Water

Introduction and specifications of water

Hardness and its determination by EDTA method (Numerical)

Alkalinity and its determination (Numerical)

Reverse Osmosis, Electro-dialysis

Disinfection by break-point chlorination

Boiler feed water

Boiler problems- scale, sludge, priming & foaming: cause & prevention

Boiler Problems- caustic embrittlement & Corrosion: causes and
Prevention

Water Softening by Internal Treatment: Carbonate & Phosphate conditioning,
Colloidal conditioning and Calgon Treatment

Water Softening b External Treatment: Lime-Soda Process (Numericals),
Zeolite & Ion-Exchange Process
 Distribution of Water in Earths Surface

Sources of Water

Surface water Underground water

 Rain water
Spring and Well water
 River Water
 Lake water
 Sea water
Types of Impurities
 Dissolved Impurities:

Inorganic impurities: sulphate and chloride of Ca, Mg and Fe

Organic Impurities:

Gases: CO2, H2S, NH3
 Suspended Impurities: clay, mud and vegetable matters

 Colloidal impurities: fine size silica, alumina and organic waste

 Pathogenic impurities: bacteria, microbes, virus, parasites

Effect of Impurities

Colour of surface water

Taste and odour
Turbidity
Pathogenecity
Specification of drinking water

Should be bacteria free

Absence of suspended impurities

Should not have bad taste and odour

Should not contain toxic metals like Pb, As, Cr, Hg etc

pH should between 7- 8.5 (slightly alkaline)

Free from dissolved gases likeCO2, H2S

Turbidity of water should less than 10ppm

Reasonably soft in nature

 Hardness of water
Soft Water Hard Water
Water that produce lather with Water that produce scum or very
soap easily little lather with soap

Definition: - Hardness of water is defined as the soap consuming capacity of water.

The hardness is usually expressed in terms of Ca & Mg salts like bicarbonate, carbonate,
sulphate, chloride etc.
Hard water is formed due to presence of minerals like Ca and Mg
Other ions responsible for hardness are Al 3+, Fe2+and Mn2+

Formation of Hard water:

When hard water reacts with soap (sodium salt of stearic acid or palmetic acid) gives
curdy precipitate of calcium stearate or magnesium stearate

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

2 C17H35COONa + MgSO4 → (C17H35COO) 2Mg↓ + Na2SO4
 Types of hardness
Temporary hardness Permanent hardness

Due to the presence of bicarbonate salts of Ca and Due to the presence of soluble salt of
Mg chloride and sulphate of Ca and Mg
This can be removed by simply boiling of water. Due Permanent hardness cannot be
to boiling bicarbonate is converted into carbonate removed by boiling of water or hydrated
(insoluble precipitate) lime
Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑
Mg(HCO3)2 → Mg(OH)2↓ + 2CO2↑
Temporary hardness can also be removed by adding It can be eliminate by water softening
hydrated lime to precipitate insoluble carbonate. techniques like
Ca(HCO3)2 + Ca(OH) 2 → 2CaCO3↓ + 2H2O  Lime-soda process,
Mg(HCO3)2 + Ca(OH) 2 → Mg(OH) 2↓ + 2CaCO3↓ +  Zeolite,
2H2O  Ion-exchange resin
It is otherwise called as Carbonate hardness or It is otherwise called as Non-
Alkaline Hardness carbonate hardness or non- alkaline
Hardness
 Degree of hardness
Degree of hardness is defined as the total quantity of hardness causing salts present in
water

Hardness is usually expressed in terms of calcium carbonate (CaCO3) equivalent

Because
i. CaCO3 have molecular weight 100 and equivalent weight 50 that is easy to calculate
ii. It is highly insoluble in water and easily precipitate.

Calculation of degree of Hardness in terms of (CaCO3) equivalent

1 mole of CaCO3 ≡ 1 mole of hardness causing salts (I mole of these salt produce same no
of Ca2+ & Mg2+ ions )
100 g of CaCO3 ≡ 111 g of CaCl2
≡ 136 g of CaSO4
≡ 95 g of MgCl2
≡ 120 g of MgSO4
≡ 162 g of Ca(HCO3)2
≡ 146 g of Mg(HCO3)2
≡ 164 g of Ca(NO3)2
 Let CaCl2 be the hardness causing salt present in water

Let Amount of CaCl2 = x g

1 mole CaCl2 ≡ 1 mole of CaCO3

111 g of CaCl2 = 100g of CaCO3
55.5 g of CaCl2 = 50 g of CaCO3
x g of CaCl2 = (50/55.5) * x g of CaCO3

