Unit 1: Water, Waste Water Chemistry and Analysis

Contents

Introduction, Impurities in water, Hardness of water and its determination (EDTA Method), alkalinity,
Chemical analysis of water: Dissolved Oxygen, Chlorides, Softening of water by Ion Exchange and
Reverse Osmosis method, Water treatment for drinking purpose: coagulation, sedimentation,
filtration, sterilization- chlorination and ozonization, Concept of break point chlorination.
Page | 1
Introduction

Water is Essential for

 Human beings, animals, plants and Industries.

 Engineering material preparation, Steam generation, Coolant in power and chemical
industries.
 Used in steel, rayon, paper, atomic energy, textile, chemicals, pharmaceutical and ice
industries.
 Used in air conditioning, bathing, drinking, sanitary, washing, irrigation, firefighting etc..

Abundance

Water is most abundant.

Earth is covered by 79 % of water. In this,

97% is locked as oceans and seas as
saline water, 2.4% is locked as polar ice
caps, giant glaciers and less than 1 % is
used as drinking, domestic, industrial
and agricultural irrigation.

Source of Water

 Surface Waters is occupied as Rain Water, River Water, Lake Water and Sea Water.
 Underground is occupied as Spring Water, Well Water etc.,

Rain water is the pure form. It contains dissolved organic and inorganic particles and dissolved
industrial gases CO2, NO2, SO2 etc.,

Sea water is very impure. Due to the too salinity, it is not useful for industrial use except cooling.

Underground water is free from organic impurities due to filtering action of the soil.

Impurities in water

Dissolved Impurities
Dissolved gases : O2, CO2, H2S etc.
Inorganic salts : Calcium (Ca2+), Magnesium (Mg2+), Chloride (Cl-), Nitrate (NO3-), Sulphate (SO42-)
Organic Matter : Humic and Fulvic Acids, Pesticides, Detergents, etc.
Suspended Impurities
Colloidal (Organic and Inorganic): Clays, Peat Acids
Inorganic: Sand Particles
Organic - Industrial, Domestic by-products
Living matter
Micro-Organisms - Bacteria, Algae, Viruses, etc.
Macro-Organisms - Fish, Shrimps, Worms, Larvae, etc.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Physical Characteristics imparted by impurities in water

Colour is caused by metallic substances like salts of iron, manganese, humus materials, tannins, pet,
algae, weeds, protozoans, industrial effluents etc..

Ex: yellow – Cr; yellowish red - iron; red-brow – peaty matter

Turbidity in the water is suspended insoluble matter including colloidal particles, coarse particles Page | 2
(mud, sediment, sand etc.).

Taste is due to some dissolved salts in water

Ex: Bitter – iron, aluminium, manganese sulphates or excess of lime.

Soapy – excess of sodium bicarbonate
Brackish – unusual amounts of salts
Odour is due to the presence of living organisms, decaying vegetation (algae, fungi, bacteria
and weeds).

Ex: Sewage water – inorganic and organic compounds of N, S and P.

Industrial waste water – org. matter (aldehydes, ketones, alcohols, phenols, esters)

Hardness of water
The water which gives lather easily with soap is called soft water

Ex: Distilled water & rain water.

The water which does not give lather easily with soap but produces a white precipitate or scum is
called hard water

Ex: sea water, well water

Hardness of water is due to the presence of bicarbonates, chlorides and sulphates of calcium,
magnesium and to a minor extent of certain heavy metals such as strontium and iron

Action of soap with hard water

Soap is the sodium or potassium salt of higher fatty acids such as stearic acid, palmitic acid etc..,

On addition of soap to the hard water, a white precipitate is formed due to the formation of calcium
or magnesium salt instead of producing lather.

2 C17H35COONa + Ca2+ → (C17H35COO)2Ca

Sodium stearate calcium stearate

2 C17H35COONa + Mg2+ → (C17H35COO)2Mg

Sodium stearate magnesium stearate
Types of Hardness:
Temporary Hardness or Carbonate hardness:

 It can be easily removed by simple boiling process.

 It is due to the presence of bicarbonates of calcium and magnesium.

Ca(HCO3)2 → CaCO3 + H2 O + CO2

Mg(HCO3)2 → Mg(OH)2 + 2CO2

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Permanent Hardness or Non-carbonate hardness:

 This cannot be removed by simple boiling.

 This is due to the presence of chlorides and sulphates of calcium and magnesium.
 The hardness can be removed by the addition of some reagents.
Disadvantages of hard water
Page | 3

Domestic use

• Washing and Bathing: Hard water does not form lather easily with soap. As a result, a large
amount of soap is wasted.

