Hardness of water

Hardness in water is that characteristic , which prevents the lathering of soap

Due to presence of salts of Ca, Mg, and other heavy metals

Sample of hard water , when treated with soap ( Na or K salt of higher fatty acid,
Oleic , palmitic or stearic) does not produce lather but on the other hand
forms a white scum or precipitate . This is due to insoluble soaps of Ca and Mg .

Water which does not produce lather with soap solution but forms white curd
called Hard water

Water which lathers easily on shaking with soap solution is called soft water
 Hardness of water
Water which does not produce lather with soap solution but forms white curd
called Hard water

Water which lathers easily on shaking with soap solution is called soft water

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

Sodium Stearate Hardness In soluble

2 C17H35COONa + MgSO4 (C17H35COO)2Mg +2NaCl

Sodium Stearate In soluble

(soap)
Temporary or carbonate Hardness

Is caused by dissolved bicarbonates of Ca, and Mg and other heavy

metals and carbonate of ion.

This hardness can be destroyed by mere boiling of water, when

bicarbonates decomposed yielding carbonates or hydroxides which are
deposited as crust at the bottom of vessel

Heat
Ca(HCO3)2 CaCO3 + H2O + CO2
In soluble
Heat
Mg(HCO3)2 Mg(OH)2 + 2CO2

In soluble
Permanent or non carbonate Hardness

Is caused by dissolved chlorides and sulphates of Ca, and Mg , iron

and other heavy metals ion.

This hardness can not be destroyed by boiling of water

Concentration of hardness as well as non hardness constituting
ions are usually expressed in terms of equivalent amount of CaCO3

This mode permits multiplication and division of concentration

and this choice is due to the Molecular weight of CaCO3: = 100;
Equivalent weight = 50

And CaCO3 is most insoluble in water and can be precipitated in

Water treatment
 Units of Hardness
1. Parts per million (ppm)
1 part of CaCO3 equivalent hardness per 106 parts of water

2. Milligrams per liter (mg/L): Number of mg of CaCO3 equivalent

hardness present per liter of water
1mg /L = 1 mg of CaCO3 equivalent hardness of 1L of water
but 1L water weights = 1Kg = 1000 g = 1000X1000mg = 106 mg
Hence 1mg/L = 1 ppm

3. Clarke’s degree (oCl): number of grains (1/7000 lb) of CaCO3

equivalent hardness per gallon (10 lb) of water
Or parts of CaCO3 equivalent hardness per 70000 parts of water
4. Degree French (oFr): parts of CaCO3 equivalent hardness per
105 parts of water
1 oFr = 1 parts of CaCO3 equivalent hardness per 105 parts of
water

5. Milli equivalent per liter (meq/L): Number of milli equivalents

of hardness present per liter
1 meq/L = 1meq of CaCO3 per L of water
= 10-3 X 50 g of CaCO3 eq per liter
= 50 mg /L of CaCO3 eq = 50 ppm
 Hardness of water

The equivalents of CaCO3 = [Mass of hardness producing substance X chemical equivalent of CaCO 3]
Chemical equivalent of Hardness producing substance

The equivalents of CaCO3 = [Mass of hardness producing substance X 50]

Chemical equivalent of Hardness producing substance

Ca(HCO3)2 : Molar Mass: 162 chemical equivalent = 81

Mg(HCO3)2 : MM =146 C.E. = 73
CaSO4 : MM = 136 C.E. = 68
MgSO4 : MM = 120 C.E. = 60
CaCl2 : MM = 111 C.E. = 55.5
MgCl2 : MM = 95 C.E. = 47.5
MgCO3 : MM = 84 C.E. = 42
CaCO3 : MM =100 C.E. = 50
 Disadvantages of Hard Water
In domestic :

Washings :
Wastage of lot of soap, white sticky precipitate adheres on the
fabric giving spots and streaks. Irons salts could cause for
staining of cloth

Bathing : White mass deposits on the bath tub and body, cleaning
quality soap is depressed

Cooking : boiling point of water is elevated due to the presence

of ions. More fuel and time is required. Pulses, beans and peas
do not cook properly with hard water. Salty material deposits
on cooking utensil. Un-pleasent taste of tea or coffee if prepared
using hard water

Drinking : Bad effect on our digestive system.

Possibility of forming calcium oxalate crystals in urinary tract is
increased
 Disadvantages of Hard Water
In industrial use :

Textile industry : Wastage of lot of soap, white sticky precipitate

adheres on the fabric giving spots and streaks. These fabrics when
dyed do not provide exact shade of color
Irons salts could cause for staining of cloth.

Sugar industry : Water containing sulphate, nitrite, alkali carbonate

refining causes difficulties in the crystalization of sugar

Dyeing industry : Ca, Mg, and Fe salts in hard water may react with
costly dyes forming undesirable precipitates. It could give impure
shades of color and spots on the fabric
Paper industry : Ca, Mg, salts in hard water tend to react with
chemicals and other material employed to provide smooth and
shining finish to paper. Iron salt could give undesired color to the
paper.
Laundry: Waste of soap; Iron salt could give undesired color to the
cloth
Concrete making: Water containing chlorine and sulphates could
affect
Hydration of cement which eventually affects the strength of
concrete

Pharmaceutical industry: Undesirable products will be obtained if

hard water is used in drug manufacturing industry
 Disadvantages of Hard Water

In steam generation in boilers:

To generate stream , boilers are extensively used. If
hard water used in boilers, many troubles arises due to
the salt content

i) Scale and sludge formation

ii) Corrosion

iii) Priming and foaming

iv) Caustic embrittlement

 Sludge and Scale
In Boiler, water evaporates continuously and salt concentration
Increases progressively.
When salt concentration reaches its saturation point, they
precipitate out of water.

