAS consumed for waste water is = A cm3

Let the volume of FAS consumed in blank titration is = B cm3

Observation and calculation

Volume of water sample taken= 25 cm3
Volume of standard FAS used in sample titration= A cm3
Volume of standard FAS in the blank titration= B cm3
Normality of FAS solution= N
Amount of K2Cr2O7 consumed in satisfying the COD in terms of FAS solution= (B-
A)cm3
N1xV=N x (B-A)
N x ( B− A )
Normality of COD of the sample N1= V
N x ( B− A )
x 8 g .dm−3
COD of the sample = V
N x ( B− A )
x 8 000 mg.dm− 3
= V
Importance:
1) The COD test is widely used for measuring the pollution level of domestic and industrial
wastes.
2) The major advantages of COD test are that the determination is completed in three hours
as compared to the 5 days required for BOD determination.
Note
 Ag2SO4 acts as catalyst in the oxidation of long chain fatty acids and pyridine like impurities
 The role of HgSO4 is to avoid the Chloride ion hindrance
Problem 1:
A 20ml of sewage sample for COD is reacted with 25 ml of K2Cr2O7 solution and the unreacted
K2Cr2O7 requires 9.0ml of N/4 FAS solution. Under similar conditions, in blank titration 15.0 ml
of FAS is used up. Calculate the COD of the sample.
Volume of sample taken= 20 ml
Volume of N/4 FAS required to react with unconsumed K2Cr2O7=9.0ml
Volume of FAS consumed in blank=15.0ml
Amount of K2Cr2O7 consumed to satisfy COD
in terms of FAS solution=15.0-9.0=6 ml
N1 V1 = N2 V2
N1X20=0.25X6.0
0 . 25 x 6
N 1=
Therefore, normality of COD Sample 20
0. 25 X 6
X 8=0 . 6 g/dm− 3 =600 mg/dm−3
COD of the sample= 20

Problem 2:
In a COD test, 28.1 and 14.0 cm 3 of 0.05 N FAS solution were required for blank and
sample titration respectively. The volume of test sample used is 25 cm 3. Calculate the COD
of the sample solution.
Volume of 0.1N FAS required to react with unconsumed K2Cr2O7=14.0 ml
Volume of FAS consumed in blank=28.1ml
Amount of K2Cr2O7 consumed to satisfy COD
in terms of FAS solution=28.1-14.0=14.1 ml
N1 V1 = N2 V2
N1X25=0.5X14.1
0.5 X 14.1
Therefore, normality of COD Sample N1= 25
0. 5 X 14 . 1
X 8=0 . 225 .6 g/dm− 3 =225. 6 mg/dm−3
COD of the sample= 25
Problem 3:
25 ml of an effluent sample requires for oxidation 8.3 ml of 0.001 N K 2Cr2O7 . Calculate
the COD of the effluent sample.
Solution: (i) Evaluate the oxygen content
1000 cm3 of 1N solution of K2Cr2O7 = 48 gm of Oxygen
48 X 0.001 X 8.3

8.3 cm3 of 0.001 N solution of K2Cr2O7 = -= 0.000398 gm or 0.398 mg of O2

1000
(ii) Calculate COD value:
25ml of effluent = 0.398 mg of Oxygen
0.398 X 1000
1000 cm3 of effluent = -------------------- = 15.93 mg of Oxygen / dm3
25
1.6 Hard water
Water which does not produce sufficient lather with soap solution readily but
forms a white or grey precipitate. The soap (potassium or sodium salts of fatty acids
like stearate) gets precipitated in the form of insoluble salts of calcium and magnesium
which is termed as scum.
CaCl2 + 2C17H35COONa (C17H35COONa)2Ca + NaCl

There are two types of hard water

1) Temporary hardness:
It is due to the presence of bicarbonates of calcium and magnesium. It can be removed
by boiling. On boiling, bicarbonates of calcium and magnesium get precipitated as
insoluble carbonates and hydroxides.
It is also called carbonate or alkaline hardness.