• Drinking: Hard water causes bad effects on our digestive system sometimes, stones formation
takes place in kidneys.

• Cooking: The boiling point of water is increased due to the presence of salts. Hence, more fuel
and time are required for cooking.

Industrial use

• Textile industry: Hard water causes wastage of soap. Precipitates of calcium and magnesium
soaps adhere to the fabric and cause problem.

• Paper industry: calcium and magnesium salts in water may affect the quality of paper

• Sugar industry: Water containing sulphates, carbonates, nitrates affects the crystallization of
sugar

• Dyeing industry: The salts of calcium and magnesium in hard water react with dyes and spoil
the desired shade.

• Pharmaceutical industry: Hard water may form some undesirable products while preparation
of pharmaceutical products

• Concrete making: Chloride and sulphates present in hard water will affect the hydration of
cement and the final strength of the hardened concrete

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Steam generation in boilers

(a) Corrosion
(b) Scale and sludge formation
(c) Priming and foaming
(d) Caustic embrittlement
Page | 4
Degree of Hardness
The number of parts by weight of calcium carbonate hardness per particular number of parts of water
is known as degree of hardness.
This is varied based on the unit employed.
Although hardness of water is never present in the form of the calcium carbonate, because it is
insoluble in water.

Hardness of water is conveniently expressed in terms of equivalent amount of CaCO3.

Hardness of water is always expressed in CaCO3 equivalents i.e..

100g CaCO3 = 162g Ca(HCO3)2 = 146g Mg(HCO3)2 = 136g CaSO4 =120g MgSO4 = 111CaCl2 = 95g MgCl2
weght of salt
CaCO3 equivalents = formula weight of salt X100

W
CaCO3 equivalents = GFW or GMW X100 (or)

W
CaCO3 equivalents = X 50
GEW

Units of Hardness

Parts per million (ppm)

1ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water

Milligrams per litre (mg/L)

1mg/L = 1ppm

Degree French (ºFr)

1°Fr = 1 part of CaCO3 equivalent hardness in 105 parts of water

1ppm = 0.1°Fr

Degree Clark (ºCl)

1°Cl = 1 part of CaCO3 equivalent hardness in 70,000 parts of water

1ppm = 0.07°Cl

Relationship: 1ppm = 1mg/L = 0.1 oFr = 0.07 oCl

1 oCl = 14.3 ppm = 14.3 mg/L = 1.43 oFr

Prob: A sample of hard water contains the following dissolved salts. Ca(HCO3)2 = 16.4 mg/L,
Mg(HCO3)2= 14.6 mg/L, CaCl2 = 22.4 mg/L, MgSO4 = 12 mg/L, CO2 = 44 mg/L and CaSO4 = 32.1 mg/L.
Calculate temporary, permanent and total hardness of the water sample.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Sol:

𝑾
Hardness causing salt Weight of salt GMW CaCO3 equivalent Weight = 𝑮𝑴𝑾 𝑿 𝟏𝟎𝟎 𝐦𝐠/𝐋
(mg/L)

Ca(HCO3)2 16.4 162 16.4

= 162
× 100 = 10.12 Page | 5

Mg(HCO3)2 14.6 146 14.6

= 146
× 100 = 10

CaCl2 22.4 111 22.4

= × 100 = 20.18
111

MgSO4 12 120 12
= × 100 = 10
120

CaSO4 32.1 136 32.1

= × 100 = 23.6
136

Temporary hardness of the water sample = hardness due to Ca(HCO3)2 + Mg(HCO3)2

= 10.12 + 10 = 20.12 mg/L

Permanent hardness of the water sample = hardness due to CaCl2+ MgSO4 + CaSO4

= 20.18 + 10 + 23.6 = 43.76 mg/L

Total hardness of the water sample = temporary hardness + permanent hardness

= 20.12 + 43.76 = 63.88 mg/L

Exercise problems

Prob:1. Calculate temporary, permanent hardness and total hardness of a sample of water containing
Ca(HCO3)2 = 40.5 mg/L, Mg(HCO3)2= 46.5 mg/L, MgSO4 = 27.6mg/L, CaCl2 = 22.4 mg/L and CaSO4
= 32.1 mg/L.

Prob:2. A sample of water on analysis has been found to contain the following in ppm. Ca(HCO3)2 =
32.4; CaSO4 = 13.6; MgCl2 = 19.0; Mg(HCO3)2 = 14.6. Calculate the carbonate and non-carbonate
hardness of water sample in degree Clark.