Mass of hardness Equivalent weight

X
producing substance of CaCO3
Hardness in terms of CaCO3 equivalent =
Equivalent weight of hardness producing substance
 Molecular weight
Mass of substance X of CaCO3
Hardness in terms of CaCO3 equivalent =
Molecular weight of substance

Mass of substance X 100

Hardness in terms of CaCO3 equivalent =
Molecular weight of substance

100
Equivalent of CaCO3 = Mass of substance X
Molecular weight of substance

Equivalent of CaCO3 = Mass of substance X Multiplication Factor

100
Multiplication Factor =
Molecular weight of substance
Hardness causing Molar mass Multiplication
salts factor
Ca(HCO3)2 162 100/162
Mg(HCO3)2 146 100/ 146
CaCl2 111 100/ 111
_
CaSO4 136 100/ 136
MgCl2 95 100/ 95
MgSO4 120 100/120
MgCO3 84 100/ 84
Mg(NO3)2 148 100/148
Al2 (SO4)3 342 100/ 114
FeSO4, 7H2O 278 100/ 278
NaAlO2 82 100/ (82* 2)
HCO3_ 61 100/ (61 * 2)
(CO3) 2- 60 100/ 60
OH_ 17 100/ (17 * 2)
Example: Calculate the total hardness in terms of CaCO3 equivalent of given sample of
water containing the following composition in ppm
CaSO4= 15.2 ppm
Mg(HCO3)2 = 2.4 ppm
MgCl2 = 8.5ppm

Ans
Constituents Amount (ppm) Multiplication CaCO3 equivalent
factor
CaSO4 15.2 100/ 136 15.2 x (100/136) =
11.17 ppm
Mg(HCO3)2 2.4 100/ 146 2.4 x (100/ 146) =
1.64 ppm
MgCl2 8.5 100/ 95 8.5 x (100/ 95) =
8.94ppm

Total hardness in terms of CaCO3 equivalent = 11.17 + 1.64 + 8.94 = 21.75 ppm
Temporary hardness in terms of CaCO3 equivalent = 1.64ppm
Permanent hardness in terms of CaCO3 equivalent = 11.17 + 8.94 = 20.11ppm
Numericals: Calculate temporary, permanent and total hardness of given sample of
water containing the following composition in mg/ L, ° Cl, ° Fr
CaSO4= 136 mg/L
Ca(HCO3)2 = 8.1 mg/L
Mg(HCO3)2 = 14.6 mg/L
MgCl2 = 9.5 mg/L
CaCl2 = 11.1 mg/L
NaCl = 50 mg/ L

Que. 2: A water sample has the following dissolved salts (mg/L} . Calculate its temporary
and permanent hardness in ppm of CaCO3.

Mg(HCO3)2= 80, MgSO4= 110, CaSO4=85, MgCl2=94, CaCl2=84, and NaCl= 50

[end term exam, 2018] (6).
CHARACTERISTICS OF WATER
As per the suggestion given by World Health Organisation (WHO) and by Indian Council
of Medical Research (ICMR), the following are the important characteristics of potable
water.
1. It should be clear, colourless and odourless.
2. It should be cool and pleasant to taste.
3. It should be free from harmful bacteria and suspended impurities.
4. It should be free from dissolved gases like CO2, H2S, NH3, etc., and poisonous
minerals like
lead, arsenic, manganese, etc.,
5. Hardness should be less than 500 ppm.
6. Chloride ion content should be less than 250 ppm.
7. Fluoride ion content should be less than 1.5 ppm.
8. Total Dissolved Solids (TDS) content should be less than 500 ppm.
9. pH of the potable water should be 6.5 – 8.5.
DETERMINATION OF TOTAL HARDNESS OF WATER BY EDTA METHOD
The hardness of water is estimated by EDTA method (Complexometric method) using
Erichrome black T as indicator. The ions involved in water hardness, i.e. Ca2+(aq) and
Mg2+(aq), can be determined by titration with a chelating agent EDTA.

EDTA (Ethylene Diamine Tetra Acetic acid )

 EDTA is usually expressed as H4Y

 It is a hexadented ligand and a strong chelating agent
 It forms 4 or 6 co-ordinate bond with Ca2+ or Mg2+ ions
 It generally present in the form of disodium salt of EDTA (Na2H2Y, 2 H2O).
 Na2EDTA forms 1:1 complex with metal ions like Ca2+ or Mg2+ irrespective of
the charge of the cation.
 EDTA forms a s very stable, colourless metal complex in basic medium
 The reactions are:
Ca2+(aq) + H2Y2-(aq) → CaY2-(aq) + 2H+(aq)
Mg2+(aq) + H2Y2-(aq) → MgY2-(aq) + 2H+(aq)

