INSTITUTE OF ENGINEERING TECHNOLOGY - KATUNAYAKE

1.1.4 WATER TESTING AND TREATMENT

It is important to control the hydrogen ion concentration of water to

minimize corrosion as it makes water acidic when the PH value is low
(discussed in the previous lecture see notes.)
Chemical additives can be added to condition the water in order to
reduce the acidity ie hydrogen ion concentration and hence the ph
value. Acids lower PH value alkalis increase ph value.
To give alkalinity to water the most common additives used are. Sodium
hydroxide caustic soda or sodium carbonate and Ca(OH)2
It is been studied in oxygen must be present to accomplish the formation
of metal oxide therefore it is very important to reduce the amount of
oxygen in the water whether it is a cooling water system or boiler water
oxygen comes mainly from the air and de aeration can be achieved by
mechanically or chemically or a combination of both.
Mechanical method may be accomplished by using an air ejector in the
system.
Chemicals used for oxygen scavenging and deaerating the water, are
usually sodium sulphite or hydrazine.
Sodium Sulphite + Oxygen

Sodium sulphate

2Na2SO3 + O2
2Na2SO4
When added to boiler water the sodium sulphate which is formed
remains in solution under normal conditions causing no problems.
(Increase boiler water density disadvantage)
Use of Hydrazine solution (60% hydrazine 40% water approximately)
Hydrazine + Oxygen
Water + Nitrogen
N 2 H 4 + O2
2H2O + N2
Advantage of using hydrazine does not increase boiler water density.
(Hydrazene reacts with any metal oxide therefore a controlled excess is
beneficial)
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It is important to know the salts presenting natural water
and
evaporated as it is widely used for cooling of man machinery and as
make up feed for low pressure boilers.
The salts dissolved in natural water are metallic salts of sodium,
Magenesium, Calcium.
The standard method of measuring the metallic salt content parts per
million or P.P.M.
FRESH WATER SAMPLE ANALYSIS

SALT

SYMBOL

P.P.M.

Sodium Chloride

Na Cl

50

Sodium Nitrite

Na NO3

35

Magnesium Sulphate

Mg SO4

30

Calcium Sulphate

Ca SO4

90

Calcium Carbonate

Ca CO3

200

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ANALYSIS OF SEAWATER
Average sea water contains approximately 32,000 p.p.m. of total
dissolved solids.
Salt

Chemical
Symbol

Sodium chloride

Approximate %
of total dissolved
solids

p.p.m.

79

25,000

Nacl

Magnesium Chloride

Mg Cl2

10

3,000

Magnesium Sulphate

Mg SO4

2,000

Calcium Sulphate
Calcium Bicarbonate

Ca SO4

Ca (HCO3)2

Less than 1

1,200
200

HARDNESS SALTS
Alkaline Hardness salts are
Hydroxides
Carbonates

Calcium
of

Magnesium

Bicarbonates

Bicarbonates of calcium and magnesium are called temporary

hardness. Because they are decomposed by heating or boiling the
water boiling they liberate carbon dioxide CO2 and leave the
carbonates.

Calcium Bicarbonate.

Ca[HCO3]2

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Calcium carbonate

Calcium carbonate + Carbon dioxide + water

Calcium carbonate has a low solubility and solubility decreased as temp

increase it can therefore form scale.
Non Alkaline or permanent hardness salts are the chlorides, Sulphates,
Nitrates due to these salts is not removed by boiling or heating the salts
can be removed by chemical treatment.
Total hardness is therefore is the sum of alkaline and non alkaline
hardness.

SCALE FORMATION AND SLUDGE FORMATION

Steam bubble is formed upon the heating surface the plate under the bubble
overheats as it is insulated momentarily from the water.
The water containing salts is in contact with the periphery of the bubble. If the
salts are those which decrease in solubility as temperature increases.

Bubble

Periphery of
bubble overheats

Overheating

Moment
insulation
from water

They are deposited in the form of

a crystal ring. This is because the
water is supersaturated locally
with the salts.
When the bubble bursts the
water comes in contact with the
plate overheated plate, local
overheating occurs and more
salts are deposited.

Therefore salts whose solubility decrease with increase of temp are those
which form scale upon heating surfaces and sludge upon the cooling surfaces.

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Salts whose solubility increase with increase in temp do not

normally form scale upon heating surfaces. But sludge may be
formed if their saturation point is reached.