Prob:3. A sample of water on analysis has been found to contain the following in ppm.
Ca(HCO3)2 = 10.5; Mg(HCO3)2 = 12.5; CaSO4 = 7.5; CaCl2 = 8.2; MgSO4 = 2.6 calculate the temporary
hardness and permanent hardness of water sample in degree Clark.

Prob:4. Calculate the temporary hardness and permanent hardness of water sample containing
Mg(HCO3)2 = 7.3 mg/L; Ca(HCO3)2 = 16.2mg/L; MgCl2 = 9.5mg/L; CaSO4 = 13.6mg/L.

Prob:5. A sample of water on analysis has been found to contain the following in ppm.
MgCl2 = 8.2; CaSO4 = 7.5; Mg(HCO3)2 = 12.5; MgSO4 = 2.6; calculate the temporary hardness and
permanent hardness of water sample.

Prob:6. A sample of water on analysis has been found to contain the following in ppm. Ca(HCO3)2 =
4.86; Mg(HCO3)2 = 5.84; CaSO4 = 6.80; MgSO4 = 8.40. Calculate the temporary hardness and permanent
hardness of water sample.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Estimation of hardness by EDTA method

Principle:

Disodium salt of ethylene diamine tetra acetic acid (EDTA) forms stable complex with Ca2+ and
2+
Mg ions in aqueous solution at pH = 9.2 and above.

Erichrome black-T solution is used as an indicator which acts as catalyst. Page | 6

The amount of EDTA consumed in the reaction gives the amount of calcium and magnesium salts
present in the hard water.

Structure of EDTA:

The indicator EBT forms a weak complex with the metal ion present in the hard water and gives wine
red colour.

Ca2+ + EBT [Ca-EBT]

wine red
Mg2+ + EBT [Mg-EBT]
wine red
When EDTA is added to the above hard water sample, the metal ions form stable metal
complexes with EDTA by leaving the indicator which apart steel blue colour to the solution, indicating
the end point. The metal EDTA complex is stable at pH 8 – 10. This pH range can be maintained by
adding ammonia buffer (NH4Cl + NH4OH).

[Ca-EBT] + EDTA [Ca-EDTA] + EBT

steel blue
[Mg-EBT] + EDTA [Mg-EDTA] + EBT
Method steel blue

Estimation of hardness by EDTA method is in four stages.

I. Standardisation of EDTA Solution

II. Estimation of Total Hardness of water sample
III. Estimation of Permanent Hardness of water sample
IV. Estimation of Temporary Hardness of water sample
I. Standardisation of EDTA Solution
Burette solution - EDTA solution
Pipette solution - standard CaCO3 solution.
Conical flask solution - Hard water sample (standard CaCO3 solution) + 5 mL Buffer (pH=10)
+ 1 (or) 2 drops EBT
Indicator - Erichrome black – T
End point - Wine red colour to deep blue

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Calculations:
Concentration of CaCO3 solution = N1
Volume of CaCO3 solution = V1
Volume of EDTA solution = V2 = x ml
Concentration of EDTA solution = N2
We knew that N1V1 = N2V2 Page | 7
𝑁1 𝑉1 𝑁1 𝑉1
𝑁2 = 𝑉2
𝑜𝑟 𝑁2 = 𝑥 𝑚𝑙

II. Estimation of Total Hardness of water sample

Burette solution – Std. EDTA solution

Pipette solution - Hard water sample
Conical flask solution - Hard water sample + 2-5 mL Buffer (pH=10) + 1 (or) 2 drops EBT
Indicator - Erichrome black – T
End point - Wine red colour to deep blue

Calculations:

Concentration of EDTA solution = N2

Volume of EDTA solution = V2
Volume of hard water sample = V3 = y ml
Volume of EDTA solution 𝑋 Normality of EDTA solution X 50 𝑋1000
𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = Volume of hard water sample
ppm

V2 𝑋N2 X 50 X1000
𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = y
ppm

III. Estimation of permanent Hardness of water sample

Burette solution – Std. EDTA solution

Pipette solution - permanent hard water sample (boiled, filtered hard water)
Conical flask solution - permanent Hard water + 5 mL Buffer (pH=10) + 1 (or) 2 drops EBT
Indicator - Erichrome black – T
End point - Wine red colour to deep blue
Calculations:
Concentration of EDTA solution = N2
Volume of EDTA solution = V2
Volume of hard water sample = V4 = z ml
Volume of EDTA solution 𝑋 Normality of EDTA solution X 50 𝑋1000
𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = ppm
Volume of permanent hard water sample

V2 𝑋N2 X 50 𝑋1000
𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = z
ppm

IV. Estimation of Temporary Hardness of water sample

Temporary Hardness of water sample = Total hardness – Permanent hardness of water sample.

