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# pH

## •Negative logarithm of H+ ion concentration

pH= -log[H+ ]

•For pH =7 , Neutral.
•For pH >7, Basic.
•For pH< 7 ,Acidic.
Conductivity
Conductivity is the current carrying
capacity of any solution.It is the direct
measure of total ionisable solids in the
water
It depends upon:
•Concentration of the electrolyte. (Cions)
•the type of ions present
• the temperature of the electrolyte.
Unit of conductivity is micromho/cm
Alkalinity

## Alkalinity is a measure to the degree to

which water will neutralized acid and is
caused by the presence of hydroxides,
carbonates and bicarbonates. e.g..
NaOH Ca(OH)2 Mg(OH)2
Na 2CO 3 CaCO3
NaHCO3 Ca(HCO 3)2
M and P alkalinity
The alkalinity of water is determined by
titration with 0.02 N sulphuric acid and using
methyl orange(MeOH) or
phenolphthalein(HPh) as indicator .
Accordingly M alkalinity and P alkalinity have
been distinguished.
•For a solution of NaOH
M value = P value
•For a solution of Na 2CO3
M value = 2 P value
P and M alkalinity
•For a solution of only bicarbonates
P value = nil
•The P alkalinity is a measure of
Total hydroxide + 0.5 carbonate
•The M alkalinity is a measure of
(Total hydroxide +0.5 carbonate)+0.5
carbonate+Total bicarbonate
P and M alkalinity
Information which can be obtained from acid
titration can be summarized in the following
table:
Result of titration Hydroxyl Carbonate Bicarbonate
mg eq/l mg eq/l mg eq/l mg eq/l
• p=0,m>0 0 0 m
• 2p< m 0 2p m-2p
• 2p=m 0 2p 0
• 2p>m>p 2p-m 2(m-p) 0
• p=m p 0 0
Hardness
Hardness is normally due to the presence
of calcium and magnesium salts, though
iron, aluminium and manganese may be
present in small quantities and may
contribute to the hardness..
Temporary Hardness
The hardness due to bicarbonates is called
temporary hardness.
If a solution containing Ca(HCO3 )2
Is boiled , the calcium bicarbonate
decomposes completely.

## Ca(HCO3 )2 = CaCO3 +H2 O + CO2

Permanent Hardness
Anions other than CO32- and HCO3- are
normally also present e.g. SO4- and Cl-.
CaSO4, CaCl2, MgSO4, and MgCl2 do not
decompose when boiled,consequently this
part of the total hardness is called
permanent hardness.
Hardness
Total Hardness is the sum of temporary
and permanent hardness.
Classification Carbonate Non
hardness carbonate
hardness
Calcium hardness Ca(HCO3)2 CaSO4
CaCO3 CaCl2
Magnesium hardness Mg(HCO3)2 MgSO4
MgCO3 MgCl2
Silica
Formula:SiO2
Silica can be present as reactive and non
reactive form(colloidal silica).
Colloidal silica can not be removed by
water treatment .It will also not detected by
silica analyzers.At high pressure and
temperature condition non reactive silica
turns into reactive silica.
Silica
The total silica present in the boiler is
distributed between the steam and the
boiler water in a definite distribution ratio
which is a function of boiler pressure and
pH.
The vaporized silica in the steam get
deposited in the last stages of steam turbine
and reduces its efficiency and power
output. In general 20 ppb is the limit for
silica in steam
Corrosion Due To Oxygen

## Oxygen cause serious corrosion in steel.

Following reaction occur below 50 0C
Fe + 2 H2 O = Fe (OH)2 + H2
At temperature more than 500C iron oxide
converts into magnetite.
3Fe (OH)2 = Fe3O4 + 2 H2 O + H2
Corrosion Due To Oxygen
At still high temperature ranging from 220
0
C to 570 0C Magnetite is formed directly
3 Fe + 2 H2 O (Steam) = Fe3o4 + 4 H2
The magnetite film forms a protective layer
and prevents further corrosion.
Corrosion Due To Oxygen