Ca(HCO3)2 CaCO3 + H2O + CO2

Mg(HCO3)2 Mg(OH)2 + 2CO2

 2) Permanent hardness.
It is due to the presence of chlorides and sulphate of calcium and magnesium. It can be
removed by using chemicals. It is also called non- carbonate or non- alkaline hardness.
CaCl2 + Na2CO3 CaCO3 + 2NaCl

CaSO4 + Na2CO3 CaCO3 + Na2SO4

Unit of Hardness
Ppm:
Number of parts of hardness causing substance in 106 parts of water. Generally, it
is mg/dm-3.
Degree French
Number of parts of hardness causing substance in 105 parts of water.
Degree Clarke
Number of parts of hardness causing substance in 7 X 104 parts of water.
1.6.1 Calcium carbonate equivalence
Any sample of water contains various types of impurity in various amounts. The degree
of harness due to all these substances are unified in the forms of CaCO3
Reasons for representing in calcium carbonate equivalence
 CaCO3 is water insoluble
 CaCO3 doesn’t impart hardness
 Its molecular weight is 100 which make calculation easy
Due to this reason harness is expressed in calcium carbonate equivalence

Mass of hardness causing substance XChemical equivalent of CaCO 3

Equivalents of CaCO 3=
Chemical equivalent of hardness causing substance
Chemical equivalence of CaCO3, CaCl2, MgCl2, MgSO4 and MgCO3 are 50, 55.5, 47.5,
60 and 42.
Equivalents are as follows
100g of CaCO3 ≡ 111g of CaCl2
≡ 136g of CaSO4
≡ 95g of MgCl2
≡ 120g of MgSO4
 ≡ 162g of Ca(HCO3)2
≡ 146g of Mg(HCO3)2
1.6.1.1 Determination of total hardness of water:
Determination of total harness of water is done using EDTA titration method. In this
method a known amount of hard water is taken in the conical flask and then Eriochrome black T
indicator is added then metal ions present in the hard water forms a wine red colored M-EBT
complex. This solution is titrated against standard EDTA solution then EDTA forms a strong
colorless complex with metal ions leaving behind the EBT. Color of Free EBT is blue and hence
color change in this titration is wine red to blue.
Procedure
Standardization of EDTA solution:
20ml of standard hard water is pipetted in to 250cm 3 conical flask. Add 5 ml of NH3-
NH4Cl buffer and 3-4 drops of Eriochrome black-T indicator solution. Titrated against standard
EDTA solution, till wine red changes to clear blue.
Determination of total hardness:
A known volume of water sample is pipetted into 250cm 3 conical flask. Add 5 ml of
NH3-NH4Cl buffer and 3-4 drops of Eriochrome black-T indicator solution. Titrated against
standard EDTA solution, till wine red changes to clear blue.

Determination of permanent hardness:

Take 100cm3 of hard water sample in to a clean conical flask and boil gently for an hour
(bicarbonates settled as carbonates). Cool, filter it. The filtrate can now used for the experiment.
Procedure:
A known volume of water sample is pipetted into 250cm 3 conical flask. Add 5 ml of
NH3-NH4Cl buffer and 3-4 drops of Eriochrome black-T indicator solution. Titrated against
standard EDTA solution, till wine red changes to clear blue.

Determination of temporary hardness.

It can be obtained by subtracting the permanent hardness from the total hardness of the
sample.
Temporary hardness = Total hardness - Permanent hardness

Observation and calculation

Determination of Total hardness:

1000 ml of 1M EDTA =100 g CaCO3

100
1 ml of 1 M EDTA = 1000 g of CaCO3
V 1 X M 1 X 100
V1 ml of M1 M EDTA = 1000
V 1 XM 1 X 100
V2 ml of water sample consists(hardness/ CaCO3)= 1000 X V 2

V 1 XM 1 X 100
106g of water contains = 1000 XV 2 X 106 ppm of CaCO3

Determination of Permanent Hardness:

Heat the V2 ml of water and filter it (permanent water) and repeat the titration. V 3 ml of
the EDTA consumed
V 3 XM 1 X 100
V2 ml (permanent water) = 1000 XV 2
V 3 X M 1 X 100
X 10 6
10 g of water contains = 1000 X V 2
6

Determination of Temporary hardness:

Temporary hardness= Total hardness-Permanent hardness:

Note:
 Colour of metal-EBT complex is wine red
 Colour of metal-EDTA complex colourless
 Colour of free EBT indicator is blue
 NH3-NH4Cl buffer is added to maintain the PH 10 because in this pH only the indicator
shows proper colour change.
OH HO
HOOC COOH N
N N N SO3Na
HOOC COOH

