Water

Technology
 Module:1 - Water Technology

 Characteristics of hard water - hardness,

DO, TDS in water and their determination
 Numerical problems in hardness
determination by EDTA;
 Modern techniques of water analysis for
industrial use
 Disadvantages of hard water in industries.
Water Fall
Dead Sea
River
Back waters
Rain water
Glacier
Availability of water on Earth
Total water on earth (3/4th part is covered by water)

97% Ocean 3% Remaining

80% Polar Icecaps

10% Rock Crevices

10% Livingbeing
Use
 Sources of Water

Surface Water Flowing Water

 Still Water
 Underground Water
 Springs


 Sea Water
 Shallow Wells
 Deep Wells
 Rain Water

 Sources of Impurities in Water


 Soil or Ground


Sewage or Industrial wastes


 Organics from plants, animals, microbes

 Atmospheric gases (for rain water)

 TDS in water bodies


 Fresh water (upto 1000 ppm)

 Brakish water (1000 - 3500 ppm)



 Sea water (more than 3500 ppm)


Impurities in Water
 Impurities in Water

o Physical
Colour, Turbidity, Taste, Odour

o Chemical
Acidity, Gases and Mineral matters

o Biological
- Microorganisms: algae, fungi, bacteria
(Pathogenic causing Malaria, diarrhoea, typhoid etc.)
 Requisites of Potable Water
Physical
a) Sparklingly clean (crystal clear) and odourless
b) Palatable - Pleasant to taste
c) Perfectly cool
d) Turbidity should not exceed 10 ppm
Chemical
a) Free from objectionable minerals like Pb, As, Cr and Mn
b) Free from dissolved gases like H2S
c) Alkalinity should not be too high (pH 7.0- 8.5)
d) Should be reasonably soft
e) TDS and hardness should be less than 500 ppm
f) Cl- and SO42- ---- 250ppm
g) F- ---- 1.5 ppm
Biological
a) Free from pathogens / microorganisms
Total Dissolved Solids (TDS)
 The source of dissolved solids is various
kinds of minerals present in water.
 It can be determined taking a known amount
(say 100 mL) of water and by evaporating
the contents carefully to dryness.
 The residue (W gm) left after evaporation of
the filtered sample shows the total dissolved
solids present in that particular water
sample. T.D.S. must be less than 500 ppm in
potable water.
 Dissolved Oxygen (D.O.)
 Dissolved oxygen is defined as the oxygen
dissolved in water. It is 48.89 mL/litre at 32 oF and
atmospheric pressure. The amount of oxygen dissolved
in water depends on physical, chemical and biological
activities taking place in water.
 According to Henry’s Law, the solubility of a gas is
directly proportional to the absolute pressure. It means,
if pressure is increased, there is increase in dissolved
oxygen at given temperature.
 Dissolved oxygen causes boiler corrosion.
 Dissolved oxygen is determined by Winkler’s
method of Iodometric titration.
 Dissolved Oxygen Assessment
by Winkler’s Method
Principle
Estimation of dissolved oxygen (DO) in water is useful in studying

corrosion effect of boiler feed water and in studying water pollution. DO

is usually determined by Winkler’s titration method.
It is based on the fact that DO oxidize potassium iodide (KI) to iodine.

The liberated iodine is titrated against standard sodium thiosulphate

solution using starch indicator.
Since DO in water is in molecular state, as such it cannot oxidize KI.

Hence, manganese hydroxide is used as an oxygen carrier to bring

about the reaction between KI and Oxygen. Manganese hydroxide, in
turn, is obtained by the action of NaOH on MnSO4.
The liberated iodine (I2) is titrated against standard sodium

thiosulphate (Na2S2O3) solution using starch as indicator.

Reactions Involved
 Estimation of Dissolved Oxygen
 100 mL of sample water in a conical flask + add 2 mL of MnSO4 and 2
mL of alkali KI solution and shake well for the rough mixing of the
reagents.
 Set aside the flask for few minutes to allow the precipitate to settle
down and then add 2 mL of conc. H2SO4 for complete dissolution of
the precipitate.
 Then, titrate against std. sodium thiosulphate solution. When the
solution turn into light yellow, add starch indicator.
 End point is the disappearance of bluish brown colour. Repeat the
titration to get the concordant value.
 Calculate the strength of dissolved oxygen from the titer value. Based
on that, calculate the amount of dissolved oxygen in the given water
sample.
 Hardness of water
o Characteristic of water to prevent formation of lather with soap
is known as hardness of water.
o It is due to dissolved salts of mainly calcium and magnesium as
well as iron and other heavy metals.
o Hardness is of two types
a) Temporary
- Due to dissolved bicarbonates of calcium and magnesium and
carbonates of iron and other heavy metals.
- Can be easily removed by boiling where CO2 gas gets expelled
removing the hardness.

