AND POWER STATION

,. ..... R TREATMENT
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NEW AGE INTERNATIONAL (P) LIMITED, PUBLISHERS
Industrial and Power Station
Water Treatment .
K.S. VENKATESWARlU
Former Head
Water Chemistry Division
Bhabha Atomic Research Centre
Bombay
Copyright © 1996, New Age International (P) Ltd., Publishers
Published by New Age International (P) Ltd., Publishers
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PREFACE
After my long association with the Bhabha Atomic Research Centre, Trombay,
several colleagues suggested that I should write a book on Water Chemistry,
considering my deep involvement with the development of this subject. Since I
felt that writing a book would be no easy task, I deferred it. Three years later
during my recovery from surgery, which restricted my outdoor movements my
wife persuaded me to start this task. In deference to her wishes and that of
other friends, I made a beginning and soon found that MIs Wiley Eastern Ltd.
would be willing to publish it. From then onwards, there wns no going back and
the result is this monograph, "Water Chemistry and Industrial Water Treatment."
Around 1970, it was realised in the Department of Atomic Energy, BARC
and Power Projects, that water chemistry research and development is essential
for the smooth and safe operation oflndia's nuclear power reactors, as they all
make use of light or heavy water as the heat transfer medium at high tempera-
tures and pressures. To co-ordinate the effort, a Working Group on Power Re--
actor Water Chemistry (PREWAC) was set up, which was later transformed
into a Committee on Steam and Water Chemistry (COSWAC). I was associated
with this effort from the beginning as the Convenor, PREW AC, Member-Secre-
tary COSWAC and subsequently as its Chairman until the end of 1989. The
International Atomic Energy Agency, refle,cting the world wide emphasis on
this subject in the nuclear industry, conducted several co-ordinated Research
Programmes on' Water Chemistry in Nuclear Power Stations during the 80s. I
was privileged to be associated with this effort on behalf of the Department of
Atomic Energy. In terms of infrastructure, BARC has set up a dedicated Water
and Steam Chemistry Laboratory at Kalpakkam (Near Madras). In addition to
chemical programmes, studies on marine biofouling were also initiated. These
experiences have given me a close feel for this interdisciplinary subject.
The Central Board of Irrigation ane Power, New Delhi has also indentified
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ACKNOWLEDGEMENTS
The author acknowledges, with thanks, the permission readily and gracioasly
given by:
The Central Board ofIrrigation and Power, New Delhi, India for making use of
technical information and data inclusive of some figures from their reports cited
at the appropriate places.
MIs. Nuclear Electric, Berkeley Technology Centre, United Kingdom for Fig.
Nos. 3.1 and 4.4,
MIs. Vulkan-Verlag GMBH, Germany for Fig. No. 4.3,
American Power Conference, USA for Fig. Nos. 4.6, 4.7, and 4.8,
Power (an international journal), USA for Fig. No. 5.1 and
National Association of Corrosion Engineers, USA for Fig. No. 9.2.
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TABLE OF CONTENTS
Preface v
Acknowledgements
v;;
List of Figures xi
List of Tables xiii
1. Introduction
2. Physico-chemical Charcterstics of Natural Waters 5
3. Properties of Water at High Temperatures and Pressures 19
4. Water Chemistry, Material Compatibility and Corrosion 26
S. Treatment of Natural Waters for Industrial Cooling 39
6. Demineralisation by Ion Exchange 56
7. Water Chemistry in Fossil Fuel Fired Steam
Generating Units 69
8. Steam Quality Requirements for High Pressure T'lJ'bines 86
9. Special Problems of Water Chemistry and Material
Compatability in Nuclear Power Stations 93
10. Geothermal Power and Water Chemistry 111
11. Analytical Techniques for Water Chemistry Montoring and
Control 120
12. Effluent Treatment and Water Conservation 127
Index 137
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LIST OF FIGURES
Fig. No.
3.1
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
5.1
5.2
6.1
6.2
6.3
7.1
9.1
9.2
Title Page No.
Plot of pK w of water vs temperature 24
Mechanism of the first step in iron corrosion 27
Possible species of iron under aqueous environment 28
Solubility of magnetite in the pH range of 3 to 13 30
Solubility of magnetitie at 300°C vs pH300 30
Conceptual representation of electrical double layer 31
Ray diagram of carry over coefficients of salts and
metal oxide contaminar..ts in boiler water 33
Caustic solubility data shown on P, T coordinates 34
Caustic solubility data shown on a Mo!;:"r diagram 3S
Dissociation of HOCI and hOBr as a fUHction of pH 41
Important problem areas in cooling water system 48
Sodium contamination in mixed bed J;egeneration 63
3 - resin mixed bed 64
Stratified bed 64
Simplified water - steam circuit in a power plant 70
Corrosion and deposition processes in water cooled
nuclear power reactors 97
Stress corrosion cracking of stainless steel 99
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LIST OF TABLES
Table No.
2.1
2.2
2.3
2.4
2.S
2.6
2.7
2.8
2.9
2.10
2.11
2.12
3.1
3.2
3.3
3.4
3.S
3.6
3.7
4.1
4.2
4.3
4.4
S.1
6.1
TItle
Water quality vs total dissolved solids
Chemical constituents of significance in natural
waters
Pale No.
6
Constituents of drinking water having significance
to health
WlIO guide lines (1984) for aesthetic quality of
drinking water
Specific conductivity vs water quality
Hardness vs water quality
Classification of natural waters
Example of river water monitoring in Andhra
Pradesh
Saline water intrusion into coastal wells in Kamataka
Chemical composition of some brine waters, Haryana
River water analysis with seasonal variations as used
by electricity generating industry, India
Typical analytical data of impounded raw water
from a reservoir, India
Thermophysicai properties of water
Changes in surface tension and viscosity of
water with temperature .
Thermophysical parameters of water as a function of
temperature and pressure
Variation in the properties of water with temperature
and pressure
Density of water: variations with temperature and
6
8
8
11
11
13
14
IS
IS
16
17
20
20
21
22
pressure 23
, Specific conductivity of water at different temperatures 23
Changes in pH of water, ammonium and lithium
hydroxide solutions as a function of temperature
PZC values of some corrosion product species
Distribution of silica between steam and water phases
Relationship between pH values at 2SoC and
concentration of alkali sing agents
Thermal decomposition ofhydrazine
Solubility trends among scale forming calcium salts
Characteristics of standard ion exchange resins
24
32
3S
36
37
SO
60
xiv
List o/Tables
Table No. Tide Page No.
6.2 Comparison of mixed bed performance 67
7.1 Water quality specifications for low pressure boilers 73
7.2 Water quality limits (max.) of medium pressure boilers 74
7.3 Reference data for conventional co-ordinated
phosphate treatment 76
7.4 pH vs percentage of different species of phosphate 77
7.5 Reference data for low level co-ordinated phosphate
treatment for high pressure boilers 78
7.6 Solubility of trisodium phosphate as a function of
temperature 78
7.7 Electric Power Research Institute, USA
(EPRI) guidelines for make up water and condensate 81
7.8 Central Electricity Generating Board, UK
(CEGB) specifications for high pressure-high heat
flux boilers cooled by sea water 82
7.9 CEGB primary targets for once-through boilers 84
8.1 High pressure steam quality specifications 87
8.2 Turbine part failures-US industry eXperience 89
8.3 Maximum permissible concentration of silica in boiler
water 90
8.4 Guidelines for reheat steam 90
8.5 Steam purity limits in industrial turbines 91
9.1 Feed and reactor water specifications for boiling
water reactors 99
9.2 PWR reactor water quality specifications 101
9.3 VVER-400 reactor water quality specifications 101
9.4 Chemical control specifications for PHT system in
PHWRs 104
10.1 Geothermal locations in India 112
10.2 Growth of installed capacity of geothermal power 112
10.3 Composition of some geothermal steam and water
phases 113
10.4 Characteristics of some geothermal steam and water
phases 114
10.5 Corrosion characteristics of geothermal fluids 115
10.6 Corrosion studies- with reference to H
2
S abatement
by iron catalyst 116
10.7 Surface corrosion rates of materials in contact with
geothermal fluids
117
12.1 Tolerance limits for discharge as per Indian standards 131
12.2 Water requirements for industrial operations
132
12.3 Water consumption in a shore based steel plant 133
12.4 Chemical contaminants in the waste water from a
coke oven plant
134
12.5 Examples of the efficacy of wet air oxidation 134
1
INTRODUCTION
In her engrossing pictorial volume titled "Eternal India", Mrs. Indira Gandhi
quotes a translation of Rig Veda's "Hymn of Creation" thus:
"Then even nothingness was not, nor existence. What covered it 1 In whose
keeping 1 Was there cosmic water in depths unfathomed ? '" All of tliem was
unillumined water, that one which arose at Jast, born of the power of heat."
The association of water with he.at..energy dates back to hundreds of miJJion
of years, if not to two billion years. There was a time in the very distant past
when the earth and its environment were so different from what we experience
now. It was a time when the atmosphere was not very dissimilar to the
composition of the gases emanating from volcanic eruptions and contained much
water vapour. A time when the north east comer of present day South America
fitted snugly into West African coast. It was a time when the isotopic composition
of uranium (U) was such that the more easily fissionable U-'23S was about 3 per
cent and not the present value of 0.7 per cent. As the temperature of the earth's
surface cooled down to below l00
o
C, water vapour in the atmosphere started
to condense and there were "rains". Rain water began to accumulate and flow
over the surface of the earth. When this happened over an area now known as
Oklo in Gabon, W. Africa, the water streams surrounded the "Jow enriched"
uranium mineral deposits and a nuclear fission chain reaction ensuec1, releasing
considerable quantities of energy. When the surrounding water evaporated due
to the heat generated by the fission process, the chain reaction stopped, since
water which acted as a neutron moderator was lost. Subsequent "rains" would
restore the chain reaction. This pulsating system, known as the Fossil Nuclear
Reactor, generated about 1 011 KWH of thermal energy. This was at a time when
there was no fire as there was no vegetation. Neither were there combustible
gases such as hydrogen or methane in the atmosphere, which was any way not a
supporter of combustion due to its low oxygen content.
2
Water Chemistry
Skipping over the chasm of two billion years, to April 1986. it was tho
short supply of cooling water relative to the accidental production of excess
heat energy in the Chernobyl nuclear reactor No.4 in Ukraine, which led to the
world's worst nuclear accident. Unlike at Oklo, in the Chernobyl plant in
addition to low enriched uranium, a combustible material, graphite, and the
metal zirconium were available in plenty. While graphite caught fire, zirconium
reacted violently with the high temperature steam, hydrogen that
combined with oxyt;en leading to a devastating explosion. There was al.o
speculation that contact of high temperature water with the molten co(e of
uranium oxide led to a steam explosion in parallel with the hydrogen burn.
Thus, the power of heat and the power of water are always competitive as
well as complementary. Their safe co-existence in modern industrial systems
having multi metal surfaces, is the subject matter of this monograph.
In nature, the purity of water varies all the way from relatively pure rain
water to sea water with high salt content. Even in the case of rain water,
depending upon the location and the prevailing environmental conditions in
the atmosphere, some impurities such as dissolved gases, (oxides of nitrogen
and sulphur), are present. With heavy industrialisation, one hears of "acid rain".
Theoretically, pure water is characterised by as Iowa conductivity as pOllible,
the limit being dictated by the dissociation constant of water at that temperature-.
At 200C the theoretical conductivity of water is 0.05 micro siemens per em
(j1S/cm). At this limit, the only "impurities" would be the hydrogen and hydroxyl
ions formed as a result of such a dissbciation. Thus, high or ultra pure water is
only a laboratory curiosity and in nature a rain drop in a clean atmospheric
environment is the neareJ;t to such an ideal. Once rain falls on the earth's surface,
the water becomes loaded with dissolved impurities leached from the surface
and the subsurface as the rain water percolates into the soil. Surface waters
such as rivers and lakes have relatively less dissolved solids, as compared to
ground waters such as bore wells. Geothermal waters have a high salt content
as well as dissolved gases. Sea water contains the maximum content of dissolved
electrolytes, specially sodium chloride. There are many examples of rivers
picking up impurities as they flow over different terrains, so that if at one place
calcium (Ca) is more than magnesium (Mg) at another location, it might just be
the reverse. The level of dissolved salts in natural waters is important since it
determines the use to which the water is put, viz., drinking, agriculture,
horticulture, health spas, etc. Different facets of the physical and chemical
characteristics of natural waters are reviewed in this book.