## If oxygen is present in steam it will destroy

the magnetite layer.
4Fe + 2 n H2 O + 3 O2 = 2 ( Fe2O3 . n H2 O )
Ferrous oxide thus formed is non protecting
and causes corrosion.
Removal Of Oxygen
Deaeration is widely used for eliminating
dissolve gases from liquid.
In order to eliminate oxygen from boiler feed
water following two methods are applied.
1) Mechanical deaeration
2) Chemical deaeration
Solubility Of Oxygen In Water
Mechanical Deaeration
Two physical laws form the basis of
deaeration :
•Henry’s law – the amount of gas dissolve in
water is directly proportional to the partial
pressure of that gas in the vapour space above
the water / gas interface.
•Dalton’s law – the total pressure of a gas
mixture is made up of the partial pressure of
those gases and this are in direct relationship
to their volume ratios in the vapour space.
Mechanical Deaeration
Thus a dissolve gas can be removed from
water by reducing the partial pressure of
that gas in the atmosphere containing the
liquid.This can be done by changing the
atmosphere to that of another gas by
introducing a new gas to the system, while
the unwanted gas is vented.
Mechanical Deaeration
Steam is used as purge gas for the
following reasons:
•It does not contaminate the water
•Only a small quantity of steam is lost for
venting
•It heats the water and consequently
reduces the solubility of the undesired gas.
Chemical Oxygen Scavenging
Mechanical deaeration is combined with
chemical deaeration to remove last traces
of oxygen from boiler feed water.
Following two chemicals are used for this
purpose:
1) Sodium sulphite ( Na2SO3 )
2) Hydrazine ( N2 H4 )
Sodium sulphite
Sodium sulphite is used for boilers upto 40
barg and dosing is done on a continuous basis.
The chemical reaction is as follows:
2 Na2SO3 + O2 = 2 Na2SO4
Theoretically 7-8 ppm sodium sulphite is
required to remove 1 ppm of oxygen but in
practice dosing should be such that a residual
sodium sulphite level is maintained to ensure
the effectiveness of oxygen removal
Sodium sulphite
The speed of the sulphite oxygen reaction is
influenced by :
•Temperature – increasing temperature
increases the reaction rate.
•Presence of excessive Na2SO3 increases
reaction speed.
•pH: the reaction proceeds most rapidly at
pH values in the range of 9.0 to 10.0.
•Presence of catalyst increases the reaction
rate.
Sodium sulphite
Sodium sulphite is not recommended for
boilers operating above 40 barg because
at high pressure and temperature sodium
sulphite decomposes forming sodium
hydroxide thus increasing alkalinity.
Na2SO3 + H2 O = 2NaOH + SO2
The application of sodium sulphite also
increases TDS of boiler water.
Hydrazine
Hydrazine is used as oxygen scavenger for
boilers above 40 bar.The following reaction
occurs:
N2 H4 + O2 = N + 2 H2O
Theoretically 1.0 ppm of hydrazine is required
to neutralized 1.0 ppm of dissolve oxygen but
in practice 0.01 –0.05 ppm of residual hyrazine
is maintained for complete removal of oxygen.
Dosing is normally done on a continuous basis.
Hydrazine
Hydrazine also prevents corrosion by
helping in the formation of the desired
magnetite protective film:
N 2H4 + 6 Fe2 O3 = 4 Fe 3O 4 + N2 + H 2O

## ( ferric oxide , red ) ( magnetite , black )

At high temperatures hydrazine
decomposes to ammonia
2 N 2H4 2 N H3 + N 2
Hydrazine
The ammonia carried over with the steam
will neutralize CO2 and reduce return
condensate line corrosion , but in presence
of oxygen copper and copper alloys will
be attacked.
Hydrazine
Factors effecting deoxygenation efficiency of
hydrazine :

## •Temperature – hydrazine will remove

oxygen at an appreciable rate only at water
temperature greater than 100o C
•pH value – at pH value less than 7
hydrazine fails to prevent corrosion and even
intensify it.
Hydrazine

## Between pH value 9- 9.5 and temperature

373-380 K hydrazine in excess of 20 ppb
eliminates all dissolve oxygen
Hydrazine
Hydrazine
Benefits of using hydrazine
Limitations of using hydrazine
•Carcinogenic
•Causes corrosion to copper metallurgy
Aquatreat 9240
•Alternative of hydrazine.
•Oxygen scavenger
•Safe to use
•Effective at low temperature
•Superior metal passivator than hydrazine
Aquatreat 9240 reactions
•Oxygen scavenging reaction
2C4H8NOH + O2 = 2C4H8O + N2O + H2O

## •Metal passivation reaction

2C4H8NOH + 6Fe2O3 = 4Fe3O4 +2C4H8O +
N2O + H2O
Corrosion due to carbon dioxide
A relatively high CO2 content in feed water or
bicarbonate and carbonate decomposes and
releases CO2 under influence of heat and
causes severe pitting of the tubes and drum of
the boiler.
The carbon dioxide in steam may cause active
corrosion of turbines and return condensate
lines.Metal loss in condensate system caused
by CO2 can be reduced or eliminated by
neutralizing amines , filming amines and
hydrazine.
BFW specifications
Parameter Range

pH 8.5 –9.5

## Hydrazine 0.02-0.05 ppm

Boiler water specifications
Parameter Range
pH 9.4 – 10.0
Conductivity < 100
PO4 4.0 –10.0 ppm
SiO2 < 1.5 ppm
Na: PO4 2.3 –2.8
M alkalinity
P alkalinity
Superheated steam
specifications
Parameter Range