b) Permanent
- Due to dissolved chlorides and sulphates of calcium and magnesium.
- Can be removed through zeolite, Lime-soda, ion-exchange processes.
 Hardness of water
o Water hardness can be identified when soap does not form lather.

o Problems of using hard water:

a) Domestic
- wastage of fuel & time
- improper cleaning (wastage of soap)
- health related issues ( Urinary infections, kidney stones)

b) Industrial
- Boiler troubles (scale, sludge, caustic embrittlement,
priming and foaming)
- wastage of fuel
- process related problems
- problems in textile, sugar, paper, laundry, pharma industries
Domestic and Industrial need of water
 Water that does not produce lather with soap solution readily but forms an
insoluble white precipitate is called HARD WATER.
Water that lathers easily on shaking with soap solution is called SOFT
WATER.
Hard water containing Mg , Ca or Fe salts when treated with soap
2+ 2+ 2+

(sodium or potassium salts of stearic acid) does not produce lather but forms
an insoluble white precipitate of calcium or magnesium stearate.

Hardness in water is caused by the presence of certain dissolved salts such

as bicarbonates, chlorides, and sulfates of Mg2+, Ca2+ or Fe2+ which under
certain conditions of temperature, pressure or reactions with other chemicals
results in the formation of insoluble scales and sludges.
sludges
Whereas, hardness in water is not caused by the salts of Na+ or K+ ions. Eg.: Na2CO3
(washing soda) is used as a water softener to reduce the hardness in water. They are
soluble in water under all conditions except when they reach the saturation level.
 Types of Water Hardness
Water hardness is of two types:
(i) Temporary hardness or carbonate hardness: is caused by the presence of
dissolved bicarbonates of Ca2+ and Mg2+ and carbonate of Fe2+.
Temporary hardness can be removed by just boiling the water. The dissolved
bicarbonates in the water are decomposed into insoluble carbonates or
hydroxides which are deposited as crust (as scales) at the bottom of vessel.

(ii) Permanent or non-carbonate hardness is due to the presence of

chlorides and sulfates of Ca, Mg, Fe. Cannot be removed by boiling. Can be
removed through zeolite, Lime-soda, ion-exchange processes.
 Measurement of hardness
o Hardness of water is measured in parts per millions
(ppm.) as calcium carbonate equivalents.
o Reasons for expressing hardness in CaCO3 equivalents:
- its molecular weight is 100 ; equivalent weight is 50
- it is the most insoluble impurity commonly found in water.

o Units of hardness:
- parts per million in CaCO3 equivalents (1 mg/L is 1ppm.).
- if 146 mg/L of MgSO4 is present in water, the hardness of
water is 146 ppm. as MgSO4.
o When expressed in CaCO3 equivalents, the formula for
conversion is:
mass of hardness causing substance X 50 (Eq. wt. of CaCO3)
Eq. wt. of hardness causing substance
 Measurement of hardness
o Hardness of water is measured in parts per millions
(ppm.) as calcium carbonate equivalents.
o Reasons for expressing hardness in CaCO3 equivalents:
- its molecular weight is 100 ; equivalent weight is 50
- it is the most insoluble impurity found in water commonly.

o Units of hardness:
- parts per million in CaCO3 equivalents (1 mg/L is 1ppm.).
- if 146 mg/L of MgSO4 is present in water, the hardness of
water is 146 ppm. as MgSO4.
o When expressed in CaCO3 equivalents, the formula for
conversion is:
Eq. wt. of CaCO3 (i.e. 100/2 = 50) X amt of hardness causing substance
Eq. wt. of hardness causing substance
 Expressing water hardness
1. ppm. measurement :
1 part of CaCO3 equiv. in106 parts of water (1 mg/L).

2. Clark’s degree:
1 part of CaCO3 equiv. in 70,000 parts of water.

3. French degree:
1 part of CaCO3 equiv. in 105 parts of water.

* Conversion:
1 ppm = 1 mg/L = 0.1 Fro = 0.07 oCl
Example : Calculate the temporary hardness and permanent hardness of a
sample of water drawn from a jute mill near Kolkata containing Mg(HCO 3)2 =
7.3 mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L; CaSO4 = 13.6 mg/L.
Solution: Convert the hardness causing salts into their CaCO3 equivalents!