The basic physico-chemical properties of water are dependent upon the
temperature. As is well known, water can be kept in the liquid phase even above
100°C by the application of pressure. Thus, high temperature water (say at
27S°C) jmplicitly means that it is also under high pressure. If it is in a boiling
condition, it will be a two phase system. Being under pressure also means that
water or a steam-water mixture at high temperatures will always be a closed
system.
In general one might say that water becomes an aggressive fluid at high
temperatures. The information that is needed to appreciate this added
aggressiveness needs to be discussed. The consequential problems of material
compatibility and corrosion in high temperature water and steam are of extreme
Introduction 3
importance in the smooth functioning of the steam generating industry. The
role of dissolved electrolytes, either added intentionally or picked up from
or through unexpected contamination IS equally relevant. Surface
oxidation, release of corrosion products and their subsequent redepositi.on
depends upon the changin"g thermal and chemical environment. These are of
special importance in nuclear power stations.
, The largest volume of water used in the industry is for cooling in chemical
processes. Process-water heat exchangers and cooling towers are employed for
1his task. Depending upon the source of water and the seasonal variations in its
composition, a cooling water treatment prbgramme is adopted, which is
compatible with the materials employed in the circuit. On the other hand, power
plants employ water for cooling the condensers, These are generally once-
\through systems, although the use of cooling towers.to dissipate heat are coming
\ipto vogue at inland locations due to the limited supply of water, as well as
environmental considerations. Even w'ith sea water cooled condensers, treatment
is essential for combating biofouling and corrosion. In fact marine biofouling
is so diverse and so persistent that studies to evolve counter measures would
take years at each of tbe coastal sites, inspite of common features.
Natural waters need to be demineraIised wholly to make them fit for use in
a high temperature heat transfer circuit. A number of techniques have been
developed over the last five decades. In addition to distillation, high purity
water can be produced on a large scale through ion exchange, while a lower
order of purity can be achieved by reverse osmosis. A combination of these two
techniques is also being advocated for use in the industry. Special techniques
have been developed to prepare ultra-pure water for use in the semi-conductor
industry. However, this book deals only with ion exchange and reverse osmosis
techniques.
Since the physico-chemical properties of water are a of
temperature and pressure, there is some difference in the feed and boiler water
treatment for low and medium pressure industrial boilers as against the high
pressure boilers employed by the electricity generating !lector. Depending upon
the requirements of the chemical process industry, both hot water and process
steam are supplied by the former class, while in thermal power stations, the
output is high pressure steam that drives the turbine. In other "high tech"
industries such as fertilisers and oil refineries, high pressure steam is also used
motive power, as well as in processes such as naptha cracking. The qualit}"
of steam is of paramount importance in all these activities. As an example:for
modern high pressure turbines, the level of sodium and chloride have been
specified to be less than 5 ppb each*.
Co-generation is an attractive concept, in which both the power and the
process requirements of industries such as fertilisers and petrochemicals
* Impurities are expressed as 'parts per million', (ppm) or at a still lower levellls 'parts per
billion', (ppb). In subsequent chapters the units used lire mgtl and Ilg/l which are more or
less equal to ppm and ppb respectively. When the specific gravity of water under
consideration is nearly 1.0, both sels of units mean the same. In saline waters, milJigrarn/
litre (mgll) is II more appropriate unit.
4
Water Chemistry
can be met by a single plant with considerable fuel savings. In this practice,
while the high pressure steam drives the turbine for power production, a part of
the exhaust steam, which is at a low pressure is used to provide the process
heat. Such systems make use of what are know.n as extraction condensing
turbines. The ("ffects of the changes in the steam chemistry within the system
due to the changes in pressure can be overcome by adhering strictly to the steam
purity limits needed at the high pressure end.
As the stearn generating system operates round the clock for prolonged
periods, material compatibility with high temperature, high pressure water/steam
is vital. The issue is taken up from the design stage itself and is finally reflected
in the selection of material and water chemistry control. Nuclear powered steam
generators and their primary heat transport systems have their own additional
and specific problems in terms of the radioactivity of the fissiop and corrosion
products. Limiting radiation exposure (0 operating personnel is the primary
objective of water chemistry control in a nuclear power In addition the
life of the plant is extended by providlftg protection against equipment corrosion.
An attractive as well as an additional source of energy is available from
geothermal wells. This natural resource is confined to a few places around the
world and is a useful supplement. Even if a geothermal well is not steaming,
the hot water effluent can still be made use of for district heating, in addition to
being a source of valuable inorganic chemicals. Hydrogen sulphide (H
2
S)
contamination of geothermal waters is a serious problem. Since, chemical control
cannot be easily effected, the designers of equipment look for materials that are
suitable in the working environment of geothermal fluids.
No discussion on water chemistry is complete without reference to the
chemical and instrumental techniques that are needed for monitoring the
properties of water and the measurement of the levels of dissolved impurities.
In modern power stations, on-line instrumentation for chemical monitoring and
computer controlled chemical addition are becoming more popular. A water
chemist would have to make a variety of measurements to enable him to render
useful advice to the management. Thus, it is necessary'to detail the chemical
and instrumental techniques needed by a water chemist.
Desalination of brackish waters, as well as sea water, has gained considerable
itnportance in water starved areas like the desert states around the Arabian Gulf.
With its high salt content, sea water poses special problems, in desalination
through multiflash evaporation or membrane technology. In India, reverse
osmosis is steadily gaining ground, especially as a precurser to ion exchange in
water demineralisation, and providing safe drinking water in villages under a
Technology Mission. An appreciation of the chemical problems in this area has
been provided in this volume.
In view of the increasing concern about polluting our environment,
particularly the aquatic environment through the discharge of liquid .effluents,
it has become absobtely necessary to devise effluent treatment processes that
trap the harmful pollutants, while the treated water is recycled. This will be a
means of water conservation, as water is a precious resource.
2
PHYSICO-CHEMICAL CHARACTERISTICS OF
NATURAL WATERS
A multiplic!ty of water characteristics is encountered in nattire. This is more
significant from a chemical point of view than from a physical perspective. From
relatively clean and pure rain water with little dissolved impurities, either
electrolytes or gases, the chemical contamination stretches upto sea water with
a very high dissolved salt content. On the other hand, the temperature ranges
only from above OOC for surface waters to a little over 100°C for geothermal
waters.
According to United States Geological Survey(l), most of the fresh water
(84.9 per cent) is locked up as ice in glaciers. Of the balar)ce, 14.16 per cent
constitutes ground water, while that in lakes and to 0.55 per
cent. Another 0.33 per cent is in form of soil moisture and atmospheric water
vapour. Thus, only a very small fraction of fresh water, viz., 0.004 per cent
flows through rivers and streams. The volume of sea water is fifteen times greater
than that of fresh water. Hence, the need for the conservation of available fresh
water is obvious.
Natural waters can be classified into two categories, viz., sea water
(inclusive of estuarian water) and fresh water. At ambient temperature they find
maximum use in industry and agriculture. Nearly 90 per cent of the water
employed in industry is for cooling purposes and the balance for steam generation.
Surface waters might possess colour, odour, taste, suspended solids etc. Ground
waters are expected to be free from organic odour and have a relatively less
variable composition at the same source. Industry employs water from all types
of water resources. This is not the case with agriculture or domestic use. The
water quality requirements are somewhat different for different uses. The
important characteristics that signify water quality are described below.
6 Water Chemistry
2.1 WATER QUALITY
Experience has shown that many diverse factors will have to be taken into account
before making comments on water quality. For this reason the concentrations of
inorganic and organic substances dissolved i,n a body of water and their spatial
and temporal variations need to be monitored. This exercise should cover not
only the major dissolved constituents. but also the minor ones such as heavy
metals, detergents, pesticides etc.
The United States Geological Survey(l) has classified different waters on the
basis of their Total Dissolved Solids (TDS) content as given in Table 2.1.
Table 2.1 Water Quality vs. Total Dissolved Solids(l)
Water Quality
Fresh
Slightly saline
Moderately saline
Very saline
Briny
TOS (mg/l)
Less than 1000
1.000 to 3.000
3.000 to 10.000
10.000 to 35.000
Greater than 35.000
The underlying chemical relationships between pH. alkalinity, hardness. the
ratio of sodium (Na) to that of calcium (Ca) and magnesium (Mg) etc. determines,
the buffering capacity. deposit formation and corrosive nature of water. The
seasonal variations in the quality of some surface waters could be large enough
to make the use of such waters more problematic. Under this category comes
silt and suspended solids. in addition to dissolved salts. The bacterial content,
specially the presence of pathogens. the self purification capacity and the water
intake structure also have a bearing on quality. Whatever might be the quality of
water available to a user. it can certainly be upgraded by properly designed and
executed treatment procedures. It is not advisable to condemn a particular body
of water as unsuitable. which may be the only available source at that location.
The United States Geological Survey(l) has given the significant concentration.
with respect to several chemicals that might be present in natural waters. Above
these levels. such chemicals can cause undesirable effects.
Table 2.2 Chemical Constituents of Significance in Natural Waters (1)
Chemical Constituent
Bicarbonate
Carbonate
Calcium
Magnesium
Sodium
Iron
Manganese
Chloride
Fluoride
Sulphate
mg/l
150 - 200
25 - 50
60 (Irrigation)
20 - 120 (Health)
Less than 3
Less than 0,05
250
0.7 - 1.2
300 - 400 (Taste)
600 - 1.000 (Laxative action)
Note: The above1are however nOllo be taken as drinking water standards.
Physioo - Chemical Characteristics 7
2.2 DRINKING WATER SUPPLIES
The quality of water for domestic use is judged from its total dissolved solids
content. The World Health Organisation has stipulated that drinking water should
have a TDS content of less than 500 mgll, although this can be relaxed to 1500
mgll, in case no alternative supply is available(3). For domestic animals, the
limits are the same as for human consumption, although the upper limit may go
up to 5000 mg/l, provided the increase is not due to the admixture of industrial
effluents containing trace toxic constituents such as chromate. Drinking water
should also be free from colour and turbidity. It should have no unpleasant
odour (dissolved gases) or taste (absence of certain dissolved solids). A case in
point is the smell of chlorine that is once in a way detected in domestic water
supply, as a result of excessive chlorination. With an increase in the hardness of
water (Ca, Mg, carbonate, sulphate), its suitability decreases with respect to
cooking, cleaning and laundry jobs. One of the well documented problems
concerning drinking water, is the presence of fluoride. In India, the Technology
Mission on Drinking Water laid special emphasis on fluoride, as well as iron
contamination in rural water supplies(4). There is also a certain amount of
avoidable confusion, since the beneficial effects of a little fluoride in dental care
are also known. What is not well publicised is the temperature effect on the
fluoride limits in drinking waterS). These are as fol!ows : The lower control
limit of 0.9 mgll at an ambient annual average air temperature of 10°C is reduced
to 0.6 mgtl at a temperature of 32.5
0
C. The upper control limit for fluoride in
the same temperature range is reduced from 1.7 to 0.8 mg/l. Thus the flexibility
in the range of fluoride control limits in India (as well as in other tropical
-:ountries) is much less than say in England or Canada. This is due to the
dependence on temperature of the rate of the biological uptake of fluoride by
body fluids.
The WHO guidelines for the quality of drinking water (1984) as given in
Table 2.3, refer to constituents of significance, both inorganic and organic as well
as of microbiological nature to health(6). Under the US law, the Environmental
Protection A ~ e n c y is charged with the task of conducting a regular review of the
guidelines for drinking water as applicable in the USA. A result of this is the
fonnulation of National Interim Primary Drinking Water Standards (NIPDWS) in
1985(7), which are slightly different from those issued by WHO in 1984 (Table
2.3). In addition WHO has also issued guidelines for the "aesthetic quality" of
drinking water (1984), which are a little difficult to quantify. These are
summarised in Table 2.4.