Prob.1: 0.28 gm of CaCO3 was dissolved in dil. HCl and the solution was made up to 1 litre with distilled
water.100 mL of the above solution required 28 mL of EDTA solution on titration. 100 mL of the hard
water sample required 33 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 the water.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Sol:

Concentration of hard water sample (CaCO3 solution)

W = 0.28 g
GEW = 50
V = 1 Ltr. Page | 8
𝑊 1 0.28 1
N = 𝐺𝐸𝑊 × 𝑉 𝑖𝑛 𝐿 = 50
× 1𝐿 = 0.0056 N
∴ Concentration of CaCO3 solution (standard hard water) is 0.0056N

Standardisation of EDTA Solution

Concentration of CaCO3 solution = N1 = 0.0056N

Volume of CaCO3 solution = V1 = 100 mL
Volume of EDTA solution = V2 = 28 mL
Concentration of EDTA solution = N2 = ?
We knew that N1V1 = N2V2

100 ×0.0056
N2 = = 0.2𝑁
28

∴ 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 0.02𝑁

Estimation of Total Hardness of water sample

Concentration of EDTA solution = N2 = 0.02N

Volume of EDTA solution = V2 = 33 mL
Volume of hard water sample = V3 = 100
Volume of EDTA solution X Normality of EDTA solution X 50 X1000
Total hardness = Volume of hard water sample
ppm
33X0.02X50 X1000
Total hardness = = 330 ppm
100
∴ 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 330 𝑝𝑝𝑚
Estimation of permanent Hardness of water sample
Concentration of EDTA solution = N2 = 0.02N
Volume of EDTA solution = V2 = 10 mL
Volume of hard water sample = V3
Volume of EDTA solution 𝑋 Normality of EDTA solution X 50 𝑋1000
𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = Volume of permanent hard water sample
ppm
10×0.02 X 50 𝑋1000
𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 100
= 100 ppm
∴ 𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 100 𝑝𝑝𝑚
Estimation of Temporary Hardness of water sample
Temporary Hardness of water sample = Total hardness – Permanent hardness of water sample.
Temporary Hardness of water sample = 330 – 100 = 230 ppm.
∴ Temporary Hardness of water sample = 230 ppm.

Problem 2: 100 ml of a sample of water required 25.0 ml of 0.01 M EDTA for the titration using
Eriochrome Black-T indicator. Calculate the total hardness.

Sol:

∴ 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 0.01𝑀

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Estimation of Total Hardness of water sample

Concentration of EDTA solution = M1 = 0.01M

Volume of EDTA solution = V1 = 25 mL
Volume of hard water sample = V2 = 100 mL

Volume of EDTA solution X molarity of EDTA solution X 100 X1000 Page | 9

Total hardness = Volume of hard water sample
ppm

25X0.01X100 X1000
Total hardness = 100
= 250 ppm

∴ 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 250 𝑝𝑝𝑚

Problem 3 : Calculate permanent hardness from the following. 500 ml of a water sample is boiled
for 1 hr. It is then cooled and filtered. The filtrate is made up to 500 ml again with distilled water.
50 ml of this solution requires 10 ml of N/50 EDTA with EBT-indicator and NH4Cl NH4OH
buffer.

Sol:
Estimation of permanent Hardness of water sample
𝑁
Concentration of EDTA solution = N1 = 50 = 0.02N
Volume of EDTA solution = V1 = 10 mL
Volume of hard water sample = V2 = 50 mL

Volume of EDTA solution 𝑋 Normality of EDTA solution X 50 𝑋1000

𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = Volume of permanent hard water sample
ppm

10×0.02 X 50 𝑋1000
𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 50
= 200 ppm

∴ 𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 200 𝑝𝑝𝑚

Problem 4
100 ml of a sample of water required 15.0 ml of 0.01 M EDTA for titration using Eriochrome Black-
T indicator. In another experiment, 100 ml of the same sample was boiled to remove the CH, the
precipitate was removed and the cold solution required 8.0 ml of 0.01 M EDTA using Eriochrome
Black-T indicator. Calculate (i) the total hardness, (ii) permanent hardness or NCH, (iii) carbonate
hardness CH, in terms of mg/lit of CaCO3.
Sol:

∴ 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 0.01𝑀

Estimation of Total Hardness of water sample

Concentration of EDTA solution = M1 = 0.01𝑀

Volume of EDTA solution = V1 = 15 mL
Volume of hard water sample = V2 = 100 mL

Volume of EDTA solution X molarity of EDTA solution X 100 X1000

Total hardness = Volume of hard water sample
mg/L

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

15X0.01X100 X1000
Total hardness = = 150 mg/L
100

∴ 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 150 mg/L

Estimation of permanent Hardness (NCH) of water sample
Concentration of EDTA solution = M2 = 0.01M Page | 10
Volume of EDTA solution = V2 = 8mL
Volume of hard water sample = V3 = 100 mL

Volume of EDTA solution 𝑋 molarity of EDTA solution X 100 𝑋1000

𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = Volume of permanent hard water sample
mg/L

8×0.01X100 𝑋1000
𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 100
= 80 mg/L

∴ 𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 80 mg/L

Estimation of Temporary Hardness or carbonate hardness (CH) of water sample
Temporary Hardness of water sample = Total hardness – Permanent hardness of water sample.
Temporary Hardness of water sample =150 – 80 = 70 mg/L.
∴ Temporary Hardness of water sample = 70 mg/L.

Problem 5
100 ml of a water sample required 20 ml of 0.01 M EDTA for the titration with Eriochrome Black-
T indicator 100 ml of the same water sample after boiling and filtering required 10 ml of 0.01 M
EDTA. Calculate the total, carbonate and non-carbonate harness of the sample.
Sol:

∴ 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 0.01𝑀

Estimation of Total Hardness of water sample

Concentration of EDTA solution = M1 = 0.01M

Volume of EDTA solution = V1 = 20mL
Volume of hard water sample = V2 = 100 mL

Volume of EDTA solution X molarity of EDTA solution X 100 X1000

Total hardness = Volume of hard water sample
mg/L
20X0.01X100 X1000
Total hardness = = 200 mg/L
100

∴ 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 200 mg/L

Estimation of permanent Hardness or non-carbonate hardness (NCH) of water sample
Concentration of EDTA solution = M2 = 0.01M
Volume of EDTA solution = V2 = 10mL
Volume of hard water sample = V3 = 100 mL

Volume of EDTA solution 𝑋 molarity of EDTA solution X 100 𝑋1000

𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = Volume of permanent hard water sample
mg/L

10×0.01X100 𝑋1000
𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = = 100 mg/L
100

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

∴ 𝑝𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 100 mg/L

Estimation of Temporary Hardness or carbonate hardness (CH) of water sample
Temporary Hardness of water sample = Total hardness – Permanent hardness of water sample.
Temporary Hardness of water sample =200– 100 = 100 mg/L.
∴ Temporary Hardness of water sample = 100 mg/L. Page | 11

Problem 6
In an estimation of hardness of water by EDTA titration, 250 ml of a sample of water required 15
ml of 0.025 M EDTA solution to get the end point. Calculate the hardness of water.
Sol:

Estimation of Total Hardness of water sample

Concentration of EDTA solution = M1 = 0.025M

Volume of EDTA solution = V1 = 15mL
Volume of hard water sample = V2 = 250 mL
Volume of EDTA solution X molarity of EDTA solution X 100 X1000
Total hardness = Volume of hard water sample
ppm
15X0.025X100 X1000
Total hardness = 250
= 150 ppm

∴ 𝑇𝑜𝑡𝑎𝑙 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 150 ppm

Exercise problems

1. 20 ml of standard hard water ( containing 15gms of CaCO3 per litre) required25 mL of EDTA
Solution for titration. 100 ml of water sample required 18 mL EDTA Solution, while same water
after boiling required 12 mL EDTA solution. Calculate carbonate and non-carbonate hardness of
water. Ans: 0.24N ; 2160ppm, 1440ppm, 720ppm
2. 0.5 gm of CaCo3 was dissolved in dil. HCl and the solution was diluted to 1000mL. 50 mL of this
solution required 48 mL of EDTA solution, while 50mL of sample water required 15 mL of EDTA
solution. On the other hand, 50mL of boiled sample water, when titrated against EDTA consumed
10 mL of the solution. Calculate each type of hardness in ppm.
Ans: 0.010417N; 156.24ppm, 104.16ppm, 52.08ppm

Alkalinity of water sample

 The alkalinity of the water is a measure of its capacity to neutralize acids.

