Water Technology and Green

Chemistry
Engineering Chemistry
Prof. Rajesh B. Jadhav
MIT-ADT UNIVERSITY'S
SCHOOL OF ENGINEERING
Engineering Sciences Department
 Unit 1: Water technology & Green
Chemistry
•Water technology:
•Impurities in water. Hardness of water and
its determination by EDTA method,
Alkalinity of water and its determination.
Numerical.
•Ill effects of hard water in boilers. Boiler
feed water treatment -1) Internal
treatment –calgon, colloidal and
phosphate conditioning
Unit 1: Water technology & Green
Chemistry

•2) External treatment- Zeolite process &

its numerical
•b) Ion exchange method.
•Desalination of brackish water
/Purification of water by Reverse osmosis
and Electrodialysis.
Unit 1: Water technology & Green
Chemistry
•Definition,
•goals of green chemistry, efficiency
parameters, Need of Green Chemistry Major
uses – traditional and green pathways of
synthesis of adipic acid, polycarbonate, indigo
dye.
WATER
 Contents

•Impurities in water.
•Hardness of water and its determination by EDTA
method
•Alkanality of water and its determination
 Impurities in Water
•Suspended impurities: like sand, oil globules, organic
wastes that can be removed by filtration. Size is greater
than 1000 A°
•Colloidal impurities: like finely divided clay, silica that
have size between 10-1000 A°, and can be removed by
coagulation.
•Dissolved impurities: a)Dissolved gases: like O2, CO2,
H2S and NH3 etc. b) Dissolves salts: like chlorides,
sulphates, nitrates, bicarbonates, carbonates of various
metal ions.
•Biological impurities: like bacteria, algae, fungi and
other microorganisms .
 Types of Hardness of water

1.Temporary or carbonate hardness

It is due to carbonates & bicarbonates of Ca, Mg and
other heavy metals. It is removed by mere boiling.
 Types of Hardness of water

2. Permanent or non–carbonate hardness

It is due to Sulphates, chlorides, nitrates of Ca, Mg &
other heavy metals. It is removed by chemical
treatment, not by simple methods.

Total hardness = Temporary hardness + Permanent

hardness
 Degree of Hardness

•It is the quantity or amount of hardness causing

impurities in water.
•Hardness is expressed in terms of CaCO3 equivalents.

•Units of hardness: ppm, mg/l

 Hardness Determination: EDTA method

•Complexometric method
•All types of hardness in water
•Rapid estimation of hardness
•More accurate results
•Very convenient method

EDTA structure: ethylene diamine tetra acetic acid

 Structure

disodium salt of ethylene diamine tetra acetic acid

Metal – EDTA complex

 3D structure M-EDTA complex ion
•Hexadentate
 Experimentation:
Part I: Standardization of Na2EDTA
•Std Hard Water: solution of 1 mg/ml CaCO3
•25 ml SHW + 10 ml buffer (pH 10) + 2–3 drops EBT
indicator –wine red color –titrated against Na2EDTA
solution.
Soln in burette: Na2EDTA solution

Indicator: 2 drops of EBT

End
=titration
‘X’mlpoint
(Part of
I)
 Experimentation:
Part II: Total hardness of sample water
•Sample Hard Water: given
•50 ml Sample HW + 10 ml buffer (pH 10) + 2–3 drops
EBT indicator –wine red color –titrated against
Na2EDTA solution.
Soln in burette: Na2EDTA solution

Indicator : 2 drops of EBT

End
=titration
‘Y’ml
point(Part
of II)
 Principle and Reactions

•Principle: At endpoint EBT–M ion complex breaks, and

EDTA forms complex with released M ion. EBT is set
free giving blue color.
•Reactions: at pH 10
 03/08/17
REACTION

1. M2+ + EBT ---------

PH 10  M – EBT + 2H
+

(Wine Red)

2. M2+ + EDTA -------- M – EDTA + 2H+

PH 10
(Colourless)

3. M - EBT + EDTA -------- M – EDTA + EBT

(Sky Blue)
PH 10

Experimentation
 Calculations

1000 ml 1 M EDTA  100 mg of CaCO3 equivalents

1ml SHW contains 1mg CaCO3, 25 ml SHW contains
25mg CaCO3
'X' ml of EDTA  25 mg of CaCO3 equivalents
1 ml of EDTA  (25/X) mg CaCO3 equivalents.
'Y' ml of EDTA  (25Y/X)=‘A’ mg CaCO3 equivalents
This ‘A’ mg of CaCO3 equivalents is present in 50ml HW.
1000 ml of HW (‘A’20) mg CaCO3 equivalents
Total hardness 20A or ( )ppm.
 Experimentation:
Part III: Permanent hardness of water
•Water is boiled (½hr) to remove temporary hardness.
•Cool & filter.
•This water sample is pipette out (50ml).
•Same procedure followed for finding permanent
hardness.
•Temporary hardness = (Total  Permanent) hardness
 Alkalinity of Water

