WATER

Lecture-1

Sources of Water
Qualities of Water
Hardness of water
 Introduction
ntroduction
Planet earth is abundantly rich in water (75% of its surface area)
Very essential for the existence of all living beings
Abundant but less than 1% of the world’s water is available for use
Oceans – 97.2% -high salt content makes it virtually unusable
Remaining- 2.98% -considerable amount in the form of ice caps at poles
Only 0.3% is available for human use.
 Hardness of Water : -
Hard Water : The water which does not produce lather with soap.
Soft Water : - The water which produces lather with soap.
Hardness of water is the Soap consuming capacity of water sample
due to presence of soluble salts of calcium, magnesium and other heavier metals in water.
Hard water does not give lather easily with soap, but produces a white scum or precipitate
with soap. The scum or precipitate is due to the formation of insoluble soaps of calcium and
magnesium ions react with soap.
 Cause of Hardness

A sample of hard water, when treated with soap does not produce lather, but forms
insoluble white scum, which do not possess any cleaning action. It is due to the
formation of insoluble salts of Ca and Mg
2 C17H35COONa + CaSO4 (C17H35COO)2Ca + Na2SO4
Sodium stearate Insoluble salt
o + MgCl2 (C17H35COO)2Mg + NaCl

cations Ca+2 and Mg+2 are completely precipitated out in

Lather is not formed until the
the form of scum. As a result large quantity of soap is required to produce lather
with hard water.
Types of hardness:
Temporary hardness : Temporary hardness is caused by the presence of dissolved
bicarbonates of calcium and magnesium.
This can be removed by boiling which converts bicarbonates to insoluble carbonates and
hydroxides which can be removed by filtration.

Ca(HCO3)2 boil CaCO3 + H2O + CO2

Also called Carbonate/Alkaline hardness.

Permanent Hardness
Permanent hardness is due to presence of chlorides& sulfates of
dissolved calcium , magnesium , iron & other heavy metals.
The salts responsible for permanent hardening are CaCl2, MgCl2,
CaSO4, MgSO4, FeSO4, Al2(SO4)3.
Permanent hardness cannot be removed by boiling. This is also known
as non –carbonate or non – alkaline hardness.
Removed by Lime soda process, Zeolite process, Ion exchange method
The sum of temporary and permanent hardness is referred as total
hardness of water.
 DEGREE OF HARDNESS

Although hardness of water is never present in the form of CaCO3 as it is insoluble

in water hardness of water is conveniently expressed in terms of equivalents of
CaCO3.

The hardness is expressed in terms of equivalents of calcium carbonate.

Reason for choosing CaCO3 as standard for reporting hardness is:

1. Ease in calculations on its molecular weight is exactly 100.
2. It is the most insoluble salt that can be precipitated in water treatment.
 CALCULATIONS

Suppose a given water sample is hard due to the presence of CaCl2. The soap
consuming capacity of this hard water and a standard hard water containing CaCo3 can
be calculated using the following equation:
2 C17H35COONa + CaCl2 (C17H35COO)2Ca + 2 NaCl
o (MW = 111g)
2 C17H35COONa + CaCO3 (C17H35COO)2Ca + Na2CO3
o (MW = 100g)
Thus, 111 parts by wt. of CaCl2 would react with same amount of soap as 100 parts by
wt of CaCO3 as 1 mole of these salts would produce same no of Ca+2 and Mg+2
CaCO3 equivalents of various salts is
100g of CaCO3 ~ 111g of CaCl2 ~ 136g of CaSO4 ~ 95 g of MgCl2 ~ 120 g of
MgSO4 ~ 162 g of Ca(HCO3)2 ~ 146g of Mg(HCO3)2
Let W g/L of CaCl2 present in water sample, then its CaCO3 equivalents will be:
1g mole of CaCl2 = 1g mole of CaCO3
111g of CaCl2 = 100g of CaCO3
1 g of CaCl2 = 100/111 g of CaCO3
Wg of CaCl2 = 100/111 × W g of CaCO3
Equivalents of CaCO3 for hardness causing CaCl2 = Eqwt. wt of CaCO3 × W g
Eqwt. wt of CaCl2
In general,

Equivalents of CaCO3 = Mass of the substance × Eq.wt of CaCO3

Eq. wt of the hardness causing substance

= Mass of the substance × Mol wt of CaCO3

Mol wt. of the substance
 Units of Hardness :
1. Parts Per Million : Parts of CaCO3 equivalent hardness per 106 parts of water.
1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water.