If precipitate is loose and slimy, it is called Sludge

If the precipitated matter forms hard , adhearing crust/coating on the inner

walls of boiler, it called Scale
 Scale and sludge formation

Sludge: It can be easily scrapped off with wire brush

It formed at colder part of the boiler
It collects in the area where flow rate is slow or bends

Scale: These are formed by the salts which has greater solubility
in hot water than cold water
MgCO3,MgCl2, CaCl2,MgSO4

Disadvantages_ Sludge

Sludges are poor conductors; wastage of heat that generated

If Sludges formed with scale, former gets trapped in the latter

and both get deposited as scales

Excessive sludge formation disturbs the working boiler . It settle

In the region of poor water circulation such as pipe connection,
Plug opening, gauge-glass connection: choking of the pipes
 Scale and sludge formation
Disadvantages_ Scale
1. Wastage of fuel
Scales are low thermal conductivity: rate of heat transfer from
boiler to water is low: To get excess heat, fuel consumption is high

2. Lowering the boiler safety

Over heating results boiler material softener and weaker and it
distorts boiler tube

3. Decrease in effeciency
Scales sometimes deposits on valves and condenser of the
boiler. It chokes them partially

4. Danger of explosion
When thick scale crack due to uneven expansion, water
comes out and touches over heated iron plates. This results
high stream supply subsequently generates high pressure which may
even cause explosion
 Sludge and Scale

Formation of Scales is due to

1. Decomposition of CaHCO3
Ca(HCO3)2 CaCO3 + H2O + CO2
Scale
CaCO3 scale is soft. This type scale forms in low pressure
Boilers.
However, in high pressure boilers, CaCO3 is soluble

CaCO3 + H2O Ca(OH)2 + CO2

soluble
 Sludge and Scale

Formation of Scales is due to

2. Deposition of CaSO4

Solubility of CaSO4 in water decreases with rise of

Temperature.

At 15oC, 3200 ppm,

At 55oC, 55 ppm
At 320oC 27 ppm

Hence, CaSO4 gets precipitated as hard Scale at heated

Portions of the Boiler soluble
This is main cause of scales in high pressure Boilers
CaSO4 scale is quite adherent and difficult to remove
 Sludge and Scale

Formation of Scales is due to

3. Hydrolysis of Mg salts

Dissolved Mg salts undergo hydrolysis at high temperature

In side the boiler forming MgOH2 precipitate as soft Scale

MgCl2 + 2 H2O Mg(OH)2 + 2HCl

Scale
 Sludge and Scale

Formation of Scales is due to

4. Presence of silica (SiO2)

Even small amount of silica in water deposits as Calcium

silicate or Magnesium silicate

Ca(SiO3) and Mg(SiO3)

These stick very firmly and very difficult to remove

Source of silica in water: sand filter

 Removal of Scale

1. With the help of scraper or piece of wood or wire brush

If they are loosely adhering

2. Thermal shocks ( heating and sudden cooling with cold water)

if they are brittle

3. Dissolving scales by using chemicals

if they are adherent and hard
CaCO3 scales: 5-10% HCl
CaSO4 Scales: EDTA (which forms soluble complexes)

4. By frequent blow down operation

if they are loosely adhering
 Prevention of Scales Formation

1. External treatment : Using softening water

2. Internal treatment (sequestration):

Dissolved salt ions are complexed with chemicals to give
soluble salts

a. Precipitate the scale forming impurities n the form of sludge

which can be removed by blow-down operation

b. Convert to dissolved compounds which stays in water but do not cause

any harm

Blow down operation:

Partial removal of hard water through top at the bottom of the boiler
Addition of fresh softened water to make up after blow-down
1. Colloidal conditioning: In low pressure boiler scale can be
Avoided by using kerosene, tannin, agar-agar gel etc.
Scale gets coated to give non sticky and loose deposits and this
can be removed by blow-down operation

2. Phosphate conditioning: In high pressure boiler, scale can

be avoided by adding sodium phosphate
3 CaCl2 + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl
Hard scale Soft sludge

Soft, non-adherent sludge of calcium and magnesium

phosphates can be removed by blow-down operation

NaH2PO4 (acidic); Na2HPO4 (weakly alkaline);

Na3PO4 (alkaline)

Choice of salt depends upon the alkalinity of boiler-feed water

 3. Carbonate conditioning: In low pressure boilers, Na2CO3
addition avoids scale formation
CaSO4 is converted to CaCO3

CaSO4 + Na2CO3 CaCO3 + Na2SO4

scale Loose sludge
Can be removed by blow down
To be continued in next class

4. Calgon conditioning

5. Treatment with sodium Aluminate

6. Electric conditioning

7. Radioactive conditioning

8. Complexometric method