 Bicarbonates represent the major form of alkalinity.
 Alkalinity is measured by titrating a sample with standard acid.
 It is due to the presence of OH-, CO32- and HCO3 - ions.
 Alkalinity (mol/L) = [HCO3-] + 2 [CO32-] + [OH-] – [H+]
 These can be estimated separately by titration against standard acid, using phenolphthalein
and methyl orange as indicators.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Estimation of Alkalinity of water sample

PRINCIPLE:

The type and extent of alkalinity of water sample is

determined by titrimetric method. The possible
combinations of ions causing alkalinity in water are i) OH- Page | 12
only, ii) CO32- only, iii) HCO3- only, iv) OH- & CO32- v) CO32- &
HCO3- but not OH- and HCO3-.

OH- and HCO3- cannot exist together because they combine instantaneously to form carbonate ions.

OH- + HCO3- CO32- + H2O

Procedure:

Burette solution : Standard acid solution

Pipette solution : 20 ml of water sample
Indicator 1 : 2 to 3 drops phenolphthalein
End point 1 : disappearance of pink color (P)
Indicator 2 : methyl orange
End point 2 : yellow to orange red (M)
• The titration of the water sample against a standard acid up to phenolphthalein end point gives
the completion of (i) and (ii) reactions only.

• The amount of acid consumed thus corresponds to hydroxide plus one half of the carbonate
present.

• On the other hand titration of the water sample against a standard acid up to methyl orange end
point makes the completion of reactions (i), (ii) and (iii).

• Hence the amount of acid used after the phenolphthalein end point corresponds to half of
carbonate plus all the bicarbonates.

• While the total amount of acid used represents the total alkalinity due to OH-, CO32-and HCO3-

Calculation
Volume of Acid(P) X Normality of Acid X 50 X1000
Phenolphthalein alkalinity = Volume of hard water sample
ppm

Volume of Acid (M)X Normality of Acid X 50 X1000

Methyl Orange alkalinity = Volume of hard water sample
ppm

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Estimation Dissolved Oxygen by Winkler’s Method

• The most famous method, although perhaps not the most popular anymore.

• usually most accurate for relatively pure waters, prone to errors due to interference from
things like Fe2+, SO32-, Fe3+

Principle: Page | 13

Procedure

1. Fill the stoppered BOD bottle with alkaline water sample.

2. Immediately add 2mL of MnSO4 solution and 2mL of alkaline iodide solution to the water in
the BOD bottle.
3. Replace the stopper in the reagent bottle to avoid air enter in to it.
4. Then is shake BOD bottle gently for the uniform mixing of reagents. Keep the flask aside for
some time to form the precipitate properly.
5. Add 2mL of Conc. H2SO4 and shake the bottle gently to dissolve the precipitate and keep BOD
bottle constantly for 8 hours in a cool dark place.
6. Then pipette out 10 mL of this solution in to a clean conical flask.
7. Fill the burette with std. hypo solution then add few amounts of hypo up to appearing of light
yellow colour in the conical flask.
8. Add 2 ml of starch indicator and continue the titration until the dark blue disappears in the
flask.
9. The titration is repeated to get concordant values.
10. From the titre value the amount of dissolved oxygen in the water sample can calculate using
the formula.
Calculations:
Concentration of hypo solution = N1

Volume of hypo solution =burette reading = V1

Volume of water sample =20 mL

16
Equivalent weight of oxygen = 2
=8

Volume of hypo solution 𝑋 Normality of hypo solution X 8 𝑋1000

𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑜𝑥𝑦𝑔𝑒𝑛 = 𝑝𝑝𝑚
Volume of water sample

V1 𝑋N1 X 8 X1000
𝑇ℎ𝑒 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑜𝑥𝑦𝑔𝑒𝑛 = 𝑝𝑝𝑚
Volume of water sample

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Chlorides in water

Chlorides are present in the water in the form of chlorides of calcium, magnesium, sodium, iron etc.,

Estimation of Chlorides in water

Chlorides in water are estimated in terms of CaCO3 equivalents.

Page | 14
Chloride contents in water can be determined by titrating a known volume of water sample with
standard silver nitrate solution using potassium chromate as an indicator.

Principle:

Silver nitrates precipitates chlorides as silver chloride.

When all the chloride ions precipitated as silver chloride, the excess drop of silver nitrate solution
reacts with the chromate ion and form brick red coloured precipitate which can be taken as end point.

Procedure

Burette solution : Standard (N1) AgNO3 solution

Pipette solution : 20mL water sample
Conical flask solution : Water sample + Indicator
Indicator : potassium chromate (K2CrO4)
End point : Yellow to brick red
Burette reading : Titre value i.e.. .volume of AgNO3 solution
Calculation :

Concentration of AgNO3 = N1
Volume of AgNO3 = V1 = Burette reading
Volume of AgNO3 solution 𝑋 Normality of AgNO3 solution X 50 X 1000
The amount of Chloride in the water= Volume of water sample
ppm
V1 X N1X 50 X 1000
The amount of Chloride in the water= Volume of water sample ppm

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis

Softening of water by Ion Exchange method

Principle:

This is known as De-mineralization process.