2.3 WATER FOR IRRIGATION
The chemical parameters that are important for water used in irrigation are, the
total dissolved solids, the relative proportion of sodium (Na) and potassium (K) to
divalent cations such as Ca and Mg and the concentration of boron and other toxic
elements. Less than 500 mgll of TDS is usually satisfactory, between 500 to 1500
mg/l needs special management, while above 1500 mg/l is not suitable for irrigation
except under severe constraints(3). The presence of toxic elements usually arises
due to contamination by effluents discharged from nearby industries.
8
Water Chemistry
'table 1.3. Constituents of Drlnkinl Water Havlnl SIIDlficane.e to Healtb(f."
Cl)nstituent Unit Limit of WHO Limit ofNIPDWS
Guideline (1984) Guideline (198S)
Mercury mgll 0.001 0.002
Cadmium mgll O.OpS 0.01
Selenium mgll 0.01 0.01
Arsenic mg/I O.OS O.OS
Chromium mgll O.OS O.OS
Silver mg/I ..
O.OS
Cyanide mgll 0.1
Lead mg/I O.S O.OS
Barium mgll
1.0
Fluoride mgll I.S 1.4 to 2.4·
Nitrate mgll 10.0 10.0 (uN)
Hexachlorobenzene IAglI
0.01
Aldrin lAg/I
0.03
Heptachlor IAglI
0.1
Chlorodane !Jg/l 0.3
I-I-dichloroethane
!Jg
II 0.3
DDT ",gil 1.0
Carbon tetrachloride !Jg/I 3.0
Lindane
!Jg/
I 3.0
Benzene
!Jg/
I 10.0
Gross ex pcill
]S.O
Ra226 + Ra228 pcill S.O
J3 + photon emitters mremly 4.0
• Level variation with climatic conditions.
Table 1.4. WHO Guidelines (1984) for Esthetic Quality of Drinklnl Water (7)
Constituent Unit Guideline Value
Aluminium mgll 0.2
Chloride mgll 2S0
Copper mgll 1.0
Hardness mgll SOO (u CaCOJ
Hydrogen Sulphide Odour not to be
detected at all
Iron mgll 0.3
Manganese mgll 0.1
pH
6.S to 8.S
Sodium mgll 200
Sulphate mgll 400
Turbidity
NTtJ. S
Zinc mgll S
Sodium and Potassium ion concentrations in natural' waters are relevant to
irrigation as these cations reduce the permeability of soils. On the other hand,
• Equivalents per million (epm), is obtained by dividing mgll (or ppm) by the equivalent
weight of the ion under consideration.
Physico - Chemical Characteristics 9
Ca and Mg ions, being divalent, are pleferentially taken up by the exchange
sites in soil, thus reducing Na and K uptake and helping to restore soil
permeability. A factor known as the Sodium Absorption Ratio (SAR), also called
Sodium Hazard, is defined as, '
Na+
SA R - --;==;:===;:0=
Ca
2
• + Mg2+
2
(2.1)
The concentrations are expressed in equivalents per million (epm)*, which is
the same as milli equivalents per Iitre('>. Since Ca and Mg concentrations are
also governed by presence of bicarbonate and carbonate ions (i.e. partial
precipitation), another criterion that has been used is known as RSC (range of
soil carbonates). This is defined as,
Rsc-(coi- + HCO;)-(ca
2
+ + Mg2+) (2.2)
The concentrations are again expressed in epm. If RSC is greater than 2.5
epm, the water is not suitable for irrigation; the optimum RSC spread being
from 1.25 to 2.5 epm.
2.4 SALINE WATERS
Sea water is r.ot suited for domestic and irrigation purposes. Sea water with a
salinity of 35 gIl has an average der.sity of 1.0281 kg/l at O°e. A variation in
salinity of 1 gil causes the density to change by 0.0008 kg/I. In recent decades,
desalination of brackish as well as sea water (an industry by itselt) has come
into vogue in arid and desert locations, for producing drinking water. ~ I s o made
use of, is coastal saline groundwater. This is used for horticulture rather than
for agricultural purposes. Sea water is used for cooling power rlant condensers,
when the power station is on the coast. In this context, the biofouling characteristics
of sea water at that particular lOCation are of much greater relevance than the chemical
parameters.
2.S ORGANIC WAD
Natural waters contain organic matter in addition to inorganic substances. This
poses several problems with respect to power station water chemistry. The two
, main areas of concern are as follows:
(a) It can lead to blocking of functional groups of the ion exchange resins of
water treatment plants because of irreversible absorption, leading to
reduction in the ion exchange capacity as well as damage to the resins.
(b) When carried into the tlOiler with the deionised water, it may get
decomposed into acidic products which can affect not only the boiler
water pH, but also its tendency to foam. This can l e ~ l d to steam
entrainment of boiler water, salination of super heaters and turbines.
In addition, corrosion in the condensation zone can also result because
of volatile decomposition products.
Several techniques have been developed to isolate organic substances from
water and to estimate them quantitatively(I). However, most of these methods
10 Water Chemistry
are expensive in terms of time involved as well as equipment. Therefore, power
plant laboratories usually determiIie only the potassium permanganate value.
The Association of Boiler Germany, (VGB) found that ultra
violet (UV) spectrophotometry cao:ieaout in the range of 200 to 340 nm may
furnish very useful information about these organic substances (hUJJlic acid, lignin
suiphonic acid etc.) without the need of isolating, identifying and quantifying
the individual constituents.
The breakdown of organics in steam generating systems is leaaing to problem
situations in several power stations. Consequently more ahd mot'
utilities are switching over to the dete.rmiqf!tionA)fTotal Organic C.mon (TOC),
rather than 'depending on potassium permat}ganate value of the raw water.
Sophisticated analysers are marketed fot this task.
In principle it is seParate organic substances from the raw
water through an appropriate,we-treatment. For this, addition of preliminary
purification stages ofDM plant is recommended. These are flocculation,
flocculation-decarbonizathmand use.Qf.anien exchangers as absorbers. Oxidising
agents such as chlorine or ozone i:an also be tried. Under certain conditions,
however, it is possible to carry out the ion exchange as well as organic substance
removal within the plant.
2.6 CHEMICAL PARAMETERS GOVERNING WATER
QUALITY
The quality of surface water from rivers and lakes is important to industry, as it
determines the chemical or de mineralisation treatment needed, to make it
compatible with the construction materials of cooling and heat transfer circuits.
Since, water qualit)"'Varies with location and seasons, water quality monitoring is an
essential activity for any industry thatmakes-use of a water source. Biofouling due
to surface water is also a problem that has to be tackled. In certain instances, sub-
surface or groundwater (from a borewell farm) is also used. In view of variations
expressed due to blending of water from different borewell farms, there are
instances where the industry in water quality on a day to
day basis. Thus, more care needs tq:biexerclsed.
It is essential to appr.eciate: -the Significance of limits set on chemical
parameters defming quality. The hydrogen ion concentration is represented
by the pH value. By IlhcHarge the pH of natural waters lies in the neutral range.
For drinking water a pH of 6.S to 8.5 is recommended, while for irrigation the
range can be slightly wider viz., 6.0 to 9.0. There are instances when, due to
contamination of dissolved gases such as SUlphur dioxide· or oxides of nitrogen,
rain water woule have a pH in the aciaic region, leading to the phenomenon of
"acid rain". Some surface waters passing over areas that are rich in sodium and
potassium exhibit an alkaline pH. Such examples of acidic or alkaline water, are
however, not common. Clean sea water usually has a pH of 8.0 to 8.2.
The electrical conductivity (EC) of water is related to its total dissolved
solids content. Since it is easy to measure this. parameter, it is a very useful
indicator and is expressed as microsiemens/cm at 25
0
C, The water quality is
usually judged on the basis of its value, as given in Tabie 2.S(9).
Physico - Chemical Characteristics
Table 2.5. Spec:ifie Conduetlvity vs. Water Quality(')
Specific Conductivity
Less than 250
250 • 750
7S0 - 2000
2000. 3000
Oreater than 3000
Water Quality
Excellent
Good
Permissible
Needs treatment
Unsuitable for most purposes
11
A commonly indicated water quality parameter is its hardness, due to presence
of Ca and Mg in combination with anions such as carbonate and sulphate. The
presence of these two divalent cations is essential for ensuring soil permeability
as well as for the growth of crops. Thus, one measures what is known as Ca
hardness, Mg hardness and the sum of these two viz., the total hardness. The
measurement of Ca and Mg is through simple volumetric procedures.- While
hardness per 1S not harmful to health, it is better to avoid hard water for
drinking. On the other hand, extra hardness will mean the consumption of more
soap in washing and also scale formation in cooling water circuits and boilers.
It should be remembered that very soft water induces corrosion in iron pipe
line. In tenns of hardness, the water quality is designated as shown in Table
2.6(9), '
Table 2.6. Hardaess VI. Water Quality(')
Hardness expressed as mgll of CaCO)
0, • 50
50 • 100
JOO • 1,Sp
150 • 200
200 • 300
Greater than 300
,
Description of Water
Soft water
Moderately soft
Neither hard nor soft
Moderately hard
Hard water
Very hard
As against the above, the United States Geological Survey Classification of
Waters(2) base'" on hardness [expressed as calcium carbOnate (CaCOJ> mill}
gives,0-60 as soft, 61·120 as moderately hard, 121-180 ¥ hard and above 180
as very hard.
I
. Itt concentrations abOve 3000 mgll, Mg is toxic. tn the presence of large
orMg, soluble silica would cause the precipitation of magnesium
silicate.
Chemical Oxygen Demand (COD), represents the total consumption of
potassium dichromate during hot oxidation of water covers a
majority of organic compounds and oxidisable inorganic
Alkalinity is usually defined'in terms of bicarbonate, carbonate and hy,droxide
ion concentrations. Bicarbonate alkalinity is also called methyl orange alkhlinity
or M-alkalinity, while P-alkalinity (Phenophalien alkalinity) signifies the presence
of carbonates and hydroxide ions. As defined P-alkalil}ity includes all the
hydroxides, but only half of carbonate content. Highqi alk,Hnity causes the
precipitation of Ca and Mg leading to the problelll of scaling on heat transfer
surfaces.
12 Water Chemistry
Coming to the presence of other anions in natural waters, chloride takes
precedence over others, especially for domestic use. If chloride is present at
over 250 mgll, it is not suitable in food processing and if it is over 1000 mgll,
the water is not suitable for industrial cooling because of the corrosive effects
of the chloride ion on several metallic surfaces.
While nitrates are needed for increa"ing agriculture productivity, more than
50 mgll is not to be allowed in water for domestic use. The problem of fluoride
has already been dealt with. In waters meant for irrigation, boron concentration
should not exceed 1 mgll, as otherwise it is harmful to plant growth.
A discussion on water quality is not complete unless mention is made of the
biological monitoring of surface waters(ll). In this technique a number of fish
are maintained in a channel through which l\ part of water stream is diverted and
their physiological responses are recorded for symptoms of stress. The fish
swimming against the stream of.water in the test channel emit signals of the
order of 10 to 15 IlA. Their muscle potentials are of the order of 60 to 80 m V
wl1ich are attenuated by the dielectric constant of water. By suitable amplication
and integration, the normal activity of the fishes can be recorded. If the water
quality deteriorates (low dissolved oxygen, presence of toxic chemical etc.),
the fish will be affected and this will be reflected in the record of their emitted
electrical impulses. While such systems have been used in many countries for
monitoring the quality of flowing river water, the best results are obtained in
less dynamic laboratory applications and in monitoring the quality of cooling
tower water in industry.
2.7 CLASSIFICATION OF WATER QUALITY
Using the specific conductivity and the SAR value of natural water, a salinity
hazard diagram has been constructed to classify waters meant for irrigation.
There are five groupings in terms of conductivity and four in tc:rms of SAR.