EDTA
EBT
NO 2

Problem:
100 ml of a sample of water requires 18 ml of 0.01M EDTA for titration using EBT
indicator. In another experiment, 100 ml of the same sample of water was gently boiled and the
precipitate was removed by filtration. The filtrate requires 9.0ml of 0.01 M EDTA using EBDT
Indicator. Calculate the total hardness of the water sample, permanent hard water.
Volume of water taken=100 ml(V2)
Normality of EDTA = 0.01N
Volume of EDTA consumed =V1
Volume Of EDTA Consumed=V3
V 1 X M 1 X 100 X 106 18 X 0. 01 X 100 X 106
=180 ppm
Total hard water = 1000 X V 2 = 1000 X 100
V 3 X M 1 X 100 6
X 10 6
9.0 X 0.01 X 100 X 10
=90 ppm
Permanent hard water= 1000 X V 2 = 1000 X 100
Temporary hardness= Total hardness-Permanent hardness
Temporary hardness = 180-90=90ppm of CaCO3

1.6.2. Alkalinity
Alkalinity of water is due to the presence of the substance which increases the
concentration of OH- , either by hydrolysis or by dissociation. Alkalinity measures the acid-
neutralizing capacity of water sample. It is an aggregate property of water sample and can be
interpreted in terms of specific substance only when a complete chemical composition of the
sample is also performed.
 The alkalinity of the water sample is due to carbonate (CO 32-),, bicarbonate (HCO3-) and
hydroxide (OH-), content. Alkalinity may also be includes contribution from borates, phosphates,
silicates (SiO32- ), or other bases. This alkalinity is very important parameter and it is very
essential for water to use in irrigation, industrial and domestic use.

OH- + H+ H2O
CO32- + H+ HCO3-

HCO3- + H+ H2O + CO2

Alkalinity of water is determined by titrating a known volume of water against standard

sulphuric acid using phenolphthalein and methyl orange as indicator one after the other.
Hence the total alkalinity (AT) of water is obtained as
AT = Ac + Ab + Ah

Procedure:
A known volume of water sample is pipette into 250cm 3 conical flasks and titrated
against standard hydrochloric acid using phenolphthalein as indicator. The disappearance of pink
color indicates the end point and titration continues using methyl orange as indicator until the
reappearance of pink color is the end point (The same solution is titrated against the standard
sulphuric acid using methyl orange as indicator).

Observation and calculation

Volume of water sample taken = V cm3
Concentration of standard hydrochloric acid solution =N1
Volume of hydrochloric acid consumed (Phenolphthalein)= V1 cm3
Volume of hydrochloric acid consumed (Methyl orange)= V2 cm3
N 1 xV 1
N2 =
Concentration of phenolphthalein, V
N 1 xV 1 x50
Phenolphthalein alkalinity in terms of CaCO3 = V g/dm3
 6
N xV x 50 x 10
p= 1 1 ppm
Vx 1000
6
N 1 x (V 1 +V 2 ) x 50 x 10
ppm
Methyl Orange alkalinity in terms of CaCO3 = Vx 1000

1.6.3. Fluoride (SPADNS method)

Fluoride is very important parameter in water if it is high in concentration causes dental
fluorosis and lower concentration (<0.8 mg/L) causes dental caries. A fluoride concentration of
approximately 1 mg/L in drinking water is acceptable.
Fluorides present in bore well water much more than river water and this is because water
comes in contact with mineral as CaF2(Fluorospar) and Na3AlF6(Cryolite). But fluorides largely
occur in industrial wastes such as coke, glass, ceramics and electronic industries.
Thus determination of fluoride is essential. The determination of amount of fluoride in
the water can estimated using SPADNS method. (sulpha phenyl azo dihydoxy naphthalene
disodium sulfonate).

Principle: In this method SPADNS molecule made to react with the zirconium chloride in
acidic media which forms a red coloured complex. When this red coloured comlex made to react
with fluoride present in the water sample then forms colourless ZrF 6 leaving behind SPADNS
which is of yellow in colour. As amount of fluoride increases red colour decreases and yellow
colour (absorption maxima is 570 nm) of SPADNS increases. By colorimetric estimation
absorption of yellow colour is measured and hence amount of fluoride can be calculated using
calibration plot method.

