Internal treatment

• Internal treatment consists of adding chemicals directly to the water in the boilers for
removing dangerous scale forming salts which were not completely removed in the external
treatment for water softening.
 
• This is mainly used as a corrective treatment to remove the slight residual hardness and also
sometimes to remove the corrosive tendencies in water.
 
• This treatment is not usually applied to raw waters, except for small boilers, but it is usually
practiced in larger power stations.
 
• In modern high pressure boilers, water of zero hardness is required, since even an egg-shell
thickness of scale may be extremely harmful.

• Different types of internal treatment for softening of water are :

 Carbonate conditioning
 Phosphate conditioning
 Colloidal conditioning
 Calgon conditioning
 Carbonate conditioning
• For a salt to get precipitated the ions constituting the salt must be present in sufficient
concentration so that the product of their concentrations (i.e. ionic product) exceeds a
limiting value known as the solubility product.
• Thus for a salt like CaCO3 to be precipitated , the product of the concentration of Ca2+
ions and CO32- ions must exceed the solubility product of CaCO3,
• This solubility product is represented by KSPCaCO3
 Continued………

• Dividing equation (i) by (ii)

Now if….
• In this condition CaCO3 will be precipitated in preference to CaSO4, because the solubility
product of CaSO4 can not be attained due to a decreased concentration of SO 42-
• This principle is used in carbonate conditioning , when Na 2CO3 is added to boiler water the
concentration of CO32- increases and when it exceeds the ionic concentration of SO 42- , only
CaCO3 is precipitated.

 Limitations of carbonate conditioning :

• In high pressure boilers, scale formation can not be avoided by adding sodium carbonate,
because in high pressure boilers two different hydrolysis reactions takes place which results
in the formation of OH- ion.
 Carbonate conditioning Continued………

• Due to the above hydrolysis reactions the concentration of OH - ions increases and CO32-
ions decreases. Hence the precipitation of CaCO3 becomes impossible.
• Sodium carbonate due to the above hydrolysis reactions forms sodium hydroxide which can
also cause caustic embrittlement
Na2CO3 + 2H2O → 2NaOH + H2CO3
H2CO3 → H2O + CO2↑
• Due to all these reasons Carbonate conditioning is not applicable to high pressure boilers.
 Phosphate conditioning
• Phosphate conditioning is applicable to high pressure boilers. In this method an excess of
soluble phosphate is added to boiler water. It react with Ca and Mg salts and form soft sludge
of Ca and Mg phosphate which can be removed by blow down process.

• The three sodium orthophosphates viz., Na3PO4, Na2HPO4 and NaH2PO4 have been used for
phosphate conditioning. Sodium pyrophosphate (Na 4P2O7) and sodium metaphosphate
(NaPO3) are also used for the same. The typical reactions of the various phosphates with the
hardness represented as CaCO3, may be summarized as follows:
2 Na3 PO4 + 3 CaCO3 → Ca3 (PO4)2 + 3 Na2CO3
2Na2HPO4 + 3 CaCO3 → Ca3 (PO4)2 + 2 Na2CO3 + CO2 + H2O
2 NaH2PO4 + 3 CaCO3 → Ca3 (PO4)2 + Na2CO3 + 2 CO2 + 2 H2O
2 NaPO3 + 3 CaCO3 → Ca3 (PO4)2 + Na2CO3 + 2 CO2
• The choice of phosphate salt depends upon the type of alkalinity of the boiler water fed.Types
of phosphate salts are mainly:
 
 Phosphate conditioning continued…………
If the feed water tends to produce an acidic condition in the boiler, the alkaline Na 3PO4
should be chosen. This treatment could be supplemented with NaOH if the required alkalinity

could not be maintained with Na3PO4 alone.

• If the feed water produces almost the right alkalinity desired in the boiler, it is preferable to
use Na2HPO4 which is practically neutral.
• If the boiler water becomes too alkaline, the acidic NaH 2PO4 would be selected.
• Both sodium pyrophosphate and metaphosphate are rapidly hydrolysed under boiler water
temperatures to orthophosphate.
NaPO3 + H2O → NaH2PO4
Na4P2O7 + H2O → 2 Na2HPO4
• Thus their behaviour in boiler is identical with that of orthophosphates as mentioned above.
• The use of internal treatment combined with suitable blow down for sludge removal, has
contributed largely to the operation of modern high pressure steam boilers without the
formation of hard scales.
• Precautions should be taken to inspect them at least once in six months to remove scale and
sludge accumulation.
 Colloidal conditioning

• Scale formation can also be minimised by adding some colloidal conditioning

agents such as glue, agar-agar, tannins, starches and sea-weed extract into the boiler
feed water. These substances act as protective colloids. They function by
surrounding the minute particles of CaCO3 and CaSO4 and prevent their
coalescence and coagulation. Thus, the precipitated scale-forming salts are
maintained in loose suspended form which can easily be removed by blow down
operation. Thus the scale formation is prevented.
 Calgon conditioning
• It involves the addition of sodium hexa meta phosphate (also known as calgon) to boiler water to prevent scale or sludge
formation. Calgon converts the scale forming impurity like CaSO4 into soluble complex compound which is harmless to the
boiler.
 
Na [Na4 (PO3)6] → 2Na+ + [Na4(PO3)6]2-
2CaSO4 + [Na4 (PO3)6]2- → [Ca2 (PO3)6]2- + 2Na2SO4
( soluble complex)
• Addition of 0.5 to 5ppm of calgon prevents scale formation in one of the following ways :

 At low temperatures and pressures it forms stable and soluble complexes with calcium salts.

 At high temperatures and pressure calgon is converted into sodium pyrophosphate which reacts with calcium salts to form
calcium pyrophosphate which appears as a loose sludge and can be removed by blow down operation.
Na2 [Na4 (PO3)6] + 6H2O → Na2P2O7 + 6H2↑

Na2P2O7
CaSO4 → CaP2O7 + Na2SO4
(calcium pyrophosphate )

Loose sludge