Consequently, water quality is often referred to as CIS
I
(Excellent) --- C
2
S
4
(Bad) etc.(IO).
The geochemical system of water quality classification rests on the basis of
the predominant cations and anions that are present in equivalents per million.
This leads to five types, viz. (a) Calcium bicarbonate, (b) Sodium bicarbonate,
(c) Calcium chloride, (d) Sodium chloride and (e) Mixed type.
Another classification makes use of the specific conductivity and Biological
Oxygen Demand (BOD) as the defining parameters(3). BOD is the quantity of
oxygen consumed at 20°C and in darkness during a fixed period of time, through
the biological oxidation of organic matter present in water samples. By
convention, BOD or BOD, is indicated, which is the quantity of oxygen consumed
during 5 days of incubation.
The BOD ofa water body, although its practical determination is open to a
number of reservations, is the most satisfactory parameter for characterising
the concentration of organic matter. WHO has imposed a limit of 4 mgll on the
BOD of raw water to be used for pubic supply. If BOD is greater than this
value, a part of the organic matter carrying bacteria and pathogens is likely to
escape removal and pass into the water distribution system. The presence of
Physico ~ Chemical Characteristics 13
toxic substances inhibits bacterial life and gives a low BOD which is not
necessarily a sign of clean water fit for consumption.
Considering specific conductivity and BOD together, natural waters have
been divided into five classes as shown in Table 2.7 :
Table 2.7 Classification of Natural Waters(3)
Specific
Conductivity
Low
(9S% ofthe time
less than 7S0 IlS/cm)
Intermediate
High
(95% of the time more
th'ln 22S0 IlS/cm)
LOW
9S% of the time
less than 4 ppm
Class I
Class 2
Class 3
@ All toxic Constituents come under this class.
BOD
HIGH
More than S% of the
time above 4 ppm
Class 4
Class S@
Class 1: Suitable for public consumption as well as other uses.
Class 2: Suitable after some treatment, but not fit for irrigation if a better source
is available.
Class 3: Not suitable without proper treatment for any purpose, except for
. watering cattle.
Class 4: Suitable for irrigation, but treatment required for drinking and for
industry.
Class 5: Unsuitable for all purposes.
2.8 EXAMPLES OF SURFACE WATER QUALITY IN
INDIA
To illustrate some of the points discussed above, water quality data assembled
by different organisations in India, are presented below. These are only typical
examples and a voluminous data is available on water quality of surface and
ground waters in India.
2.S.1 RiverWaters
In a study of the Cauvery river by the Soil Mechanics and Research Division,
PWD. Government of Tamil Nadu(9), it has been shown that all along its course,
the water is of the calcium bicarbonate type, except at certain locations in Salem
and Tiruchirapally districts where the discharge of industrial effluents into the
river, turns it into sodium bicarbonate type. Obviously water drawn from these
locations, will be less suitable for irrigation. The water quality as a function of
the beginning and end of flow season in the river all along its course indicated .
that TDS is less at the end of the flow season. A study was also conducted of
the water quality in 14 reservoirs and an attempt was made to correlate the
electrical conductivity with either bicarbonate, chloride and sulphate. In most
14
Water Chemistry
cases, the correlation was good with bicarbonate, while some showed a good
correlation with chloride. There was one reservoir which showed sulphate correlation
with EC. The reservoir waters are mostly of the CIS I or C
2
S 1 type. Interestingly the
C. SI type were mildly acidic in nature, C
2
S
1
type were alkaline.
The Maharashtra Engineering Research Institute has carried out water quality
studies of Krishna, Godavari, Bhima and Tapi rivers as well as of several
reservoirs(12). Krishna, Bhima and Tapi river water was mostly of CIS I or C
2
S
l
type with only a few locations showing C
3
S I' On the other hand the water quality
in the Godavari ranged all the way to CSS
I
indicating that in some locations, the
river water is not suitable for irrigation because of salinity. In addition, heavy
pollution was noticed down stream at Nasik.
Several variations of water quality can be seen from, the data on Godavari
and Tungabhadra river waters at relatively unpolluted locations. This study by
the Andhra Pradesh Engineering Research Laboratories(13), clearly shows the
effect of rainfall on the water quality of the Godavari at'the sampling
as shown in Table 2.8.
Table 1.8. Data or River Water Monitoring In Andhra Pradesh(U)
Parameters Godavari River River
AErn'I2
June '82
.'
SeEt. '82
Temperature 0c 39 31 28 29
pH 7.9 7.6 7.S
-
8.0
Sp. Conductivity 1380 920 SSO
"00
Ca mgll 134- 68 20
"7
Mg mgll 18 24 18 S.S
Na mgll 182 180 64 62
K mgtl 14
HC0
3
' mgtl
34.8 464 201 189
CI' mgtl 298 120 39 SO
SO.l.
mgll 127 137 104 47
NO, mgll 1.8 0.6 5.1 2.4
F' mgll 1.4
1.3
0.8 0.4
Silt mgll 117 186
SAR 3.9 4.9 2.4 2.3
In Godavari's sample locations, the rainfall lowered the specific conductivity,
calcium and chloride, while an increase is seen in bicarbonate and silt. At
Tungabhadra's sample location, however, the parameters do not vary much
between the beginning and the end of the rainy season indicating scanty rainfall.
These studies were extended to locations down stream of paper mill discharges
into both the rivera. It was seen that the change in water quality after mixing
with the effiuents was more marked for Tungabhadra than' with Godavari. While
the bicarbonate value diPPed from 44 percent to 17 per cent of the total anions,
the chloride went up from 9 to 13 percent(1J).
Physico - Chemical Characteristics
2.8.2 Coastal Wells
Intrusion of highly saline water into the wells along the coast is a fairly well
known phenomenon. The quality of otherwise good groundwater in wells is
brought down by such intrusion due to withdrawal. A study of 334
wells along the coast line ofDakshina Kannada district, Karnataka is illustrative
of this phenomenon (Table 2.9)(14).
Table 2.9. Saline Water Intru.ion Into Coastal Well. In Karnataka(14)
pH 5.S • 6.5 (113) 6.S • 7.0 (101) 7.0· 7.S (61) 7.S • 8.0 (48) > 8.0 (II)
EC ( IlS/em) 200 (142) 200· SOO (7S) SOO· 800 (49) 800· 1200 (38) > 1200 (30)
Chloride (mgll) 30 (17S) 30·70 (60) 70· ISO (47) ISO· 300 '(IS) > 300 (37)
Note: The number within parentheses indicates the number of well in the range of the
parameter measured.
Similar studies on sea water intrusion have been reported from Thane District
in Maharashtra(15).
2.8.3 Highly Saline Ground Waters
In the arid and semi-arid regions ofIndia, there are examples of wells
where the groundwater is highly saline, so that they may be termed as "brine
wells". About 50 km southwest of Delhi, in the Gurgaon District of Haryana, a
number of such brine wells exist and are being used as a base for thriving salt
industry. The chemical composition of some of these well waters is given in
Table 2.10(16).
Table 2.10. Chemical Composition 01 Some Brine Waters, naryana(16)
.
Constituent Sultanpur Muharikpur 8asirpur
in mg/I
TOS 28,182 29,312 24,555
Chloride 16,210 16,300 12,670
Sulphate 2,400 2,530 3,320
Calcium 11,500 930' 11,400
Magnesium 2,110 1,760 1,350
Sodium 5,970 7,480 5,540
2.8.4 Cooling Water Quality in Electrical Utilities in India
As mentioned earlier, large quantities of natural waters are employed by the
electricity generating units for cooling condensers(17). From the same source of
raw water, they make use of a smaller amount for the production of demineralised
water. As such it would be instructive to have data of the type of water quality
available to such utilities. Table 2.11 gives six examples of raw water quality
from different parts of India(18).
A few comments on the data in Table 2.11 are required. Sourc,e. A although
it is from a canal drawn from a big river, is also a partial dumping ground for the
sewage of a metropolis. This is clearly reflected in higher value of specific
conductivity, as well as the highest permanganate value the set indicating
a high organic 10ad.The latter poses problems for the demineralisation plant.
'"'-
0.
Table 2.11. (River) Raw Water Analysis with Seasonal Variations as used by Electricity Generation Industry, India(l8)
Chemical A B C D E F
Parameters Jan. Apr. Sept. Jan. Apr. Sept. Jan. Apr. Sept. Jan. Apr. Sept. Jan. Apr. Sept. Jan. Apr. Sept.
Specific
Conductivity 438 479 277 158 136 84 85 126 177 470 400 306 970 771 877 309 348 278
IlStcm
pH 8.0 8.0 8.0 7.2 7.5 7.4 7.9 8.0 7.5 8.6 8.6 8.2 7.3 76 7.3 8.5 8.6 8.6
Total Hardness 102 146 119 83 76 60 49 51 32 92 98 85 268 222 523 113 112 101
mgll as CaC0
3
Total Alkalinity 146 156 112 72 63 49 59 65 43 126 120 127 257 247 233 123 134 121
mgll as CaC0
3
Chloride mgtl 34 34 35 10.8 11.9 10.8 5.5 5.0 5.2 48 50 45 245 146 50 17.4 19.5 15.6
Permanganate
Value meq/I 4.5 2.2 7.3 1.0 1.8 '2.6 3.1 0.7 0.6 0.6 0.6 0.8 0.9 0.8
A: River water by the side of an urban metropolis in North India.
B. River water in East India.
C: River water in Central India with other industries nearby.
D: River water in South India.
~
E: Ground water (Borewell farm) in South India by the side of an urban metropolis and sea.
~
F: River water in Western India.
""t
g
~
:!
a
~
Physico - Chemical Characteristics
17
Sources Band C are fairly clean. Organic load is seen in Source C, probably due
to the locations of industries nearby. Source D, although river water, has a greater
content of dissolved impurities as seen by high values for specific conductivity
and chloride. Source E is from a groundwater farm (typical borewell waters)
and one can readily see the high salt content. This imposes a considerable load
on the demineralisation plant of the utility. Source F is moderately "clean". The
power plant condensers are cooled by the same raw water in case of A,B,C,D
and F, while at location E, the condensers are cooled by sea water. Apart from
E, in all other cases, seasonal variation is seen. In general, the values of specific
conductivity are lower in September, indicating the general dilution effect of
the monsoon.
A nuclear power station located near an artificial reservoir created by a dam
on a river in India uses raw water whose typical analysis is shown in Table
2.12(17).
Table 2.12. Typical Analytical Data of Impounded Raw Water from a Reservoir,
India (19)
Specific conductivity uSI<;m 275
pH 8.2
M Alkalinity 110
P Alkalinity Nil
Total dissolved solids mg/I 145
Total suspended solids mgll 5
Silica in mgll as Si0
2
\0
Turbidity in mgll in silica units 5
Total hardness mgll as CaC0
3
90
Cations Anions
Ions mg/I as mgll as Ions mg/I as mg/I as
the ion CaC0
3
the ion CaC0
3
Ca 22 54 Bicarbonate 134 110
Mg 9 36 Chloride 11 16
K 2 3 Nitrate 2.5 2
Na 21 45 Sulphate \0 10
Total 138 Total 138
This type of analytical information is needed for designers of demineralisation
plants, where the balance between cations and anions is clearly established, as
well as the nature of these ions. While all the cations belong to what is known as
the class of strong cations, the major anion, the bicarbonate, belongs to the
class of weak anions. As seen later, during the demineralisation process,
bicarbonate decomposes after the passage of w ~ t e r through a strong acid cation
exchanger giving rise to carbon dioxide which needs to be vented off.
REFERENCES
I. Heath. R.C. (1982). Basic Groundwater Hydrology. USGS Water Supply Paper. 2220.
2. Heath. R.C. (1982). Basic Groundwater Hydrology. USGS Water Supply Paper, 2200.
3. Kemp. P.H. (1971). Chemistry of Natural Waters - \.'1. Water Research. 5. 943.
4. National Environmental Engineering Research Institute Staff (1987). Report on
Technology Mission on Drinking Water in Villages and Related Water Management.
Nagpur. India, WTM/CSIRINEERII004
18
5.
6.
7.
8.