Ion exchange resins are cross linked giant organic molecular polymers which are insoluble in water.
Page | 15
Electrostatic forces hold ions to charged functional groups on the surface of the ion exchange resin.

The functional groups attached to these resins exchange cations and anions.

This plant contains two tanks in which the first chamber middle part is packed with cation exchange
resins while the second chamber middle part is packed with anion exchange resin.

First the hard water is passed through cation exchange resin bed which removes all cations present in
the water and their equivalent amount of H+ ions released in to the decationised water.

2 RCOOH + Ca2+ → (RCOO)2Ca + 2H+

2 RCOOH + Mg2+ → (RCOO)2Mg + 2H+

After the removal of cations, the water contains anions such as sulphates, chlorides, bicarbonates
etc.. The water is passed through anion exchange resin bed which removes all anions present in the
water while their equivalent amount of OH- ions released in to the deionised water.

2 ROH + SO42- → R2SO4+ 2 OH- ROH + HCO3- → RHCO3 + OH-

2 ROH + CO32- → R2CO3 + 2 OH- ROH + Cl- → RCl + OH-

The H+ ions and OH- ions which are released into the water at ion exchange process unite with each
other and form water molecules.

H+ + OH- → H2O

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis
Thus the water obtained from this process is free from the cations and anions. Hence this water is
called demineralised water and the process is called demineralisation of water.

Regeneration of Exhausted resins

On continuous use f ion exchange resins, the resins may lost their exchange capacity of ions, which
are called exhausted resins. Page | 16
The exhausted resins can be regenerated by passing dil.HCl solution through the exhausted cation
exchange resin while dil.NaOH solution through the exhausted anion exchange resin.

Regeneration of Exhausted cationic resins

(RCOO)2Ca + 2HCl → 2 RCOOH + CaCl2

(RCOO)2Mg + 2HCl → 2 RCOOH + MgCl2

Regeneration of Exhausted anionic resins

R2SO4 + 2 NaOH → 2 ROH + Na2SO4

R2CO3 + 2NaOH → 2 ROH + Na2CO3

RHCO3 + NaOH → ROH + NaHCO3

RCl + NaOH → ROH + NaCl

Advantages

Removes all cations and anions from water which is fit for high pressure boiler use.

Highly acidic and alkaline water can be treated by this process.

Disadvantages

Equipment is costly and required chemicals are also expensive.

Turbid water cannot be treated by this process

Brackish water

The water which contains dissolved salts with salty taste is called brackish water.

The water which contains about 3.5% of salts with brackish taste is comes under brackish water. The
brackish water is unfit for drinking. Ex. Sea water, ocean water etc..

Water attains brackishness due to presence of dissolved sodium chloride and small amounts of other
salts. The removal of those salts from the water is known as desalination of water or demineralisation
of water.

Reverse osmosis and electro dialysis are commonly used methods for the desalination of water.

Osmosis: The diffusion of solvent through a semi permeable membrane from pure solvent to solution
(or) dilute solution to concentrated solution (or) less concentrated solution to high concentrated
solution is called osmosis.

The external pressure applied to the solution in order to stop the osmosis of pure solvent into solution
(or) dilute solution into concentrated solution (or) less concentrated solution into high concentrated
solution, separated by a semipermeable membrane is called osmotic pressure.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis
Softening of water by Reverse Osmosis

The process of forcing of the follow of solvent from concentrated solution to pure solvent or high
concentrated solution to lower concentrated solution or concentrated solution to dilute solution by
applying pressure greater than its osmotic pressure, through the semipermeable membrane is called
Reverse Osmosis.
Here, semipermeable membrane allows only solvent but not solute. Page | 17

In this method, to obtain drinking water from brackish water, the pressure in the range of 15-40
kg/cm2 is applied. Cellulose acetate or other polymer matter may be taken as semipermeable
membrane.

From the sea water, salts are arrested by permeable membrane and only water comes to bottom on
reverse osmosis of brackish water. The water which comes to the bottom is soft water.

Advantages

 Removes ionic, non-ionic, colloidal and high molecular weight organic matter.
 Low maintenance cost with high reliability.
 Microscopic parasites (including viruses) are usually removed by properly functioning RO
units.
Disadvantages

 Two to four gallons of "waste" water are flushed down the drain for each gallon of filtered
water produced.
 Damaged membranes are not easily detected, so it is hard to tell if the system is functioning
normally and safely.