2. Milligrams per litre :- Number of milli grams of Calcium Carbonate equivalent hardness present in 1 litre of water.
1 mg / L = 1 mg of CaCO3 equivalent hardness present in 1 liter of water.
1 L = 1 Kg = 1000 g = 1000 x 1000 mg = 106 mg
1 mg /L = 1 mg of CaCO3 eq per 106 mg of H2O
1 mg/L = 1 ppm

3. Clarke’s degree : (°cl) parts of the of CaCO3 equivalent hardness per 70,000 parts of water.

1°Clarke = 1 part of CaCo3 of hardness per 70,000 parts of water.

4. Degree French (°Fr) : It is in the parts of CaCO3 eq hardness per 105 parts of water.

5. Milliequivalents per litre : - No of milli equivalents of hardness present per litre of water.
 1 m eq/L = 1 meg of CaCo3 per / litre of water.
= 10-3 x 50 g of CaCo3 / litre
= 50 mg /L of CaCo3 eq = 50 ppm

Relation between various units of hardness:

1 ppm = 1 mg /L = 0.1 °Fr = 0.07°°Cl = 0.02 meq / L

 WATER
Lecture-2

Estimation of Hardness of water

 Estimation of hardness of water by EDTA Method:
This is a complexometric method. Ethylene diamine tetraacetic acid (EDTA) in
the form of its sodium yields the anion.

Principle of EDTA titrations:

The quick, complete and 1:1 interaction of metal ions with EDTA leading to the
formation of stable complex is the basis for complexometric titrations.

Theory: The hard water is buffer to a pH value of ∼10using NH4OH-NH4Cl buffer

and few drops of EBT indicator solution are added. EBT forms a weak complex
with metal ions that has a wine-red colour.
EDTA –Ethylene diamine tetraacetic acid, H4Y
It is insoluble in water so not used in complexometric
titration

Disodium salt of EDTA, Na2H2Y

This salt is used in estimation of hardness due to
1. Its purity
2. Its high solubility in water

Indicator – EBT (Eriochrome Black T)

METAL-EDTA COMPLEX

It combines with metal ions in 1:1 ratio

During the course of titration of water sample against EDTA, first EDTA combines with free
Ca2+ or Mg2+ ions to give very stable and colour less metal-EDTA Complex. After all the free
metal ions are consumed, the next drop of added EDTA solution displaces the indicator to
form Metal-EBT complex.
Metal – EBT + EDTA →Metal – EDTA + EBT
Wine red blue

At the equivalence point, there is change in colour from wine-red to blue.

Procedure:
Step – 1: Standardisation of EDTA solution:
The burette is filled with EDTA solution after washing and rinsing. Pipette out 50mL of
standard hard water (1mL of it must contain 1mg of CaCo3) into a 250mL conical flask, 10mL
of buffer solution and 2-3 drops of EBT indicator are added and titrated against EDTA
solution until the wine-red colour changes to blue. Let the volume of EDTA solution
consumed be V1 mL.
Step – 2: Determination of total hardness of water:
As per the same procedure (Step-1), 50mL of the unknown water sample is titrated
against EDTA. Let the volume of EDTA solution consumed be V2 mL.

Step -3: Determination of permanent hardness of water:

250mL of the water sample is taken in a 500mL beaker and boiled it till the volume
is reduced to about 50mL. [The step causes all the bicarbonates to decompose
respectively into insoluble CaCO3 and Mg(OH)2]. Filter and wash the precipitate
with distilled water and quantitatively collect the filtrate and washings in a 250mL
conical flask and made up the volume to 250mL with distilled water. 50mL of this
water sample is titrated against EDTA solution as in Step-1. Let the volume of
EDTA solution consumed be V3mL.
 Principle of EDTA titrations
 The hard water is buffered to a pH 10 using NH4OH-NH4Cl buffer and a few drops of EBT indicator
are added.
 A) EBT is a blue colored dye and forms a weak complex with Ca+2/Mg+2 which is wine red in color
Ca+2/Mg+2 + EBT --------  [Mg/Ca-EBT] complex
(wine red), unstable
b) In the course of titration of water sample with EDTA, EDTA first combines with metal to form Ca/Mg-EDTA
complex (stable and colorless) and the indicator is set free. After all the metal ions are consumed, the next
drop of EDTA solution displaces indicator to form metal-EDTA complex.
Mg/Ca-EBT complex + EDTA --------  Mg/Ca-EDTA + EBT
(wine red) (colorless, stable) Blue
Stability- M-EDTA > M-EBT
The total hardness is thus determined.
For the determination of permanent hardness, temporary hardness is first removed by boiling
followed by filtration of the ppt. The filtrate is then titrated with EDTA as above. Temporary is then
determined by subtracting.
Calculations:
Step – 1: Standardisation of EDTA Solution:
V1mL of EDTA = 50mL of standard hard water
= 50mg of CaCO3 ( 1mL contains 1mg of CaCO3) 1mL of EDTA = 50 / V1 mg of CaCO3
equivalent hardness
Step -2: Determination of total hardness of water:
50mL of unknown hard water sample = V2mL of EDTA
= V2 x 50 / V1mg of CaCO3 eq.

Step-3: Determination of permanent hardness of water: 50mL of boiled water = V3mL of

EDTA
=V3 x 50/V1mg of CaCO3 eq.

Step-4: Determination of temporary hardness: Total – Permanent Hardness

 Alternative calculations
Molarity of Standard Hard water (M1) = 1mg CaCO3/100g/mol = 0.01 M
1 mL

 Standardization of EDTA-
M1V1 (SHW) = M2V2 (EDTA)
0.01 × 50 = VA mL × M2
Molarity of EDTA, M2 (EDTA) = (0.5/VA) M ------(1)
 Determination of Total Hardness
M3V3 (unknown water sample) = M2V2’ (EDTA)
M3 × 50 = VB × 0.5/VA (Substitute M2 from (1))
Molarity of unknown water sample M3 = VB × 0.5/VA × 1/50 = (0.01 VB/VA) M

Strength = Molarity (M3) × mol. Wt. = 0.01 VB/VA × 100 g/L × 1000 = 1000(VB/VA) mg/L or ppm
 Determination of Permanent Hardness
M4V4 (Boiled water) = M2V2” (EDTA)
M4 × 50 = 0.5/VA × VC
Molarity of boiled water sample M4 = (0.01Vc/VA ) M

Strength = Molarity × Mol.wt = 0.01 Vc/VA× 100 = Vc /VA g/L × 1000 = 1000 (VC/VA ) mg/L or ppm

Determination of Temporary Hardness = Total-Permanent = 1000 (VB-VC) / VA ppm

 Disadvantages of Hard water
Disadvantages of hard water in Domestic use :

 Washing : When we use hard water for washing purpose, the water does not lather freely
with soap and produces sticky precipitate of Ca and Mg soaps. This cause wastage of soap
 Bathing : Hard water does not lather freely with soap solution and produces sticky scum
on the body.
Thus, cleansing quality of soap is depressed and lots of water is wasted too.
 Cooking : Due to the presence of dissolved hardness, the boiling point of water is elevated.
Therefore, more fuel and time are required for cooking.

 Drinking : Hard water causes a bad effect on our digestive system and also the possibility
of forming calcium oxalate crystals in urinary tracks is increased.
Disadvantages of hard water in Industrial use :

 Textile industry : Hard water cannot produce good quality of lather. It precipitates of calcium and magnesium
soaps and adhere to the fabrics. These fabrics when dyed do not produce exact shades of colour.

 Sugar industry : it causes difficulties in the crystallization of sugar and the produced sugar may be deliquescent.
 Dyeing industry : Use of hard water, yields impure shades and gives spots on the fabrics being dyed.
 Laundry : Hard water used in laundry causes much of the soap used in washing and may even cause colouration
of clothes.
 Concrete making : It affects the hydration of cement and the final strength of the hardened concrete.

 Pharmaceutical industry : If hard water used for preparing pharmaceutical products like drugs or injection may
produce certain undesirable products in them.
Disadvantages of hard water in steam generation in boilers :

If hard water directly fed into the boilers it may cause many troubles
following below :
 Scale and sludge formation
Corrosion
Priming and foaming
Caustic embrittlement