9:
10.
II.
12.
13.
14.
Water Chemistry
Purdom. P.W. (Ed.). (1971). Water and its Impurities. Academic Press. pp. 154 •
155.
World Health Organisation. (19!l4). Guidelines for Drinking Water Quality. 2nd
ed .• WHO. Geneva.
Environmental Protection Agency. USA. ( 1985). National Interim Primary Drinking
Water Standards as given by Laws E.A. In Water Pollution & Toxicology.
Encyclopedia of Physical Science and Technology. 2nd ed .• 17.525.
Strauss. S.D. (1988). Monitoring Organics· An Overview. Power. (Sept. 1988),5 I.
Soundarapandian V. V. V. Re .. athi, Sheela and A Shyamala (1985). Quality of River
and Reservoir Waters of Tamil Nadu. Proc. Seminar on. Water Quality and Its
Management. pp. 91 . 95. Central Board of Irrigation Powe'r. New Delhi.
US Salinity Laboratory Staff (1954). Diagnosis and Improvement of Saline and
Alkaline Soils. US Dept. of Agriculture Hand Book. p. 60.
Reiff, B. (1981). Biological Monitoring of Surface Waters, Water Pol/ution and
Management Reviews. pp. 41 - 46.
Kokani. S.G. (1985). Study of Water Quality of Ri vers and Reservoirs in Maharashlra
State. Proc. Seminar on Water Quality and its Management. pp. 91-102. Central
Board of Irrigation and Power. New Delhi.
Rameshwar Rao C. and T.V. Narisimha Rao (1985). Studies on Pollution of River
Waters (Godavari and Tungabhadra) by Effluents From Paper Mills. Ibid., pp. 103
- 110. Central Board of Irrigallon & Power. New Delhi.
Gurappa. K.M .• I.V. Nayak. G. Ranganna. G. Chandrakantha. M.R. Gajendragad
and C. Nliganna (1985). Seasonal Variation of Water Quality Along the Coastal
Tract of Karnataka - A Case Study. Ibid .. pp. III - t 16. Central Board of Irrigation
and Power. New Delhi.
15. Padhye - Gogate. M.P. and K. Sila (1987). Salinity Ingress Coastal Parts of Thane
District. Maharashtra. TrailS. Inst. Indian Geographers. 9(2), pp. 19 - 23.
16. Biswas, A.B. lind A.K. Saha, (1982), Ground Water Resources of India With Special
Reference to Their Salinity and Pollution Hazards, Water Pollution & Management
Reviews. pp. 113 - 127.
17. V. Ramshesh and K.S. Venkateswarlu (1975), Importance of Water·Quality in the
Use of Large Volumes of Water for Condenser Cooling in Power Station, Ind. J. of
Power and River Valley Development. 25. 124 - 127.
18. K.S. Venkateswarlu (1985), From Raw Water to Pure Steam: Problems in Thermal
Power Stations. Corrosion and Maintenance. 8. 187 - 192.
19. B.K.S. Nair (1983), Demlneralisation of Water: Principles, Production and Quality
Control, Proc. Workshop on Water Chemistry in Thermal Power Stations, pp. 13 -
19, Central Board of Irrigation and Power, New Delhi.
3
PROPERTIES OF WATER AT HIGH TEMPERATURES
AND PRESSURES
The physico-chemical properties of water arise as a result of the structure of the
water molecule and its ability to fonn hydrogen bonds in condensed phases. The
two hydrogen atoms are bonded to the oxygen at an angle of 104.5°; close to that
expected in a tetrahedral arrangement. The O-H bond length is 0.957 AU. The two
lone pairs of electrons on the oxygen are positioned to give a psuedotetrahedral
arrangement. The bent shape of the water molecule bestows it with a high dipole
moment and bigh dielectric constant. These two properties make water an excellent
solvent in which elctrolytes such as NaCI dissociate into ions, which in turn are
hydrated (specially the cations) due to the co-ordinating ab.ility of the lone pair
of electrons on the oxygen. The hydrogen bonding often leads to he formation
of a secondary shell of hydration, around the first hydration shell.
An important example of anion solvation 'is the formation of a hydrated
electron (commonly referred to as the solvated electron) wherein the positive
ends of the water dipoles surround the electron. These properties are unique to
water. The only other substances that have such proclivity to a limited extent
are liquid ammonia and liquid hydrogen fluoride.
3.1 THERMOPHYSICAL AND THERMOCHEMICAL
PROPERTIES OF WATER
The trermophysical properties of water are listed in Table 3.1 (I).
When water is employed in industry for cooling, through the use of cooling
ponds, cooling towers etc. in combination with process water heat exchangers,
the temperature of water ranges from the ambient to about 60°C. In view of
20 Water Chemistry
this, properties of water at higher temperatures (well beyond 100°C) under
pressure are of no consequence in this segment of water use. On the other hand,
when water is used to make steam, the temperature in the boilers and the
associated steam turbines is in the range of 250-320oC. Thus when one
considers steam generation either for production of electrical or motive power,
the properties of water and steam at high temperatures and pressures become
relevant for understanding the chemistry involved.
Table 3.1 Thermophysical Properties or Water (I)
____ Property Liquid Vapour
Heat ot formation at 25
0
C K.callmole -68.32 -57.8
Energy of formation at 25
0
C K.cal/mole -56.69 -54.64
Sp. Heat cal/gfOC 0.998 1. 007
Critical temperature, °c 374.15
Critical pressure, Kg/cm2 212.2
Critical density, g/cml 0.32
Critical volume cml/g 3.28
In view of the temperature difference between cooling water systems and
the steam generating systems, it is appropriate to consider the dependence of
the physical and chemical properties of water in two temperature ranges, viz.,
upto 100°C and the other beyond 100°C where pressure i5 to be applied to
keep water in the liquid phase, either fully or in equilibrium with the steam
phase. The behaviour of water and steam beyond the critical point of 374°C is
also of interest.
3.2 PROPERTIES OF WATER BELOW lOOoe
In the temperature range of 0 to 100°C, the density of water is maximum (1.000)
at 4°C, while at OoC it is 0.9999. This is due to the collapse of some of the
l,drogen bonds and the release of water molecules trapped in the cavities. Beyond
4°C the density decreases to 0.9971 at 25°C and 0.9584 at 100°C. The decrease
in density results in a decrease in the surface tension and viscosity, as shown in
Table 3.2:
Table 3.2 Changes in Surface Tension and Viscosity of Water with
Temperature(l)
Surface tension (Dynes/cm)
Viscosity (Centipoise)
OOC
75.6
I. 79
100°C
58.9
0.28
The combined effect of such decreases in density, surface tension and viscosity
of water (25 to 100°C) is to increase the mobility of the cations end anions
present. In the case of high purity water, this would mean an increase in the
mobility of H+ and OH" ions that are present due to water dissociation. At
ordinary temperatures, the ionic product (Kw) of water is very small (pKw or
-log IOKw = 14). The pH is defined as log IOH+ and Kw is the product of [H+) and
[OIl") concentrations. Thus a simultaneous and equal increase in the values of
[H+] and [OH"] due to the \ increased dissociation of wate.r with temperature,
would mean that the pH scale, as wei: as pH as defined wIll be effected by an.
Properties of Water at High Temperatures and Pressures
21
increase in the temperature of water. The known range of the pH scale of 0 - 14
at 25°C begins to contract with increase in temperature. For example, the ionic
product, whose value at 25°C is 1 x 10-
14
, increases to 52 x 10-
14
at 100°C.
Consequently, the pH of pure neutral water defined to be 7.0 at 25°C decreases
to 6.25 at 100°C. It should be made clear at this juncture that pure water at
100°C will continue to remain neutral and because of the compression of the
pH scale at 100°C, the neutral point shows only an apparent decrease. The very
fact that the hydrogen ion concentration increases with temperature in pure
water, makes it much more aggressive to metallic surfaces at higher temperatures
than at room temperature.
As is well known, electrolytes such as sodium chloride dissociate into their
component ions on dissolution in water, due to its dielectric constant. This
important property of water also undergoes a change with temperature. At
OOC,the value of the dielectric constant of water is 88.0, which decreases to
78.5 at 25°C and to 55.3 at 100°C (and 760 mm Hg.) This means that water
loses its ability to effect the dissociation of electrolytes and a fraction of the
dissolved substances remains as an undissociated or neutral chemical species.
While in the temperature range under consideration this effect might not be of
that much importance for strong electrolytes such as NaCl, for weaker
electrolytes such as the hydroxides of corrosion products, it has some relevance.
Examples are Fe(OH)3' Zn(OH)2 and Ni(OH)2.
The overall effect is that pure water at 50 to 60°C is a more aggresively
corrosive fluid than at room temperatures and steps will have to be taken to
keep the corrosion rates in the cooling water systems within acceptable limits.
This will be dealt with in greater detail in a later chapter.
3.3 PROPERTIES OF WATER ABOVE 100°C
In steam generating systems operating at temperatures well above 100°C, the
need for thermal efficiency requires the application of pressure, so that a higher
temperature can be reached. Pressure in itself has only a marginal effect on the
water chemistry (except with respect to the elevation of its boiling point), but
has a profound effect on what has come to be known as steam chemistry. In the
two phase system of water and steam, the distribution of solutes is a fucntion of
temperature and pressure, rather than temperature alone. The thermophysical
parameters and other properties of water as a function of temperature and
pressure are given in.Tables 3.3, 3.4 and 3.5(2,3).
Table 3.3 Thermophysical Parameters oCWater as a Function oCTemperature
and Pressur-e(l)
Parameter Specific Volume Gibbs Free Energy Entropy Enthalpy
c m 3 / ~
KJMoJ-t JMoJ-toK·t KJMo)-t
Pressure K. bar 1.0 1.5 1.0 1.5 1.0 1.5 1.0 1.5
Temperature OOC
100 1.000 0.984 1.18 2.07 15.7 15.1 7.03 7.72
200 1.0114 1.060 -1.29 0.33 33.1 32.3 14.4 14.9
300 1.213 1.169 -5.36 -4.28 47.8 46.5 22.0 22.4
Table 3.4 Variation in the Properties or Water with Temperature and Pressure(2)
Property Thermal conductivity Static dielectric constant
mJ m-I sec-
10
K-I
Farad Steradiam per meter
Pressure K.Bar 0.1 0.25 0.6 0.75 0.1 0.25 0.5 0.75 1.0
Temp.oC
100 689 694 703 712 55.7 56.2 57.0 57.8 58.4
150 697 706 719 733
200 677 690 713 736 34.8 35.4 36.4 37.3 38.0
250 629 650 684 718 27_1 28.1 29.4 30.5 31.4
300 554 582 628 674 20.1 21.5 24.2 25.2 25.3
350 14.8 17.7 19.3 20.5
• To convert values into centipoise mUltiply by 10-
3
@ Phase transition
Viscosity·
J1N Sec mm
2
0.1 0.5 1.0
287 296 308
185 194 205
137 148 162
110 121 132
@ lOl 113
....
....
~
~
....
~
:!

~
Properties o/Water at High Temperatures and Pressures
23
Table 3.5 Density or Water : Variation with Temperature and Pressure(3)
Density of Water at 4 K bar Density of Water at 500°C
TempoC Density Pressure Density
gm/cc Bar gm/cc
100 1.10 10 0.01
200 1.05 10
2
0.10
300 0.95 10
3
0.5(\
400 0.87 10
4
1.00
500 0.82
lOs
2.00
In the temperature range of interest to the steam generating sytems, viz.,
250 to 300°C, the density of water decreases from 0.6 gmlcc at 250°C to 0.5
sm/cc at 300°C, both measured at a constant pressure of 100 kg/cm
2
(1450
psi). The decrease in density and viscosity coupled with the increase in the
dissociation constant of water with increase in temperature results in increased
conductivity of pure water as given in Table 3.6. Compared to a value of 4.5 x
10-
8
~ S / c m at 25°C, the conductivity of pure water at 275°C increases to 7.6 x
1 0-
4
~ S / c m . This in turn makes water very aggressive to the metallic surfaces
with which it comes into contact and thus promotes corrosion.