EFFECTS OF USING SEA WATER AS BOILER FEED WATER

As studied earlier sea water contains following. Dissolved solids, ie
sodium Chloride - Nacl, Magnesium Chloride Mg Cl 2, Magnesium
Sulphate, Calcium Sulphate, Calcium Bicarbonate Ca(HCO3).
Sodium Chloride (NaCl)
Heavy concentrations Solubility Variable
-

Cause foaming and priming

Increase of temp and Pressure

Solution Of Each Salt Is Variance With Tem

Some chlorides some not of solution
2Na Cl2 + Mg SO4
Mg Cl2 + Na2SO4
Mg Cl2 insoluble under normal boiler conditions.
Mg Cl + 2H2O
Mg (OH)2
HCL

Mg (OH)2 + 2H Cl
Low Solubility

can deposit and form scale

Can cause corrosion

2 HCL + Fe

Fe CL2 + H2

Fe Cl2 + 2 H2O

Fe (OH)2 + 2HCl

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Corrosive Cycle continues
Magnesium Sulphate (Mg SO4)
Soluble under normal boiler conditions
If density too high
Nacl + Mg SO4

Deposit form scale

Mg Cl2 + Na SO4

Calcium Sulphate (Ca SO4)

Most dangerous -

Forms scale - Tenacious & Hard

Effects heat transfer - Failure of heating surface.

Calcium bicarbonate (CaHCO3)
Decomposes when heated
Ca(HCO3)2
CaCO3 -

CaCO3

+ CO2 +H2O

Has low solubility decreases with increase of temp can form scale
(soft and porous) not be bad as CaSo4 when heat transfer is
concerned.

Fresh water as boiler feed water

It is better than using sea water as the dissolved salts are much less than in
sea water chance of forming and priming reduced hardness salts will cause
scale formation to a lesser much degree than sea water. (Most low pressure
boilers use fresh water for their feed).
Distilled water as feed water
Obviously very much less dissolved solids (must for high pressure boilers. With
high evaporation rates etc.)

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(Blowing down of boiler regularly)

THE PRINCIPAL OBJECTS OF BOILER WATER TREATMENT

(1).

To prevent scale formation in boiler and feed system.

(a). Using distilled water (B) Precipitating all scale forming salts
into the non adhering sludge.

(2).

To prevent corrosion in the boiler and feed system by maintaining

the boiler water in an alkaline condition and free from dissolved
gases.

(3).

To control the sludge formation and prevent carry over with steam.

(4).

To prevent foreign matter entering the boiler oil, waste, mill scale,
iron oxide, copper particles sand, weld spatter.

Before pre commissioning clean well

Watch the drains
Do not allow corrosion in condensate system.

PHOSPHATE

TREATMENT

3CaCO3
3Na2CO3

2Na3PO4

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Ca3(PO4)

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Calcium Carbonate + Tri Sodium phosphate

3CaSO4

+2Na3PO4

Calcium sulphate + Tri Sodium phosphate

3CaCl2

+ 2Na3PO4

Calcium Chloride + Tri Sodium phosphate

Mg SO4

+2Na3PO4

Calcium sulphate + Tri Sodium phosphate

Calcium
Phosphate

Sodium
carbonate

Ca3(PO4)2 +
Calcium
Phosphate

3Na2SO4

+
Sodium
sulphate

Ca3(PO4)2 +

6NaCl

Calcium
Phosphate

+
Sodium
chloride

Mg3(PO4)2 +

3Na2SO4

Magnesium +
Sodium
Phosphate
Sulphate

By using in sodium phosphates sodium carbonate is formed. Due to the sneak

down of the sodium carbonate sodium hydroxide is essentially formed and their
makes the water moderately alkaline.
Tri Sodium phosphate is directly add to the boiler since they are guide to
react and could form scale in the feed water system.
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Other phosphate Sodium Hecata phosphate
Sodium Phosphate
Di Sodium phosphate Poured directly into
Tri sodium phosphate the BLR.
Due to the calcium removal by the phosphate the tendency for these silicate
present at the water to form scale is greatly reduced. They tend to remain in
solution.
Phosphate treatment is suitable for low as well as high pressure boilers.
LIME

AND SODA TREATMENT.

Internal softening : Traditionally this is achieved by Injecting lime - Ca(OH)2

and soda
Soda may be in the form of Na2 Co3 or caustic soda NaOH
Lime react with temperarory hardnes salt
Soda react with permanent hardness salt.
These chemicals are used in conjunction with the suitable coagulants such
as starch and tannin to condition the sludge finaly to form a flocculent flock.
Sodium aluminate is used to remove the traces of oil from the boiler if
such contamionation has taken place.
.