•Hydroxides, carbonates and bicarbonates

•Estimated by titration against std acid
OH⁻ + H⁺ → H2O⁻ …(1)
CO3–2 + H⁺ → HCO3¯ …(2)
HCO3¯ + H⁺ → H2O …(3)
a) Only single ion : OH⁻ or CO3–2 or HCO3¯
b) Any two ions: OH⁻ & CO3–2 , CO3–2 & HCO3¯, OH⁻
&HCO3¯
OH⁻ & HCO3¯ react & form H2O + CO3–2 do not coexist.
c) All three ions : OH⁻, CO3–2 & HCO3¯ do not exist
together.
 Principle

•All OH⁻ and ½ of CO3–2 gets neutralized first

Indicated by phenolphthalein (P), pink to colorless
•Remaining ½ of CO3–2 (now present as HCO3¯) &
complete HCO3¯ (present in sample water) is
neutralized on further titration -Indicated by methyl
orange (M), yellow to orange
•Reactions occurring are P
OH⁻ + H⁺ → H2O⁻ …(1) M
CO3–2 + H⁺ → HCO3¯ …(2)
HCO3¯+ H⁺ → H2O …(3)
 Amount of alkalinities

•Alkalini es due to the OH⁻, CO3–2 and HCO3¯

Endpoint
Alkalini
ty
P&M
OH¯ CO3–2 HCO3¯
P=0 – – M
P=M P – –
P=½M – 2P –
P>½M 2P–M 2(M–P) –
P<½M – 2P M–2P
 Part I: Phenolphthalein end point

•10 ml of water sample + 1–2 drops phenolphthalein.

Soln in burette : Acid solution

Soln in pipette : Sample water (10ml)

not throw the

•DoIndicator : solution. Do of
1–2 drops notphenolphthalein
refill the burette.
•P ml is equivalent to OH⁻ and ½ of CO3–2 alkalinity.
End point : pink to colorless
End point of
titration (part I)
= ‘P’ml
 Part II: Methyl Orange end point

•Part I Solution + 2 drops of methyl orange indicator

–If yellow solution, then continue to titrate.
–If orange solution, then end pt is reached.
•End point of titration (part II) = ‘M’ml
•End point indicates complete neutralization of HCO3–
which are already present in water & which are
produced due to half neutralization of carbonates.
•M ml is equivalent to complete neutralization of
sample water.
 Calculations

1 ml 1N acid solution  50 mg of CaCO3 equivalent

P Alkalinity: (50PN11000/25) ppm
M Alkalinity: (50MN11000/25) ppm
•Volume of acid required to neutralize OH⁻, CO3–2 &
HCO3¯ is determined respectively using the table given
earlier.
•Alkalinity of each type is calculated.
 03/08/17
ALKALINITY OF WATER SAMPLE

Water become Alkaline due to presence of OH-, (CO3)-2

& (HCO3)-1 ions.
Types of Alkalinity
1. Only OH-
2. Only (CO3)-2
3. Only (HCO3)-1
4. (CO3)-2 & (HCO3)-1 together
5. OH- & (CO3)-2 together

Note: OH- & (HCO3)-1 together are not possible as they

react with each other to form (CO3)-2

Reactions
 Reactions

I.OH- + H+ H2O
(CO3)-2 + H+
P
(HCO3)-1
pH decreases to 8.7 Neutralization of OH- &
(CO3)-2 M

II. (HCO3)-1 + H+ H2O + CO2

pH 4 Neutralization of (HCO3)-1

P : Phenolophthalein M : Methyl Orange

03/08/17
Relation bet P & M
 03/08/17
Different Relations between P & M

Alkalinity Quantity of Quantity of Quantity of

OH- (CO3)-2 (HCO3)-2

P=0 0 0 M

P=½M 0 2P 0

P=M P 0 0

P<½M 0 2P M – 2P

P>½M (2P – M) 2(M – P) 0

Ill effect of water

 03/08/17
Calculation

Phenolphthalein Alkalinity

P = V1 / V * Z * 50 * 1000

Methyl Orange Alkalinity

M = V2 / V * Z * 50 * 1000

Reactions
Calculations