Table 3.6 Specific Conductivity orWater at Different Temperatures
Temp OOC Sp. Conductivity J.l.S/cm
20 4.5 X 10-
8
31 2.1 x 10-
7
49 1.1 x 10-
6
86 7.2 x 10-
6
156 5.3 x 10-s
274 7.6 x 10-
4
The limiting equivalent conductances of several ions in water have been
determined as a function of temperature at saturation vapour pressure. Of the
different ions, hydronium (H30+) and hydroxyl (OH-) ions show a large increase
in A.o. Since the number of ions of a given electrolyte are proportional to the
dielectric constant (due to increase in temperature), the effect ofincreased ionic
mobility due to the reductions in density and viscosity gets nullified at a certain
temperature. In other words, the conductivity ofan elctrolyte, like NaCI in water,
goes through a maximum when measured as a function of temperature. It so
happens that the maximum conductivity of different electrolytes in water, lies in
the temperature range of interest (235 to 325°C) to steam generating systems
of power stations.
3.4 EFFEcrs OF TEMPERATURE ON THE IONPRODUcr
OFWATER
The effects of high temperature are nowhere more striking than on the pH value
or the pH scale of water and alkali sing weak electrolytes such as ammonium
and lithium hydroxides dissolved in water. Figure 3.1 shows the temperature
24
12.0
11.5


Co
11.0
Water Chemistry
a. Mesmer, Baes and
Sweeton(5)
b. Cobble(4)
c. Helgeson(7}
d. Marshall and Frank(6)
b
a
473 573
T E M PER AT U R E (OK)
Fig. 3.1 Plot of pKw of Water Vs.
dependence of the exponential of the ion product of water (pKw) in the range of
170 to 340°C. Although there is some difference in the pKw values as determined
by different workers, the trend is the same, viz., the pKw of water decreases (or
Kw increases) upto a certain temperature and then increases (or Kw decreases)
as the temperature is increased further. The minimum ofpKw (or maximum of
Kw) lies in the temperature range of230 to 250°C. As seen earlier, since the pH
scale and the point of neutrality of pure water are defined in terms of pKw and
the minimum of pKw value as seen in Figure 3.1 being a little over 11.1, the
pH value of high purity water at say 240°C is 5.55. Thereafter the neutral
point shifts to higher values. It is once again emphasised that pure water will
continue to remain neutral under such conditions, though both H+ and OH-
concentrations will be at their maximum in equal measure. Thus, water would
be most aggressive in the range of 230 to 250°C. An ammonical solution of
water that exhibits a pH of 9.5 at 25°C is reduced to 6.4 at 220°C. Similarly
water spiked with LiOH that shows a pH of 10.5 at 25°C is lowered to 7.76 at
220°C (Table 3.7). The consequences of such changes are discussed later.
Table 3.7 Changes in pH of Water, Ammonium and Lithium Hydroxide
Solutions as a Function of Temperature
TempoC
Pure Water NH
4
0H LiOH
25 7.00 9.50 10.50
100 6.16 7.77 8.80
156 5.83 6.96 8.12
218 5.67 6.41 7.76
306 5.89 6.28 8.12
The dielectric constant will continue to decrease with increase in temperature
in the range of 100 to 300°C. On the other hand, the dielectric constant of
steam will increase wfth an increase in presssure required to maintain such a
Properties of Water at High Temperatures and Pressures 25
temperature. At the critical temperature (374.2°C), the ratio of the two dielectric
constants (DC of steam / DC of Water) is unity. In other words, under such a
condition, a given solute will be distributed equally between the two phases.
However, this is a limiting condition. What is of greater interest is the range of
235-320
o
C, in which the ratio is a function of temperature and pressure. The
vapour transport of solutes like silica are attributed to this dependence and the
higher the ratio, the greater is the solute content of the steam phase, which
deposits the solute at a different part of the steam water circuIt where temperature
and presssure are lower.
It is obvious from the above discusssion that the properties of water undergo
significant changes as a function of temperature a'ld presssure. In natural systems
such phenomena are encountered in geothermal waters/steam, volcanic activity
etc. In modern industrial practice, we come across the of high
temperature - high pressure water fm ,1 the classical steam engines used for
locomotion, to highly complex steam-water circuits of power plants, whether
they are fired by fossil fuels or nuclear energy. A certain amount of individuality
characterises each system that arises from the interaction of specific materials
of construction of the steam-water circuit. However, there are enough common
points to broadly discuss and understand the application of the basic concepts
of physical chemistry of water and its dilute electrolyte and non-electrolyte
solutions to industrial practice, so as to achieve maximum efficiency and economy
in energy generation ..
REFERENCES
l. Sudarsanan M. and R. K lyer, (1991). Water in the Environment. Bull. Ind. Soc.
Analytical Scientists, pp.ll-19.
2. Todheide K. (1972). Water at High temperaturess and Pressures, Water A
Comprehensive Treatise, Vol. I, 463 ed. F. Franks. Plenum Press.
3. Rice M. H. and J. M. Walsch, (1957), Dynamic Compression of Liquids From
Measurements on Strong Shock Waves, J. Chem. Phys, 26, 815-823 (from the
experimental Hugoniot Curve for water in this paper, where specific volume, cm
3
/g
is plotted against shock pressure in Kilobars, the density of water at 20°C as function
.of pressure can be computed).
4. Cobble J.W. (1964). The Thermodynamic Properties of Aqueous Solutions - VI, J.
Am. Chem. Soc., 86. 5394.
5. Mesmer. R. E .• C. F. Baes and F. H. Sweeton (1970), Acidity Meassurements at
Elevated Temperatures, J. Phys. Chem, 74, 1937.
6. Marshall W. L. and E. U. Franck (1985), J. Phys. Chem. Reference Data, 10,295.
7. Helgeson H. C. (1957), Thermodynamics of Complex Dissociation in Aqueous
Solution At Elevated Temperatures, J. Phys. Chem, 71, 3121.
8. Thornton E. W. and M. V. Polley. (1986), A Review of!>H Calculation and Corrosion
Product Solubilities Under PWR Primary Coolant Chemistry Conditions, Report
No. TPRDIBI08781R 86, MSP (85)3. Central Electricity Generating Board, U.K.
4
WATER CHEMISTRY, MATERIAL COMPATIBILITY
AND CORROSION
Water chemistry is a relatively new sub-branch of physical and inorganic
chemistry, that signifies different things to different professional chemists. On
the other hand, corrosion signifies essentially the same to all professional
metallurgists and chemists. Material compatibility is the interface between the
two specialities of watei: chemistry and corrosion s·ince what one is concerned
with is basically an interfacial phenomenon, between a metaJlic or a fine oxide
surface (solid) and water (liquid) and steam (gas)(1).
To an environmental chemist, water chemistry would mean the analytical
determination of impurities especially the trace toxic inorganic and organic
contaminants in water and the detoxification proC'esses thereof. For a chemist
involved in a chemical process industry, water chemistry is equivalent to effluent
chemistry and treatment. On the other hand to a chemist in a power
plant or other industries such as fertilisers, water chemistry would immediately
signify the chemical regime that is reqUired to be maintained in the steam-water
circuits so as to minimise corrosion and material transport. The latter, although
on a very small -scale is of serious concern to the chemists associated with the
nuclear power industry. Here it would lead to the generation of radioactive
nuctides and their transport to unshielded locations where maintenance and repair
are needed(l). The focus of the present monograph is on water chemistry in
such a high based industry, while effluent treatment and environmental
chemistry of natural waters is touched upon only for the sake of completeness.
4.1 CORROSION IN AQl}EOUS SYSTEMS
Corrosion in an aqueou!> SY3tem occurs due to the interaction between the surface
of the mr.terials which come IOtO contact with the aqueous environment, many
Water Chemistry, Matenal Compatibility and Corrosion 27
times under conditions of stress. The stress could be chemical in the sense that the
aqueous environment may be acidic or alkaline. The chemical stress can be viewed
or understood in terms of thermodynamic and electrochemical concepts. The stress
could be metallurgical in the sense that the material surface has defects, either inherent
or as a result of the manufacturing process. It might be thermal stress as in a steam
generating system. In reality, corrosion would be the consequence of a combination
of all the above stress factors. To avoid or minimise corrosion, great care has to be
taken in selecting the construction materials as well as in controlling the chemistry
of the aqueous environment. The problems posed by faulty water chemistry or
material incompatibility are the same in thermal and nuclear power stations as
well as in chemical process industries such as fertilisers{3}.
Basically, corrosion is a process where the metal atoms leave their location
on the surface and stabilise in the form of ions in solution. In high purity water,
where no other electrolyte is present to any significant extent, it is the solubilising
action of water on a metal surface like iron, which is the first step in the corrosion
process. The polarisability of the water molecules on contact with the iron surface
leads to the weakening of the O-H bond and gives rise to reactions below, which
show the combined effect of solubilisation and hydrolysi3(l).
n Fe (Bulk) -+ (n - I) Fe (Bulk) + Fe
2
+ + 2eo (4.1)
(4.2)
The primary corrosion product is [Fe (H
2
0)s OH]+, which gives the second
hydrolysis product, Fe (OH)2' Fig 4.1. These two chemical species appear later,
in many forms due to secondary reactions as shown in Fig.4.2.
1'"
StopS I 1. ClOClDATION
ME1l'L ""''It II
t
"'F :®
::;<

(!)H,O DIPCU
1
.. to. Dipolo.
ran60111ly
D1I,dbutod
_ I'Ol.AIUSATION Of IIt.O
_ WlTH F.(U:
II
2. sa.VATION - DlSSOLIJTION.
III
o-H aond in H .. O
,nolec.w.akened
SHl:ATH
IN PRESEN:£ OF
SPEClflCALL Y
IIBSOlIBtD ANION.
Fig. 4.1 Mechanism of the First Step in Iron Corrosion
28 Water Chemistry
The secondary products are FeO.OH, FeO, Fe
3
0
4
, Fe
2
0
3
etc. These secondary
reactions being pH dependent, the percentage of iron present in each of the
ab0ve forms also shows a pH dependence. Reaction (4.1) in terms of the
fundamental galvanic dissociation of metal atoms (in this case Fe) from a surface
in contact with water is anodic. Corresponding cathodic reactions may be written
as,
2e' + 2Hp ~ 20R' + H2
2e' + 1/
2
°
2
+ H
2
0 ~ 20R'
(4.3)
(4.4)
Reaction (4.3) points to the pl)ssibility of hydrogen formation in a corrosion
process, while reaction (4.4) gives a clue as to the role of dissolved oxygen
present in water. The lower the dissolved oxygen content of water, the smaller
will be the cathodic reaction (4.4). In general, corrosion is less, if the water is
deoxygenated.
In high temperature, slightly alkaline and deoxygenated aqueous
environment, the principal corrosion product formed on an iron surface (carbon
steel, stainless steel) is magnetite, Fe
3
0
4
(Fig.4.2). Under the ccnditions
specified, there is a possibility for Fe (OH)2 to exist as neutral molecules in
solution, which get converted to magnetite in a short time,
A • AGEING
Ht· HEATING
(4.5)
P • PRECIPITATION
H • HYDROLYSIS
• OXIDATION
R • REDUCTION
D • DEHYDRATION
Fig. 4.2 Possible Species of Iron under Aqueous Environment
\
Water !hemistry, Material Compatibility and Corrosion 29
This reaction is known as Schikkor reaction(4). a thermodynamically
favoured standard free energy change, A GO of -9.9 kcal at 298°K (2S°C).
The hydrogen generated in.reaction (4.S) is in addition to that from (4.3). In
actual practice, the determination of the hydrogen content of steam (in view of
the very limited solubility ofH2 in water) serves to monitor the overall corrosion
process in the steam water cycle. There is evidence to indicate that magnetite is
also formed directly on iron surfaces as follows:
3 Fe + 4 OH- Fe
3
0
4
+ 2 H2 + ne - (4.6)
H
2
0 (Bulk) + ne- H2 + nOH- (Bulk) (4.7)
Compared to the bulk density of Fe (-8g/cc) that of:nagnetite is lower (-S.2
g/cc). Hence the direct formation ofFe
3
0
4
on ,an iron surface leads to a sudden
volume expansion.