Water treatment for drinking purpose

The water which is obtained from river, lakes, ponds, dams etc.. May contain suspended impurities
and pathogenic microorganisms. For the drinking and domestic purpose, the water should be treated
in two stages.

1. Removal of suspended impurities

2. Disinfection or sterilisation
1. Removal of suspended impurities: The suspended impurities are removed by four stages
completely.

i. Screening
ii. Plain Sedimentation
iii. Sedimentation by coagulation
iv. Filtration

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis
i. Screening

Water is sent through the screen and arresting the floating material in the water.

Large size floating matter s arrested in the screening.

ii. Plain sedimentation

Page | 18
In this process screened water is stored and stand for few hours to few days.

Due to gravitational force of suspended particles, most of the particles settle down at bottom, and
the water is send for coagulation sedimentation

iii. Sedimentation by coagulation

Plain sediment water may contains dissolved salt. These salts are removed by adding coagulants like
alums, sodium aluminate, ferrous sulphate etc..

By adding alums, suspended salts got coagulation with alums and form flock like substance which
settle down at bottom.

Sodium aluminate acts as coagulant at pH less than 7 for salts which are dissolved in water

Ferrous Sulphate also works as coagulant at pH > 8.5

iv. Filtration

Suspended sediments, remaining suspended particles are filtered by sending the water through the
filtration bed. The filtered water is send for sterilization tower.

2. Sterilization or Disinfection

The killing of pathogenic bacteria, viruses, other microorganisms present in the water is called
sterilization or disinfection of water. This can be don in various methods.

 By adding bleaching powder

By adding bleaching powder to the water, bleaching releases free chlorine, which produce free
nascent oxygen through hypochlorous acid. Nascent oxygen kills all the pathogenic germs.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis
Advantages

 Cheapest and easiest method

Disadvantages

 Water becomes more hard.

Page | 19
 Excess of bleaching gives bad taste and bad smell to the water.

 By Chlorination

The tower which is used for chlorination is called chlorinator.

 Chlorinator contains baffle plates which are useful for proper mixing.

 Chlorine solution and water are sent from the top of the chlorinator and collected at
bottom. Here chlorine liberates nascent oxygen through hypochlorous acid, which act as
powerful germicide.

Advantages

 Storage requires less space.

 Effective and economical.
 Ideal disinfectant.
 Stable and does not deteriorate.
Disadvantages

 Excess chlorine causes unpleasant taste and odour.

 More effective at pH < 6.5 and less effective at high.
 By Ozonisation

Ozone is a powerful and an excellent disinfectant, which is produced by ozoniser.

Ozone is highly unstableand give nascent oxygen on breaking.

Advantages

Oxidises other reducing substances such as organic or inorganic matter.

Disadvantages

Method is costly and which is not useful for large scale.

Storage of ozone is difficult due to its unstableness.

Break point chlorination or free residual chlorine

Break point chlorination involves in addition of sufficient amount of chlorine to oxidise (a) Organic
matter, (b) reducing substances in raw water, (c) free ammonia in raw water, leaving behind free
chlorine, which possess disinfecting action against pathogenic germs.

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in
Unit 1: Water, Waste Water Chemistry and Analysis
When increasing the dosage of chlorine to water which contains organic matter or reducing
substances or free ammonia, gradually some changes takes place which shown in the following figure.

Page | 20

From the graph, initially the applied chlorine is used to destroy reducible substances present in water
and there is no free residual chlorine (Section 1)

As the amount of applied chlorine increases, the amount of combined residual chlorine also increases.
This is due to the formation of chloramine and other chlorocompounds. (Section 2)

On further increase of chlorine dose, the combined residual chlorine decreases i.e.. Monochloramines
destroyed and converted to dichloramines (Section 3)

Dichloramines give bad taste and odour to water due to volatile in nature. Due to this combined
chlorine reaches to minimum point, which is known as break point chlorination.

After break point of chlorination, free residual chlorine is increase with dosage of chlorine (Section 4).

Advantages

Before reaching the break point of chlorination

 Oxidising the reducing substances, organic matter and fee ammonia completely.
 Removes colour, taste and odour from the water.
After the break point of chlorination, destroy the all pathogenic bacteria and other germs.

☺ All the Best ☺

Dr. K. Chandramohan, Assistant Professor, Department of Chemistry, MITS, Madanapalle-517325 Chittoor Dist., AP.
drkchandramohan@mits.ac.in