Structure of disodium salt of EDTA and metal- EDTA complex

Eriochrome Black T (EBT):

 Metal – ion indicator constitute of an Azo dye

 Blue colored in unionized form and change to wine red colour in ionised form

Sodium 1-[1-hydroxy- 2- naphthylazo]-6-nitro-2-naphthol-4-sulfonate

 Principle of EDTA titration

1. Eriochrome Black-T forms an unstable wine red complex with Ca2+ or Mg2+
ions present in hard water at pH of 8 to 10.

Mg2+ / Ca2+ + EBT ------→ [Mg/Ca—EBT]

pH = 8 - 10 Unstable Complex
(Wine Red)
2. During titration against EDTA, EDTA forms a soluble, colourless, stable
complex with free Ca2+ or Mg2+ ions present in water

Mg2+ / Ca2+ + EDTA ------→ [Mg/Ca—EDTA]

Stable Complex
(Colorless)
3. When all free metal ions ( Ca2+ or Mg2+ ) are complexed, then next drop of
EDTA replaces EBT from Metal—EBT complex, and the colour change from
wine-red to blue.

[Mg/Ca—EBT] + EDTA ------→ [Mg/Ca—EDTA] + EBT

(Wine Red) (Blue)
 Experimental Procedure :
PREPARATION OF SOLUTIONS:

1. Standard hard water: 1 gm of dry CaCO3 is dissolved in minimum quantity of dil. HCl
and evaporate the solution to dryness on a water bath, and then diluted to 1 lit with water.
1 ml of Std. hard water = 1mg of CaCO3 eq. hardness

2. EDTA solution: Dissolve 3.7 gm of disodium salt of EDTA (molar mass 372.25g) in
distil water to make 1 lit EDTA solution

3. EBT Indicator: Dissolve 0.5 gm of EBT in100 ml of alcohol.

4. Buffer solution: 67.5 gm NH4Cl + 570 ml of Con. Ammonia solution diluted with
distilled water to 1 lit.
 Procedure and Calculation

Step 1: Calculation of Molarity of standard hard water (SHW)

Weight of CaCO3 = 1 g
Molecular Weight of CaCO3 = 100 g
No of Moles of CaCO3 = Weight / molecular weight = 1/ 100 = 0.01
Volume of water (V) = 1L
Molarity of standard hard water (M1) = No of moles / Volume of water = 0.01/1 = 0.01 M

2 : Standardization of EDTA solution

(50 ml of standard hard water Titrated against EDTA (wine-red colour → Blue)
+ 10-15ml buffer solution
(Volume of EDTA consumed be
+ 1-2 drops EBT indicator ) in
Ve)
a conical flask
SHW EDTA solution
where,
M1V1 = MeVe M1 = Molarity of standard hard water
0.01 × 50 = Me × Ve V1= Volume of standard hard water
Me= (0.01 × 50) / Ve Me = Molarity of EDTA
Molarity of EDTA = (0.01 × 50) / Ve Ve = Volume of EDTA consumed
Step 3: Determination of Total Hardness of Sample water
Same Procedure as step 2
Let the volume of EDTA consumed on titration with sample hard water = V’e
Sample hard Water EDTA solution
M2V2 = M’eV’e
where,
M2 × 50 = (0.01 × 50) × (V’e / Ve) M2 = Molarity of sample hard water
V2= Volume of sample hard water
M2 = (0.01 × 50) × (V’e / Ve) / 50) = 0.01 (V’e / Ve) M’e = Molarity of EDTA
V’e = Volume of EDTA consumed
Total Hardness in terms of CaCO3 eq.

=Molarity × molecular mass of CaCO3 × 1000 ppm

= 0.01 (V’e / Ve) × 100 × 1000 ppm

= 1000 (V’e / Ve)

 Step 4: Determination of Permanent Hardness

i. 50ml sample water in conical flask -→ boiled till the volume reduce to 10ml -------→ cool,
filter and wash -------→ make up the volume of filtrate to 50ml with distilled water

ii. Same procedure for titration against EDTA solution

iii. Let the volume of EDTA consumed on titration with boiled water = V’’e

Boiled Water EDTA solution where,

M3V3 = M’’eV’’e M3 = Molarity of boiled water
V3= Volume of boiled water
M3 × 50 = (0.01 × 50) × (V’’e / Ve)
M’’e = Molarity of EDTA
V’’e = Volume of EDTA consumed
M3 = (0.01 × 50) × (V’’e / Ve) / 50) = 0.01 (V’’e / Ve)

Permanent Hardness in terms of CaCO3 eq.