Constituent X factor CaCO3 eq. Hardness type

Mg(HCO3)2 = 7.3 100/146 7.3 x 100/146 = 5 mg/L Temp. Mg2+
mg/L
Ca(HCO3)2 = 16.2 100/162 16.2 x 100/162 = 10 mg/L Temp. Ca2+
mg/L
MgCl2 = 9.5 mg/L 100/95 9.5 x 100/95 = 10 mg/L Perm. Mg2+
CaSO4 = 13.6 mg/L 100/136 13.6 x 100/136 = 10 mg/L Perm. Ca2+
H 1
Final Answer:
C 12 Temp. hardness = 5+10 = 15 mg/L or ppm
O 16 Perm. Hardness = 10+10 = 20 mg/L or ppm
Total hardness = 35 mg/L or ppm
Mg 24
Cl 35.45
S 32
Ca 40
 EDTA method of water hardness estimation
o After titration with EDTA, EBT gets replaced with EDTA since EDTA forms a
stronger complex with the metal ions.
o This is indicated by the formation of a steel blue coloured complex.
pH 9-10
Ca2+/Mg2+ EBT + EDTA Ca 2+/Mg2+ EDTA + EBT
Wine red (Stable complex) Steel blue
Procedure:
o First EDTA Solution is standardized using 50 ml standard hard water (1
mg/ml of CaCO3 equivalents is prepared as standard hard water).
o For this, first known aliquot of Standard hard water is taken and 10-15 mL of
ammonia buffer is added to bring the pH between 9-10.
o Then a few drops of EBT solution is added to form the unstable complex
giving wine red colour.
o This solution is titrated with the EDTA solution till the solution turns to steel
blue indicating the formation of stable EDTA-Metal ion complex. This volume
of EDTA is noted as V1.
o The above procedure is repeated with sample hard water of unknown
hardness. Volume of EDTA is noted as V2.
Ethylenediaminetetraacetic acid (EDTA)
In its protonated form, Eriochrome Black T is blue.
It turns wine-red when it is in ionized form in aq
medium and forms a week complex with calcium, 
magnesium metal ions at pH around 9-10.
 EDTA method of water hardness estimation
o Then sample hard water of 250 mL is taken and evaporated to a volume of
50mL when the temporary hard salts settle down.
o The solution is filtered and washed thoroughly and made up again to
250mL. From this solution, 50 mL is pipetted out and titrated in similar
manner as done with standard hard water. Volume of EDTA is noted as V 3.

Calculations:
a) Total hardness:
o 50 ml of SHW = V1mL of EDTA = 50 mg of CaCO3
o 1 mL of EDTA = 50/V1 mg of CaCO3
o 50 ml of sample water = V2mL of EDTA = 50/V1 x V2 mg of CaCO3

1 ml of sample water = 50/V 1 x V2/50 mg of CaCO3

Therefore, 1000 mL of sample hard water = 50/V 1 x V2 x 1000 mg/L

i.e. Total hardness of sample hard water = V2/V1 x 1000 mg of CaCO3 (ppm.)
EDTA method of water hardness estimation
Permanent hardness

50 mL of sample hard water after removing temporary hardness consumed

V3 mL of EDTA.

1 mL of EDTA = 50/V1 mg of CaCO3

Therefore, V3 mL of EDTA = 50/V1 x V3 mg of CaCO3

50 mL of sample hardwater after boiling contained 50/V 1 x V3 mg of CaCO3

50 V3
x X 1000mg/L
Therefore, 1000 mL of sample hard water contains
V1 50
V3
X 1000 mg/L of CaCO3 (ppm.)
Permanent hardness =
V1
EDTA method of water hardness estimation

Temporary hardness

Temporary hardness = Total hardness – permanent hardness

{ V2
V1
X 1000
{
{
V3
V1
X 1000
{

= 1000 X { V2 {
{
V2 { ppm.
V1
[[[[
[[[[

V1
[[[[
[[[[

{
V 2 – V3 {
= 1000 X ppm.

V1
 Numerical on EDTA method

 0.5 g (or 500 mg) of CaCO3 was

dissolved in HCl and the solution was
made up to 500 ml with distilled
water. 50 ml of the solution required
48 ml of EDTA for standardization
titration. 50 ml of hard water sample
required 15 ml of EDTA and after
boiling and filtering, required 10 ml of
EDTA solution. Calculate the hardness.
 Total hardness = (V2/V1)x1000
 = (15/48)X1000
 = 312.5 ppm
 Permanent hardness = (V3/V1)x1000
 = (10/48)X1000
 = 208.3 ppm
 Temporary hardness = 104.2 ppm