pH 8.5 – 9.5

Conductivity < 10

## SiO2 < 0.02 ppm

Corrosion vs Boiler pH
•The pH of BFW and condensate is kept
around 9.0 and for boiler water it is kept
around 9.5 –10.0
•pH of BFW is maintained by dosing
ammonia , morpholine or amines .
•pH of boiler water is maintained by
dosing phosphates or caustic.
Corrosion vs Boiler pH
Phosphate treatment
Ortho phosphates
Mono-, di-, tri- sodium phosphates
Poly Phosphates
Sodium hexa meta phosphate
Sodium hepta meta phosphate
Sodium tripoly phosphate
Tetra sodium pyro-phosphate
 Easy to monitor and control
 Does not require high purity makeup
 Used in high pressure Boiler
 Phosphate Chemistry Well understood
 Can handle feedwater hardness
variations
 Residual PO4 is non corrosive
 Large PO4 residual - buffer for excursions
 Relatively low cost ingredients
Phosphate treatment
 Produces precipitates in boiler water
 Excess alkalinity can produce corrosion
 May require more blowdown
 If so, more heat lost, more chemical
used
 Possibility of scaling
 Normally used with sludge dispersant
Phosphate-pH Controls

Co-ordinated Phosphate-pH
&
Congruent Phosphate
Co-ordinated Phosphate
• Control of pH comes from hydrolysis of
trisodium phosphate in water

in water

## • Does not ensure absence of caustic under

concentrating conditions, less solubility of
DSP
Congruent Control
•This program was developed to prevent
free caustic in boiler water during concent
rating conditions
•At sodium:phosphate ratio of 2.85 in
boiler water, precipitated solids have same
concentration
•Safe range is between ratio 2.3 - 2.6
•Control is based on pH and PO4 values.
Co ordinate phosphate / pH control
A safe boiler water pH value should be
achieved without producing measurable
residuals of caustic. Sodium phosphate salts
provide the desirable pH and also react with
rest hardness to form calcium and
magnesium phosphates , which precipitate
out as a non adherent sludge.
Mechanism Of TSP
Trisodium phosphate reaction:

## The Ca salt ( sludge) can be removed with the

boiler blow down.
CO ODINATED pH/PHOSPHATE CONTROL
pH

10.8
10.6 “Free” Caustic
MOLAR RATIO
Region 2.8 : 1
10.4 4 Na/PO 4
10.2
CONTROL BOUNDARY 3.0:1 Na/PO
10.0
2.7 : 1
9.8
Na/PO 4
9.6
9.4
2.6 : 1 cau TSP
9.2 Na/PO 4 CONTROL BOUNDARY 2.2:1 Na/PO4 MOLAR RATIOstic
9.0
DSP
8.8
Captive
8.6 Alkalinity
8.4 Region
MSP
blow down
8.2
1 2 3 4 5 6 7 8 10 15 20 30 40 50 60
ppm Orthophosphates, as PO 4
Phosphate treatment
Trisodium phosphate and disodium phosphate
reactions :
Na 3PO4 + 2 H2 O = 2 NaOH + NaH2 PO4
Na 2HPO4 + H2 O = NaOH + NaH2 PO4
In both the reactions considerable amount of
caustic alkalinity is produced .Caustic can not
concentrate beyond a certain level in the
presence of acid phosphate ions because as
the pH value rises the above reactions reverse
from right to left thereby removing caustic.
Phosphate treatment
Phosphate dosing to work it is essential
to have disodium hydrogen phosphate
available to combine with free caustic
to form trisodium phosphate.Thus the
dosing rate should be such that pH
value and phosphate concentration are
at a point should be below the curve in
which area only trisodium phosphate
and disodium hydrogen phosphate
coexist.
Phosphate vs pH curve
pH Boosters
•Ammonia ( NH3 )
•Caustic ( NaOH)
• Derivatives of Amines
•Cyclohexylamine
•Morpholine
Film Forming Amines
PROTECTIVE FILM BARRIER
AMINE FILM

N R
N R
N R

WATER
SURFACE
METAL

LEGEND
N R = AMINE MOLECULE
N+ = AMINO GROUP
R- = ALKYL GROUP
PROTECTION AGAINST OXYGEN
PITTING
Molecular Configuration
of Amine Film Size of Molecule

Oxygen
1A0
12A0

Triangular

Carbon Dioxide
14A0

5A0
Square
FILM FORMING AMINE

## Film forming amines are used to provide

protection from both carbon dioxide and
oxygen .The thin film forms a protective
barrier against carbon dioxide and
oxygen .
Filming amines are normally feed
Dispersing Amine
DISPERSION