The density gives an idea of the total dissolved solids.

An electric salinometer may also be used.
The range of scales are,
TYPE OF BOILER
WATER TUBE

PRESSURE

SCOTCH VERTICA
upto
17.5-31.5 31.5-42
~
17.5 bar
bar
bar
PPM

PPM

PPM

PPM

PPM

42-60

60-84

bar

bar

PPM

PPM,

ALKAIANITY TO
PHINOPTHALIN
ENOLF IN FHA-

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300-700 300-500 150-300 150-300 100-150 50-100

50-H

CAUSTIC
ALKALINITY

150-500

150-400

75-200

100-250

50-1.00

40-60

40-60

3000

INO

300

150

I50

50

30

7000

3000

1500

1000

500

500

300

50-100

50-100

50-100

50-100

20-50

0.1-1.0

0.1-1.0

10-50

20-30

CHLORIDES
(MAX.)
DISOLVED
SOLIDS (MAX.)
HARDNESS(MAX.)
SULPHITE

or
HYDRAZINE
PHOSPHATE

30-70

30-50

BOILER WATER TESTS

Boiler water should be regularly tested and the treatment of the boiler water
should be conducted according to the results obtained from the tests.
For low pressure boilers such as the multitubular Scotch, verti cal Cochran or
thimble tube, salinometer and litmus papers are still frequently used as
testing equipment.
Salinometer
The range of the scale is normally from 0 to -J~ and when the salinometer is
floating in pure water at 93C which has a relative density at that
temperature of unity, the salinometer reading is zero. When the
salinometer is floating in solutions of common salt at 93C the salinometer
reading is -A7 (approx. 32,000 p.p.m.) when the relative density of the
solution is 1.025. (The relative density of salt water at 93C is
approximately 1.025 or- on the salinometer.)

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If sea water is used as make up feed for low pressure boilers it is
recommended that the boiler density should be maintained as close as
possible to A- (approx. 125,000 p.p.m.). This would be attained by resorting
to blow down. The use of sea water as make up feed for boilers should be
avoided as far as possible, but if it has to be used a certain amount of
protection for the boiler can be provided by using soda ash.

Litmus Papers
These are used to ascertain the degree of acidity or alkalinity of the water. A
litmus paper when inserted into a sample of boiler water may change colour,
turning blue if the water is alkaline, or red if the water is acidic. The degree of
colouration is a very rough indication of the pH value of the boiler water.
For accurate testing of the boiler water, the foregoing salinometer and litmus
paper methods are inadequate. Table 4.9 gives recommended values for low
and high pressure boilers, to ascertain whether these values are being
maintained, more refined testing methods are used.
Alkalinity
Tests for alkalinity are as follows:
(1) Alkalinity to Phenolphthalein
Take 100 ml sample of boiler water,
add N/ 50 sulphuric acid to clear the sample.
Calculation: ml of N/ 50 acid used x 10 = P-P- In- CaCO3

Phenolphthalein is less alkaline than hydroxides or carbonates, and when it is

added to a sample containing hydroxides and or carbonates it will turn pink in
colour. The acid used after this colouration will first neutralise the
hydroxides, forming salts, it %~ III then react with the carbonate molecules
present forming bicarbonate molecules. Bicarbonate molecules are less
alkaline than phenolphthalein, hence, the pink colouration will disappear
once all the hydroxides and carbonates have been dealt with by the acid. One
bicarbonate molecule is formed from two carbonate molecules, hence in the
test the quantity of acid used is a measure the alkalinity due to the
hydroxides (caustic) present and half the carbonates.
(2).

Total alkalinity
Take alkalinity to phenolphthalein sample,

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add 10 drops of methyl-orange, result yellow colouration, add N 50
sulphuric acid until pink
Calculation: ml of N / 50 acid used for both tests x 10 = p.p.m. CaCO3.

(3) Caustic Alkalinity

Take 100 ml sample of boiler water,
add 10 ml of barium chloride,
add 10 drops of phenolphthalein, result pink colouration, add N; 50
sulphuric acid to clear the sample.
Calculation: ml of N / 50 acid used x 10 = p.p.m. CaCO3.
In this test barium chloride is first added to the boiler water sample in order
to precipitate all the carbonates which are present. The test is then carried out
as for the alkalinity to phenolphthalein test but in this case only the hydroxides
(caustic) will be measured.