This follows Beers lambertz law which states that “when monochromatic light falls on
homogeneous absorbing medium rate of decrease on intensity of light with respect to the
thickness of the medium is directly proportional to intensity of incident radiation”.

Reaction

SPADNS + ZrOCl2 --------------------- [ZrO-SPADNS complex] [red colour]

[ZrO-SPADNS complex] + NaF ----------- ZrF6 + SPADNS [Yello colour]

Solution preparation:

Standard sodium fluoride solution:

0.221 g of sodium fluoride (NaF) in one liter of distilled water. The stock solution is further
diluted to 10ppm.

SPADNS solution:
Dissolve 958 mg of SPADNS in 500 ml of distilled water
Zirconyl chloride solution:
Dissolve 133 mg of Zirconyl chloride octahydrate (ZrOCl2.8H2O) in 25 ml of distilled water.
Add 350 ml of conc HCl and dilute to 500 ml with distilled water.
Procedure
Stock solution is prepared according to the table given below.

Sl Standrd NAF SPADNS + NaAsO2 Colorimetric Red color Yellow

No solution ZrOCl2 solution reading color
( 5%)

Decreases
1 0 5+5 mL

2 1ml 5+5 mL

3 2ml 5+5 mL
1 drop each

4 3ml 5+5 mL

5 4ml 5+5 mL

6 5ml 5+5 mL

7 Test solution 5+5 mL

Increases

Measurement:
Sample solution is prepared in series of 25 mL standard flasks and each flask filled with 5+5 mL
of SPADNS + ZrOCl2 red coloured solution. Then each bottle is added with different concentration of
fluoride as mentioned in table. One drop of NaAsO 2 is added to avoid the hindrance of the chloride ion in
NaF solution. Then standard flasks are made up to the mark and then used for colorimetric estimation. As
concentration of the fluoride ion increases red colour decreases and yellow colour increases. The
increasing yellow color is measured calorimetrically. A graph is plotted concentration of fluoride ion
verses colorimetric reading and then unknown concentration of fluoride ion is determined using
calibration plot method.

Colorimetric reading
Volume of
unknown solution
Concentration of fluoride ions

1.7 Membrane Technology

Membrane also known as selective barrier between two phases that
have thin barrier that permits selective mass transport and the phase that acts as a barrier
to prevent mass movement, but allows restricted and / or regulated passage of one or
more species.

The basic membrane separation process

The membrane technology deals with the use of polymer membranes
for the water purification. The basic principle involved in the membrane technology is
osmosis.

Advantages of membrane technology.

 Energy savings. The energy consumption is very low as there is no phase change.
  Low temperature operation. Almost all processes proceed at room temperature,
thus they can deal with compounds that are not resistant at high temperatures.
 Recovery. Both the concentrate and the permeate could be recovered to use.
 Water reuse. When applied to recover water, they avoid the transport of large
water volumes and permit the reduction of the Chemical Oxygen Demand (COD)
loading in sewage plants.
 Compact operation. This permits to save space. Easy scale-up. Because usually
they are designed in modules, which can be easily connected.
 Automatic operation. The most of the membrane plants are managed by expert
systems.
 Tailored systems. In many cases, the membranes and systems can be specifically
designed according the problem.
The membrane operations more widely used are those based in
applying a pressure difference between both sides of the membrane. The membrane
separation process broadly classified in to micro filtration, ultra filtration, nano filtration,
and reverse osmosis based on the pore size of the membrane as well as external pressure
applied.
 Types of membrane separation process

1.7.1 Reverse osmosis:

Many company of drinking water in our country used the concept of
Reverse Osmosis (RO). Reverse Osmosis (RO) is a process for desalting water that
uses membranes that are permeable to water but essentially impermeable to salt.
Pressurized water containing dissolved salts contacts the feed side of the membrane;
water depleted of salt is withdrawn as a low-pressure permeates. The ability of
membranes to separate small solutes from water has been known for a very long time.
In 1931the process was patented as a method of desalting water and the term reverse
osmosis was coined. This Reverse Osmosis has the smallest pores 0.0001- 0.001
microns and has the highest-pressure requirement 10-100 bar.
The movement of solution molecule through semi permeable
membrane from higher concentration to lower concentration or the process which
reverse to the natural spontaneous osmosis is called reverse osmosis.
RO system tube contains a semi permeable membrane made up of
polymethylacrylate and polyamide. Brackish water and fresh water is separated by
semi permeable membrane. When the brackish water (1000ppm) supplied with high
pressure, water flow from brackish water to fresh water, Fresh water is collect from
 fresh water outlet and brackish water (2000ppm) is discharged in to the environment.
The flow of pure water propositional to the applied pressure. The mechanism of
reverse osmosis is represented below.