Agglomeration
Dispersion
Neutralizing Amine
Neurtalising amines
Neutralizing amines are used to neutralize
carbon dioxide.
•The most commonly used neutralizing
amines are morpholine , diethylamino-
ethanol, cyclohexylamine and ammonia.
•The distribution ratio ( D.R)
of a particular amine plays an important role
in the selection of an amine.
Neurtalising amines

Amine DR
Morpholine 0.4
diethylamino-ethanol 1.7
Cyclohexylamine 4.0
Ammonia 10.0
Neurtalising amines
In order to neutralize CO2 the amine must be
present in the water phase.Ammonia has a
high DR and a significant amount will be lost
during the deaeration step. Morpholine ,
preferring the water phase is often applied
for systems where the major part of the
steam is used for turbine supply.Two or more
amines may be applied simultaneously .
Neutralizing amines are normally fed to the
Priming, Foaming and Carry over
Foaming
Foaming is the formation of stable foam on
the evaporating surface in the boiler drum.
Bubbles are formed continuously and
possess high surface tension .They retain
their shape even after their disengagement
from the water surface.
Foaming
Factors responsible for foam generation
are:
•High salt content in boiler water
•Presence of oils and grease in boiler water
•Presence of suspended sludge in a finely
dispersed state in boiler water
•High alkali concentration in boiler water
Priming
Priming is the infiltration of boiler feed
water into steam lines of the boiler drum

## Priming is the state of unstable foam

formation resulting in the discharge of
steam contaminated with excessive amount
of water droplets.
Priming
Causes of priming:

## •Sharp pressure drop in the drum because

of abrupt increase of steam load

## •Penetration of oil or alkali in the boiler

feed water in amounts exceeding the
allowable standard
Carry over
Boiler water solids are also carried over in
the moisture mixed with steam even when
there is no indication of priming or
foaming.This is known as carry over.It is
partly a chemical and partly a mechanical
problem.

## Steam washers and mechanical separators in

the boiler drum effectively control carry over
within reasonable and tolerable limit.
Carry over
Mechanical causes Chemical cause
• High water level • High TDS in boiler
• Incomplete separation water
of steam and water • High alkalinity in
• High steaming rate boiler water
• Boiler design • Leakage of organics or
• Uneven heat oil
distribution
Effects of carry over

## •Poor steam quality

Caustic embrittlement
Caustic embrittlement
Caustic embrittlement is the weakening of
boiler steel as a result of inner crystalline
cracks. This is caused by long exposure of
boiler steel to a combination of stress and
highly alkaline water.
Caustic embrittlement can be prevented by
eliminating free NaOH from boiler water.The
pH value of boiler water so controlled by
adding phosphates that any solid material
Caustic embrittlement
deposited is tri sodium phosphate and not
free NaOH.

## The another method is to add special

chemical inhibiting agents like sulphate
liquor, quebracho tannin and sodium
nitrate.
Phosphate hide out
Phosphate hide out is the precipitation fo
dissolve phosphates on spots with high local
surface temperatures and consequently high
local evaporation rates.In those locations the
concentration of the dissolve phosphates
exceeds the solubility limit and precipitates,
especially in the presence of porous
deposits.Excessive phosphate dosing rates to
maintain phosphate level in the boiler water is
an indication of phosphate hide out.
Phosphate hide out
Phosphate hide out tendency can be
checked by putting the boiler on a low
condition.This gives a higher solubility
of phosphate at a lower evaporation
rate .If the phosphate level in the boiler
water increases , this is an indication that
the boiler has phosphate hide out
tendencies.
Blow down
Blow down
Blow down is the removal from a boiler
unit or evaporator a fraction of the boiler
water either continuously or intermittently
in order to prevent an excessive
concentration of undesirable dissolve
substances in boiler water
There are two types of blow down :
•Continuous blow down
•Intermittent blow down
Blow down
From the salt balance of the system :

## Mass of salts entering a boiler unit

=
Mass of salts removed from the boiler unit
Blow down

## •Gfw = mass flow rate of feed water (t/h)

•Gs = mass flow rate of steam (t/h)
•Gbd = mass flow rate of blow down water
(t/h)
•Cfw = concentration of salts in feed water
•Cs = concentration of salts in steam
•Cbw = concentration of salts in blow down
water
Blow down

## Cfw Gfw = Cs Gs + Cbw Gbd

Blow down
Blow down is to be accurate because:

## •Blow down means loss of water

•Blow down means loss of heat
•Blow down means loss of fuel oil
•Blow down means loss of money
Flash type blow down
The blow down flash tank is maintained at
a pressure considerably lower than the
boiler pressure and because of this pressure
difference a fraction of blow down water
gets evaporated in the flash tank.This flash
steam can be used for deaeration purpose.
Flash Type blow down system

Boiler drum

Steam vent
Regulating
valve
Flash tank

drain