Chloride Test
Take alkalinity to phenolphthalein sample,
add 2 ml of sulphuric acid,
add 20 drops of potassium chromate indicator,
add N / 35.5 silver nitrate solution until a brown colouration
results.
Calculation: ml of N / 35.5 solution used x 10 = p.p.m. C1
or ml of N / 50 silver nitrate solution used x 10 = p. p.m. Ca CO3

Sulphite Test
Take 100 ml of boiler water sample,
add 2 ml of sulphuric acid,
add 1 ml of starch solution
add potassium iodide-iodate solution until sample is blue in colour
Calculation: ml of iodide-iodate solution used x 12.5 = p.p.m.
Na2SO3.

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Phosphate Test
Take 50 ml of hot water sample,
add 4 grams of potassium nitrate crystals, put 25 ml
of the above into a test tube,
stand test tube in a water bath at 38 to 40C, add 5 ml
of ammonium molybdate reagent.
A sample of boiler water which contains sodium phosphates
and dissolved potassium nitrate will turn cloudy when ammonium
molybdate is added. This reaction to produce a cloudiness in the
sample is quicker the larger the quantity of phosphates present.
If the cloudiness does not result until after five minutes have
elapsed, the phosphate reserve in the boiler water is too low
(below- 20 p.p.m.). If the cloudiness results before two minutes
have elapsed, the phosphate reserve is too high (above 70
p.p.m.). It will be appreciated that the sample of boiler water
must be hot in order to dissolve the crystals.
Hardness Test
Take 100 ml of boiler water sample,
add 0.2 ml at a time, standard soap solution,
shake vigorously after each addition of soap until a lather
persists for at least five minutes.
Calculation: ml of soap solution used x 10= p.p.m. CaCO3
equivalent.
pH Value
A boiler water's pH value can be obtained by three basic methods.
(1) Litmus papers.
(2) Colourl metrically.
(3) Electrolytically.
The litmus paper method has already been described but the test does not
give a very accurate pH result, indicating merely if the water is acidic or
alkaline. Tests (2) and (3) however give a reasonably accurate pH value
Total Dissolved Solids
These are ascertained by use of a hydrometer or electrical conductivity
meter.
Hydrometer: vdrometer: Usually graduated in grains per imperial gallon (to convert
grains per imperial gallon to p.p.m. multiply by 14.3). Care must be taken
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when using the hydrometer to account for the water meniscus and to
ascertain accurately the temperature of the sample. Temperature correction
tables for the hydrometer are usually supplied with it.
Conductivity Meter: A portable, battery operated, electrical conductivity
meter is used in this test. The removable conductivity cell is washed out and
filled with a treated boiler water sample (treatment consists of cooling to
15 to 20 C, adding phenolphthalein and removing pink colouration
with acid). The filled cell is plugged into the meter, its temperature
checked and the temperature control set to correspond. A range switch is set
to approximate range of reading expected, then a central control is operated
until 'null' balance of the electrical bridge circuit (the cell forms one
resistance) is achieved. Position of the central control indicates the
total dissolved solids in the water usually in p.p.m. but it may be
conductivity in micromhos (to convert; p.. p.m. total dissolved solids =
conductivity in micromhos x 0.7)

WATER SIDE ATTACK IN DIESEL ENGINES.

Great importance is attached to the need for water treatment and it is

recommended that specialist advice is always taken to protect engine from

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damage that can be caused by the use of untreated water in engine spaces,
where damage has occurred but is only correct water treatment can be
expected to arrest it. For modem large slow speed two stroke engine the
builder recommend to use evaporated water. Evaporated water has a l o w
salinity,
w h i c h c a n p ro v i d e t h e l i n e r s u r f a c e w i t h a protective
coating.
Cast iron cylinder liners and jackets are subjected to the following forms of
attack.
I.

Corrosive attack
2. Galvanic attack
3. Cavitations erosion
4. Velocity erosion or impingement attack
Corrosive attack
This results from the use of unsuitable coolant and/or the incorrect application
of the water treatment. The presence of free or dissolved oxygen will
accelerate the attack. The pH value of coolant is of particular importance,
acidic waters with pH below seven will attack ferrous metals and
alkaline waters with pH above 9 will attack aluminum alloy. Presence of
free carbon dioxide can also cause this form of attack. CO2 is released when
dissolved by carbonate are heated above 710C.