Representation of process of Reverse Osmosis

Advantages of reverse osmosis:

1) Removes nearly all contaminant ions and most dissolved non-ions,

2) Relatively insensitive to flow and total dissolved solids (TDS level and suitable for small
systems with a high degree of seasonal fluctuation in water demand,
 3) RO operates immediately, without any minimum break-in period,

4) Low effluent concentration possible,

5) Bacteria and particles are also removed, and

6) Operational simplicity and automation allow for less operator attention and make RO
suitable for small system applications.

7) Some of the limitations of RO are:

Disadvantages:
1) High capital and operating costs,
2) Managing the wastewater (brine solution) is a potential problem,
3) High level of pre-treatment is required in some cases,
4) Membranes are prone to fouling and
5) Discharged Brackish is harder than the previous one
6) Produces the most wastewater at between 25-50 percent of the feed.
7) Colloidal silica is not removed by this process.

Pictorial representation of cross sectional view of water purification by RO method

1.7.2 Poly-sulfone and polyurethane based membranes in membrane

technology
 There are many polymers are used in membrane technology for the
purification of water. Amongst all polysulfone and polyurethane membranes are
commercially important because of their unique structure which is essential for the salt
rejection. Also, their structure can be modified according to the requirement.
In fabrication of the membranes for water purification following
important parameters are considered
 Membrane materials. Organic polymers, inorganic materials (oxides, ceramics,
metals), mixed matrix or composite materials.3
 Membrane cross-section. Isotropic (symmetric), integrally anisotropic
(asymmetric), bi- or multilayer, thin-layer or mixed matrix composite.
 Preparation method. Phase separation (phase inversion) of polymers, sol–gel
process, interface reaction, stretching, extrusion, track-etching, micro-fabrication.
 Membrane shape. Flat-sheet, hollow fiber, hollow capsule.

There are different methods of preparation of membranes are available in the literature
they are as follows
 Precipitation in a non-solvent (typically water) induced, NIPS;
 Solvent evaporation induced, EIPS;
 Vapor phase induced, VIPS;
 Precipitation by cooling-thermally induced, TIPS.
Generally, the membrane prepared using NIPS methods are used in high pressure RO
purification techniques.
1.7.2.1 NIPS method
The preparation of polymer membrane in NIPS method involves following steps
 Selection of suitable polymer (Eg: polysulfone, poly urethane)
 Dissolution of polymer in polar solvents such as DMF (Dimethyl formamide) of
NMP (N-methyl pyrolidinone)
 Pouring of this polymer solution on clean glass plate
 Spreading of polymer solution uniformly on the glass plate using different
technique
  After partial drying the films are kept in the oven at high temp to remove the
solvent
 Dipping the film along with glass plate in bowl containing pure water
 Removal of pealed film and drying of film
When we dip this polymer film in water then solvent molecule present
in the films try to come to the upper surface of membrane by making a pore or void in the
polymer film which is essential in the RO method of water purification
The following figure represents the membrane prepared in NIPS method

Pores and voids in polymer memranes

Cross sectional view of polysulfone nano fiber in polymer membranes

1.7.2.2.Polysulfone
Poly sulfone is a polymer which contains both hydrophilic and
hydrophobic functionalities. Where sulfone group behaves as hydrophilic and two methyl
side group along with aromatic rings acts as hydro phobic functionalities. If polysulfone
is used as membrane for water purification then these methyl groups acts as brushes and
avoids the deposition of salts and hence fouling of membrane. Structure of polysulfone
as follows.

1.7.2.3. Poly urethanes

Polyurethanes are the amide containing polymers. In this polymer back
bone aromatic and methyl functionalities acts as hydrophobic and amidic NH acts as
hydrophilic functionality. Also this polymer is linear and no major side group and hence
it is more flexible and fabrication of films are easy than polysulfone.