=Molarity × molecular mass of CaCO3 × 1000 ppm

= 0.01 (V’’e / Ve) × 100 × 1000 ppm

= 1000 (V’’e / Ve)

 Step 5: Determination of Temporary Hardness

Temporary Hardness = Total Hardness - Permanent Hardness

Summary
Step 1: Calculation of Molarity of standard hard water (SHW)
MSHW = 0.01M

2 : Standardization of EDTA solution

MEDTA = Molarity of EDTA = (0.01 × 50) / Ve

Step 3: Determination of Total Hardness of Sample water in terms of CaCO3 eq.

Total Hardness = 1000 (V’e / Ve)

Step 4: Determination of Permanent Hardness in terms of CaCO3 eq.

Permanent Hardness= 1000 (V’’e / Ve)

Step 5: Determination of Temporary Hardness

Temporary Hardness = Total Hardness - Permanent Hardness

Where [Ve, V’e, V’’e = Volume of EDTA consumed in step 2,3 and 4]
Example: l00mL of a water sample consumed 25mL of centi molar EDTA for titration
using EBT as an indicator. After boiling water sample consumed 5mL of the same EDTA
solution for titration. Calculate total, permanent and temporary hardness in ppm [end
term exam,2019] (6.5).
Ans

Step 1: Molariy of EDTA solution = 0.01M

Step 2: Titration of EDTA with sample hard water:

Hard water EDTA solution Given

MhwVhw = MedtaVedta Volume of sample hard water (Vhw) = 100ml
Molarity of EDTA (Medta) = 0.01M
Mhw × 100 = 0.01 × 25 Volume of EDTA consumed (Vedta) = 25ml
Mhw = (0.01 × 25 ) / 100
Total Hardness in terms of CaCO3 eq.
= Mhw × 100 × 1000 ppm
= [(0.01 × 25 ) / 100] × 100 × 1000
= 250 ppm
 Step 2: Titration of EDTA with sample hard water after boiling

Hard water EDTA solution Given

MbwVbw = M’edtaV’edta Volume of sample hard water after boiling (Vbw) = 100ml
Molarity of EDTA (Medta) = 0.01M
Mbw × 100 = 0.01 × 5 Volume of EDTA consumed (V’edta) = 5ml
Mbw = (0.01 × 5 ) / 100
Total Hardness in terms of CaCO3 eq. = Mbw × 100 × 1000 ppm
= [(0.01 × 5 ) / 100] × 100 × 1000
= 50 ppm

Step 3: Determination of Temporary Hardness

Temporary Hardness = Total Hardness - Permanent Hardness
= 250 – 50 = 200 ppm
Examples 2
Que. 1 gm of CaCO3 is dissolved in dil. HCl and evaporate the solution diluted to 1 lit with
water. 50ml of this solution requires 42ml of EDTA solution while 50 ml of sample water
requires 15 ml of EDTA. On the otherhand when 50 ml of boiled water sample titrated
against EDTA consumed 9 ml of the solution. Calculate total, permanent and temporary
hardness of water in ppm. [end term exam,2015] (6)
Ans :
Step 1: 1 L of standard hard water contains 1 gm of CaCO3
⇒ 1 ml of standard hard water contains 1 mg of CaCO3

Step 2: Strength of EDTA:

42 ml of EDTA required for = 50 ml of standard hard water = 50 mg of CaCO3
∴ 1 ml of EDTA required for = 50/ 42 mg of CaCO3

Step 3: Total Hardness

50 ml of sample water requires 15 ml of EDTA
1 ml of EDTA required for = 50/ 42 mg of CaCO3
15 ml of EDTA required for = (50/ 42) × 15 mg of CaCO3
50 ml of sample water requires = 15 ml of EDTA = (50/ 42) × 15 mg of CaCO3
1000 ml of sample water requires = (50/ 42) × (15/ 50) × 1000 mg of CaCO3
= (15/ 42) × 1000 mg of CaCO3 = 357.14 mg /L
Step 3: Permanent Hardness
50 ml of boiled water sample requires 9 ml EDTA solution
1 ml of EDTA required for = 50/ 42 mg of CaCO3
9 ml of EDTA required for = (50/ 42) × 9 mg of CaCO3
50 ml of sample water requires = 9 ml of EDTA = (50/ 42) × 9 mg of CaCO3
1000 ml of sample water requires = (50/ 42) × (9
9/ 50) × 1000 mg of CaCO3
= (9// 42) × 1000 mg of CaCO3 = 214.29 mg /L

Step 4: Temporary Hardness

Temporary Hardness = Total Hardness - Permanent Hardness

= 357.14 – 214.29 = 142.85 ppm