Galvanic action
This occurs between dissimilar metals unsuitable water conditions.
Cavitations erosion.
It is the result of vibration of the cylinder liner wall. This cause the
collapse of small air or vapor bubbles and subjects the wall to localize
hydraulic hammering. This form of attack is usually confined to the thrust
face of the cylinder wall. Attention must be paid to over come the cause
of abnormal vibration excessive piston slap may also cause this attack.

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Velocity erosion
This can result from excessive coolant velocity created by restriction in
the water system. This is aggregated by the presence of abrasive particals.
Cylinder heads
Corrosion of the cylinder head water spaces will invariably result from
untreated Water. The resulting reduction in material section can result in
fatigue cracking allowing leakage of water into the combustion space
cylinder head cracking can also be caused by local overheating due either
to the deposition of scale, loss or reduction of water circulation or retention
of air in the coolant passages in the head.
It is essential that water treatment be employed in all engine cooling
system as soon as the engine goes into service. Some inhibitors provide
chemical protection and pH control while others deposit a protective film
on the waterside surfaces. Some inhibitors contains anti-freeze chemicals
like sodium benzoate or sodium nitrate.
The instruction supplied with an inhibitor must be strictly adhered to
particularly in respect to dosage/ strength. The presence of chlorides in
the water can greatly aggravate corrosion. Normally the maximum limit
of 250-300 ppm should be observed and better if it is less than 100 ppm.
Mechanical consideration.
If piston or ring clearances are allowed to become excessive increased
vibration of the cylinder walls may result in acceleration of cavitations attack.

Hard water
Hard water contains salts in solution and when heated these salts come out
of solution to forma hard deposit of scale in the jackets and cylinder heads in
the engine.
Control of acidity and alkalinity
Sodium benzoate and sodium nitrite both these compounds have good
corrosion inhibiting properties. But their efficiency is very much improved
when employed in combination/. They form an invisible film of insoluble
products on the surface.

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Sodium Nitrite and sodium silicate

Here sodium nitrite provides protection of cast iron and steel and sodium
silicate prevents attack on soldered joints.
Soluble oils:
This is a special anticorrosion oil which is completely immulsifiable in water
and acts as a corrosion inhibitor. When introducing soluble oil to an engine
already in service it is very essential to ensure that all rubber hoses are
nitrite lined and other rubber joints and seals in contact with the coolant are
of nitrite rubber.
Recommendation for scale and corrosion control in diesel engine
cooling system;
Present practice is to reduce the risk of scale formation and corrosion attack in
cooling systems using a combination of acceptable quality cooling water
and a suitable corrosion inhibitor. If hard water is Used calcium scale
deposits, which can accumulate and act as an insulator, which may
cause overheating resulting in excessive cylinder liner wear and possible
fracture corrosion may also cause serious damage to cylinder jackets,
piping, pumps etc. The water used in the engine should not have hardness
contain as calcium carbonate above 100 ppm and the chloride contain or
the sulphate contain should not exceed 50 ppm.
There are three corrosion inhibitors, which are suitahle.1br engines.
1. Nitrite Borate
2. Chromates
3. Soluble oils.
Nitrite borate has the following advantages.
n Effective inhibitor with no increase in corrosion caused by, over or under

treatment.
n Dosage concentration easily determined by simple test.
n It is safe to handle, will not cause skin deceases.
n Approved for diesel engines when water is used as a heat source in fresh

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water generators.
n Acts as pH buffer against leakage of combustion gases in to the cooling
water.

The disadvantages are.

This mixture cannot be used in galvanized pipe work or if sacrificial zinc
anodes are fitted. Also it attacks soft solders.
Chromatic has the following advantage
n Very effective inhibitor.
n Concentration easily determined by color
n Can be used in presence of zinc coating or sacrificial anodes.

The disadvantages are

n Must be handle with caution to avoid skin contact.
n
n
n
n

Low concentration will promote pitting attack

Can not be used if the engine water is used in a freshwater generator
Poisonous, therefore care must be taken when dumping
Foes not act as pH buffer.

Soluble oils has the.f6flowing advantages.

n Safe to handle
n Approved for engines where water is used in fresh water generators.
n Reduce cavitations effects
n Gives good protection on clean metal surfaces.

The disadvantages are.

n If water quality is not good, the emulsion can loose stability and oil gets

separated out.
n The system must keep absolutely clean.

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n Tendency to form beat insulating layers of solid substances with

separated oil acting as bonding agent.

n High concentration can cause overheating.
n Foaming may take place if water has very low hardness.

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