On stainless steel surface, Fe304 unC:ergoes a series of substitution reactions
with the alloying elements (Cr and Ni) and complex ferrites such as CrFe
2
0
4
and NiFe
2
0
4
have been identified in the corrosion products.
Before dealing with the behavior of magnetite and other oxides in high
temperature aqueous environment, it would be advantageous to complete the
discussion on corrosion, which as noted earlier could have its origin in chemical,
electrochemical and metallurgical parameters. What was discussed so far is a
general at&tk occurring uniformly over metallic surfaces on contact with water.
There are other specialised forms of corrosion(5). Pitting is one such, extremely
localised attack resulting in pits and even pin holes such as in chloride induced
pitting of stainless steel under stagnation. Another form is known as stress
corrosion caused by a synergistic effect of tensile stress and conosive
environment. Examples are, caustic cracking of boiler, tubes, cracking of stainless
steel in a chloride environment etc. Concentration of impurities in crevices and
under deposits leads to an attack termed as crevice corrosio;- :f two dissimilar
metals I alloys are in contact through an aqueous environment, galvanic
will cause one of the surfaces to corrode rapidly. The use of sacrificial electrodes is
a direct application resulting from this form of corrosion. From a metallurgical view
point, intergranular corrosion and selective leaching need (0 be mentioned. The
former is a localised phenomenon occurring along the grain boundaries such as the
corrosion of stainless steel in heat affected zones of a weld. The de-zincification of
brass is an example of selective leaching from an alloy, as a result of which porosity
is developed. A purely mechanical form of attack is the erosion - corrosion, as
experienced at inlets of condenser tubes of a sea water cooled power station.
4.2 SOLUBILITY OF MAGNETITE (FE
3
0
4
)
In the temperature range of interest to power station water chemistry the
solubility of magnetite and other corrosion product oxides is proportional to
the temperature and pH(6.7). Since pH scale as defined undergoes a change with
temperature, one must be very clear about what is specified by pH, e.g., measured
at 2SoC or say at 300
o
C, as illustrated in Figs. 4.3 and 4.4
Different sections of the steam water circuit are at different temperatures.
Thus changes in solubility of magnetite would mean that in a closed, but
circulating heat transport system, magnetite gets transported (solubilised and
redeposited) from relatively hot to cold sections of the system. Thus, a process
of material transport, although on a small scale, is set up in the closed, circulating
JO
Water Chemistry
C(Fe)lI/mo1 dIi;'
lfl
ld
1.573K
1;f
2.523K
3.413K
lei
4.423K
5.373 K
1O'
6.32:1K
1 ~
,,1
lrJ.
,,/ 2
10'
,lI!
···s
la
1
6
3 4 5 6 1 6 9 10 11 12 13 14
pt4298K
Fia. 4.3 Solubility of MaaDetite in tbe pH RaDae 3 to 13 <')
1 I I I I I
8
-
0
'i
100 - at
~

0
1
8
10 -
I-
:::1
-
-
0
1 -
8
~
l-
.... 0
LL.
t:
0.1 -
0
0
~
~
0 0
l-

0
~
U-
8 ~
8
- '!
0
c1
0.01 -
'$
~ 0
8
I-
!l
0
8
I I
3 4 5 6 7 8 9 10 11
pHaoo
Fia. 4.4 Solubility of Maanetite at 300 ·C VI. pHJOO <')
Water Chemistry, Material Compatibility and Corrosion 3/
high temperature and high pressure water (and steam) circuit. In fossil fuelled
power stations, this phenomenon is of no serious consequence, except that unde:
deposit attack is promoted by the formation of deposits allover the place. However,
in a nuclear power station, this would mean the transport of corrosion protlucts
through the reactor core and their activation »Y neutrons, leading to radioactive
nuclides. These are transported to ollt-of-core surfaces and get deposited on them,
thereby contributing to a radiation field which prevents accessibility to the system
for maintenance. This is popularly known as the 'man-rem' problem and is a direct
consequence of water chemistry at high temperatureS<2).
4.3 DEPOSIT FORMATION VS. ROLE OF ZETA
POTENTIAL
The deposit forming species are oxides, hydroxides and frequently hydrous
oxides. The latter are as a result o( normal chemical, electrochemical and
metallurgical faclors operating at the interface of a metal and high temperature
waterS). Two major forces are responsible for the deposition of such particles,
viz., the mass forcos and the surface forces. The mass force is directly
proportional to the mass of the particles (i.e., to the cube of the diameter of the
particles), while the surface forces is proportional to the surface area of the
particles (i.e. square of the diameter of the'! particles). As the size of the particle
decreases, the surface forces prevail over the mass forces. When any solid is in
contact with an electrolyte solution, it acquires a surface charge which is
balanced by in equal and opposite charge in the liquid layer near the surface,
but arranged in two layers which is known as the electrical double layer. The
first one is the adherent monoionic layer of counter ions held by chemical forces
and immovable with respect to the solid. The second one is a diffuse outer
layer of counter ions mobile with respect to the surface as shown Fig. 4.'.
FIRST LAYER
ZlTA POTENTIAL
iE---t------SHEAR PLANI
BULK OF THISOLUTION
l' 1----- DII'I'UIE LAYlR
Fig. 4.5 Conceptual Reprentation 01 Electrical Double LayerS)
32 Water Chemistry
The difference of potential existing between the shear plane and the bulk of
the solution is called the Zeta potential The magnitude of is a measure of
surface charge on the solid surface and its sign is the resultant of the charge on
the surface and the charge on the first layer.
corrosion products, as seen earlier, have MOR groups at the surface.
The acidic property of these MOH g;:::lUPS becomes pronounced as the pH
decreases. At a particualr pH, and hence the surface charge becomes zero and
this pH is known as the Point of Zero Charge(PZC) of the oXide. At PZC, the
surface has an equal tendency to reiease H+ or OH- ions. Hence, at a constant
temperature can be represented as
= K (PZC - pH) (4.8)
Where K is the proportionality/constant and pH is that of the aqueous phase
in contact with the oxide surface. From equation (4.8) it can be seen that the
oxide surface is positively charged when pH is less than PZC and negatively
charged when pH is greater than PZc. Table 4.1 lists the PZC values of several
corrosion product oxide and hydroxide species, with H+ or OH- as the only
potential determining ion(8).
Metal
Cr
Mn
Fe
Co
Ni
Cu
Table 4.1 PZC Values of some Corrosion Product Species
(8
)
Species PZC at 30°C PZC at 90°C
(in pH units)
hydrous Cr
2
0
3
7.0
Mn(OH)2 7.0
Mn0
2
4.0 to 4.5
FeOOH 5.4 to 7.3
Fe(OH)2 12.0 ± 0.5
a. - Fe
2
0
J
6.7
y - Fe
2
0
3
6.7 ± 0.2
Fe
3
0
4
6.85 5.4
CoO 11.5 10.8
Co (OH)2 11.4
NIO 10.3 ± 0.4
Nl (OH)2 11 to 12
Cu(OH)2 9.4 ± 0.4
CuO 9.5 ± 0.4 8.2 ±0.4
Cu
2
0 8.44 7.36
The apparent decrease in pH of water and dilute aqueous solutions is also
seen in the values of PZC as a function of temperature, since PZC is expressed
in units of pH.
4.4 DISTRIBUTION OF IMPURITIES BETWEEN
WATER AND STEAM
While efforts are made to keep impurities such as NaCl, NaOH and Si0
2
at
minimum values in the water phase of a steam water circuit, they can never be
Water Chemistry, Material Compatibility and Corrosion 33
brought down to zero level. By implication, a steam generating system promotes
concentrations of such impurities in the water phase. Dependil'g upon their
solubility in the steam phase under the conditions of pressure and temperature
of the steam, the distribution of such impurities between the two phases is of
special rele\ ance to the per.formance of the turbine. This is so since the pressure
and temperature decrease in the various stages of the turbine leading to the
deposition of substances like NaCl and Si0
2
on the turbine blades. If allowed
to go unchecked, such deposition will lead to the failure of the turbine blades.
Hence the basic information on solubilities of salts and metallic oxides in steam
and their distrIbution coefficIents, needs to be discussed for a proper
understanding.
The distribution coefficient K IS defined as the weight ratio of the
concentration in the steam phase to that in the water phase.
K = ppm(steam) or K = mole / Kg.steam
ppm(water) mole / Kg. water
(4.9)
For neutral compounds such as oxides, the distribution coefficient depends
only upon the solubility. On the other hand, for electrolytes such as NaCl, NaOH
etc., an equilibrium between the neutral form and the respective ions also comes
into play. As seen earlier decrease in the dielectric constant of water with
temperature will effect this equilibrium in favour of the neutral species. Thus
in general, K increases with temperature which would automatically
the pressure of the steam phase. Martinova(9) has described what are known as
the carryover coefficients into steam from water as a function of pressure.
This is generally known as a 'ray diagram' and is shown in Fig. 4.6.
10
0
,
10-
1
10.
2
K
10-
3
10-
4
10-
5
10"'
10-
7
"

-". :"""- -"-

-
-.
-- .. ===::::::..;::
=-
I .... Ii!
• 1 ,II.
-....:
--- I 4 a!.
It1\!
1
+ -
" I; [a,a
J-
-
-
I I
I
I
-
-
--I-
-
--I--
::::::::::::
......


"il!!
I-
-..
.,
I
::::::::

ii:l!I.,..

aa
Fa
3
0.
Al
2
0
3
B
2
0
3
N10
CuO
BaC
L
I i r I
-[ J
I
I ..... [ i a,
MgO
CaSO. Na
2
SO. CaCI
2
NaCI NaOH
220 200 160 120 80 60 40 30
DRUM PRESSURE, ATM
LICI
20 10'
Fig. 4.6 Ray Diagram of Carryover Coefficients of Salts and Metal Oxide
Contaminants in Boiler Water(9)
34
Water Chemistry
From Fig. 4.6 it may be noted that in general, the carry over of metallic
oxides to the steam phase is much greater than of salts. This is to be expected
since in the water phase also, the oxides exist as neutral molecules. In ~ l e context
of a power plant, the carry over coefficients of Fe304 arid other Fe oxides,
Si0
2
• NaCI and NavH are of special importance.
The International Association for the Properties of Steam has compiled
extensive data on the distribution coefficients and other relev.ant information
pertaining to Fe
3
0
4
, Si0
2
, NaCI and NaOH in steam-water cycles of power
plants(10.1J). The data are basic in nature and valuable in understanding the vapour
carry over of oxides and salts. As an example Fig. 4.7 shows the solubility data
of NaOH on pressure(P), temperature (T) coordinates.
LIQUID
CONCENTRATION
1000
SATURATED
VAPOR
WATER
CONCENTRATION
tOO
!
1000ppb
87%
Ii
100
I
80%
I
100ppb
400
I
I
I
I
I
20CI
I
10ppb
I
I
/
,/ ,/
,/ 1 ppb
400 100 800 1000
TEMPARATURE. OF
Fig. 4.7 Caultic Solubility Data Shown on P, T Coordinatel(lO)
The caustic solubility constant composition lines approach the saturation
curve asymptotically. If one considers only those area!! with a very small amount
of superheat, concentrated caustic solutions are possible at virtually every stage
of pressure decrease (turbine expansion) that crosses the saturation lines.
Calculated data on the vapour pressures of concentrated caustic solutions are
also shown in Fig. 4.7. The same data and extrapolations are shown in Fig. 4.8,
on a Mollier diagram. The overall conclusions are the same through either method
of data representation. If one proceeds from the assumption that the
concentration in the liquid phase can attain very high values locally, considerable
quantities of the substances can be camed over into steam. Thus from Fig. 4.8,
it may be seen that at 290
0
C (550Of) and a concentration of 50 percent in the
water phase, upto 1000 ppb of NaOH can be expected to be present in the
steam.
Water Chemistry. Material Compatibility and Corrosion 35
1300
III
~
1250
!
.... 87%
....
....
....
1200
1.4 U 1.8 1.7 1.8
ENTROPY. BTU/LB. IF
FII. 4.8 Caustic Solubility Data shoWD OD a Mollier Dlalram(lO)
Silica is one of the impurity deposits that causes considerable damage to
turbine blades. The steam carry over ofSi0
2
is essentially due to the distribution
of this compound between high temperature water and steam phases. Table 4.2
shows the data on this distribution coefficient as a function of pressure.
Table 4.1 DistributloD of Silica betweeD Steam aDd Water Phases
(Kgleml)
+-
Pressure ..... (psig) Cone. of Si0
2
in Steam
Cone. 'of Si0
2
in water
86.0 1273 0.0045
103.0 1529 0.0075
121.1 1793 0.012
137.8 2039 0.020
148.2 2193 0.030
172.3 2550 0.050
190.2 2815 0.080
206.7 3059 0.160
Since the solubility ratio decreases noticeably with decrease in pressure (a
condition in the steam turbines from the inlet of steam to its e ~ a u s t ) deposits
of silica on the turbine blades are to be expected. Suffice to say here tha[
increasing concern for low pressure turbine blade and rotor damage by stress
corrosion and corrosion fatigue has caused new limits on allowable steam
contamination by NaCI, NaOH and Si0
2
to be recommended. Such limits
have an impact on the required purity of steam generator feed water.
4.5 ROLE OF ALKALINITY IN STEAM-WATER
CIRCUITS
It has been known for some time that mild steel or carbon steel (one of the main
36 Water Chemistry
components of the steam-water circuit) exhibits a minimum rate of corrosion at
25°C in the pH range of 8 - 10. Thus it has been a practice to make use of
volatile alkalising agents such as ammonia, morpho line end hydrazine,(ll) in the
cycle. The volatile compounds, as compared to the non-volatile alkalies such as
NaOH have the advantage of being easily carrieo over into the steam phase.
They thus give corrosion protection to that part of the cycle where steam comes
into contact with the surface of the construction materials. Because of their
differing dissociation constants, different quantities of each of these reagents
ate required to attain the sam!" pH, as given in Table 4.3.
Table 3 Relationship between pH values at 25°C and Concentrations of
Alkalising Agents(ll)
pH Value Concentrations in mg/l
attained Ammonia MorEholine
7.S 0.05 0.02
8.0 0.03 0.20 0.08
8.5 0.075 1.00 0.60
9.0 0.30 ]0.00 5.50
9.S 1.0 80.00 50.00
Bearing in mind the role .)f dissolved oxygen in promoting corrosion,
hydrazine is often added as an oxygen scavenger. Somehow, its role in increasing
the pH of the water - steam circuit has not been well recognised.
A study of the distribution coefficients of these three volatile compounds
between water and steam showed that for ammonia, the ratio (concentration in
steam / concentration in water), decreases sharpl) in the region of 25°C to
100°C after which it decreases asymptotically with temperature. This means
that sufficient alkalisation in the condensing phase is not achieved with ammonia.
On the other hand, the value of this ratio for morpholine increases with
temperature. However, the magnitude of the ratio is smaller than that for
ammonia. while pH is upgraded during the condensation process, the
concentration of morpho line required is more than that for ammonia. Hydrazine,
on the other hand is a good compromise candidate. Its distribution ratio increases
with temperature, while a concentration lower than morpho line, but higher than
ammonia is required to attain the same pH value in the condensate. Despite this
obvious advantage, is rarely considered as a.n alkalising agent in the
steam generating industry, because of its tendency to decompose under the
cond:tions of temperature prevalent in the boiler side(ll. 13). The main
decomposition reaction is,
3 N2 H4 ...... 4NH3 + N2
(4.10)
A small part also decomposes as
N2 H
4
...... N2 + 2H2
(4.11)
The typical values for the halftimes of the de('omposition reaction (4.10) of
hydrazine and the associated rate constant are given in Table 4.4.
Wate, Ch,mlstry, Material Compatibility and Corrosion 37
Table 4.4 Thermal DecompositloD of Hydrazine(l1)
Temperature °C
t 112 (Sec)
k(sec·
I
)
160 307.7 0.0025
200 41.0 0.0169
250 6.5 0.1066
300 1.5 0.4620
Thus in the temperature range of interest (:!50oC - tJOO°C), hydrazine
decompo.e. faster and the need for replacement will be high, if employed as an
alkalisina agent.
4.5 DEOXYGENATION
As mentioned earlier, dissolved oxygen is the main culprit in causing corrosion
of iron and ferrous alloys on contact with water, especially at high temperatures.
To minimise this problem, deoxygenation is an established practice. At present
hydrazine and several forms of catalysed hydrazine ~ e employed for this
purpose(l2.13) .
The deoxygenation reaction is given as,
N2H4 + °
2
.... N2 + 2H
2
0
(4.12)
Although the above equation denotes a simple bimolecular homogenous
reaction, tnere are several parameters which have a marked effect both on its
rate, as well as on its initiation; these include temperature, pH, reagent
concentration, presence and concentration of catalysts etc. The reaction has a
period of induction and proceeds very slowly at room temperature.
Two additional mechanisms appear to operate during the process of
deoxygenation in addition to the one given in equation 4.12. A heterogeneous
surface absorption (on metal or metallic oxides) reaction has been postulated.
N
2
H
4
.... [N2H4.02] .... N2 + 2H
2
0 (4.13)
Surface
Another heterogeneous process is where heamatite (Fe
2
0J) in the steam-
water circuit is reduced to Fe
3
0
4
, which further reacts with oxygen.
N2H4 + 6 Fe
2
0
3
...... N2 + 2H
2
0 + 4 Fe
3
0
4
(4.14)
Experience indicates the involvement of all three mechanisms.
Coming to the parameters that govern the deoxygenation the effect of
temperature is appreciable. While the reaction is hardly perceptible at 20°C, it is
complete in a few seconds at 170°C. The deoxygenation is most effective in the pH
range of9 - 10. As the purity of water increases, the rate falls showing that impurities
present in water catalyse the reaction. The effect ofhydrazine concentration is very
pronounced. Thus, while 10 percent excess hydrazine requires 40 hours for
scavencing dissolved oxygen (at a particular temperature), the time is reduced to
less than 10 hours with 200 percent excess. In general, metal ions are found to
catalyse the reaction. This is especially true of Cu
2
+ and other 3d transition
38
Water Chemistry
element cations. It has been observed that certain organic additives (derivatives
of catalyse the process. Catalysed hydrazine is available in the
market.
The discussion in this chapter clearly indicates that water chemistry and
corrosion are closely interlinked, leading to a favourable material compatibility
(or the lack of it) in high temperature and high pressure water-steam circuits. A
large amount of basic physico-chemical information has been generated and
collateci. The proceedings of several conferences organised by the International
Association for the Properties of Steam, provide, valuable data in this regard.
REFERENCES
I. Venkateswarlu K. S.. (1979), Corrosion in Power Industry, Corrosion &
Maintenance, 4, 1089.
2. Venkateswarlu K. S., (1980) Corrosion and Compatibility of Materials in Nuclear
Power Stations. Proc. of Symposium 3, CHEM TECH '80, International Congress,
Bombay.
3. Venkateswarlu K. S., (1982), Role of Water Chemistry in Corrosion Control, Proc.
DAE Symposium on Corrosion alld its Control in Power and Chemicallndustries,.
Baroda.
4. Schikkor G., (1929), Z. Electrochem, 35,25 and (1993), Z. Allorg. AUgem. Chem.,
212,33. .
5. Sundaram C. V. and H.S. Gactiyar. (1981), Materials Behaviour in Nuclear Reactor
Water Systems., Proc. Topical Meeting on Water Chemislry in Nuclear Power
Stations, pp.19-67.
6. Bohnsack, G., (1987) The Solubility of Magnetite in Water and in Aqueous Solutions
of Acid alld Alkali, Vulkan Verlag, Essen, pp. 143-48
7. Thornton E. W. and M. V. polley, ( 1986), A Review of pH Calculation and Corrosion
Product Solubilities Under PWR Primary Coli ant Chemistry Conditions, Central
I::lectricity Gelleratillg Board Report, TPRDIBI08781R 86, MS P (85) 3. and
References therein.
8. Venkateswaran G. and K. S. Venkateswarlu, (1976), Physico-chemical Interactions
at the Mctal-Water Interface alld Their Significance to Deposition Problems in
Nuclear Power Stations, Proc. DAE Symposium, C,hemistry and Physics of the
Surface of Metals and their Oxides, Kalpakkam, pp. 176-186.
9. Martinova O. T., (1973), Solubility of Inorganic Compounds in Sub-Critical and
Supercrillcal Water, Pro('. Symposium High Temperature/High Pressure
Ell'ctr(;chemi.l'try ill Aque'Jus SolutiollS, UK, January (1973).
10. Gould G. c., R. W. Potter and F. J. Pocock, (1978), Activities of the International
Association for the Propertics of Steam, Amercian Power Conference, Chicago,
April, 24-26.
II. Heitmann H. G., (1978), Fundamental Research in the Field of Water Chemistry in
Power Plants During the Last Years and its Demands: Proc. 8th International
COllferellce Oil the Properties of Steam, lAPS, pp. 533-546.
12. Ramshesh V. and K. S. (1986), Use of Hydratine for Deoxygenation:
. A Status Report, Technical Report No. 53, Central Board of Irrigation & Power,
New Delhi.
13. Venkatcswarlu K. S., (1988), Deoxygenation: An Essential Ingredient in Steam
Generating Industry, Chemical Business, February (1988).
TREATMENT OF NATURAL WATERS FOR
INDUSTRIAL COOLING
5
Water finds extensive use as a heat trasfer and cooling medium in chemical
process industries and power generation through the deployment of heat
exchangers, condensers and c o o l ~ n g towers. In addition, after special purification
procedures, it is also made use for generating high pressure steam in thermal
and nuclear power stations. It has been roughly estimated that 90 percent of all
the water used by industry is for heat transfer and cooling while about 8 per
cent is used for process requirements and about 2 percent for steam generation.
Tile water quality criteria and hence the treatment procedures are different for
these three end uses. Stringent control of water chemistry., io; essential for steam
generation, while this is not so for the other two uses. In this chapter, attention
will be focussed on the chemical treatment and quality of water needed for
industrial cooling.
Although water from a particular source may be acceptable for drinking or
for agriculture, certain suspended and dissolved impurities present in it, will
have to be removed by suitable pretreatment procedures, so that it is acceptable
for industrial cooling with or without further chemical conditioning. The type
of treatment to be adopted depends upon the quality of the available source of
natural water, as well as on tbe capital and operational costs and environmental
requirement of the industrial location. Thus, some site-specific variations of the
general water treatment procedures are ullavoidable. Efforts are constantly being
made to envolve improved water conditioning programmes that are environmentally
friendly, efficient and cost effective.
Water from rivers, lakes and even underground borewells, is employed for
all the three purposes mentioned above, after proper chemical treatment(1). On
the other hand, sea water is used only for cooling the condensers and process
40
Water Chemistry
water heat exchangers (once-through) of power plants and oth,; .. heavy chemiea)
industries such as petrochemicals located along the coast. Because of the l a r g ~
volume of running sea water in once-through systems. there is no question of a
chemical treatment. Only at a few locations, depending upon the material of
condenser tubes, a chemical treatment of sea water is practised. On the other
hand, biofouling prob'lems are severe with sea water applications and antifouling -
practices are all pervasive(l). Surface and groundwaters also experience
biofouling, though of a different nature and magnitude. We shall first deal with
the problem of biofouling encountered in the use of natural waters for coolin,
condensers. heat exchangers etc.
5.1 BIOFOULING IN NATURAL WATERS
Power stations at inland locations make use of surface waters from rivers, dams
and lakes for condenser cooling, with or without the aid of cooling towers.
Such raw waters contain their natural flora and fauna. The flora mainly comprises
phytoplankton in association with bacteria and fungi fed' '.Jy nutrients like
nitrates, phosphates, iron, silica and carbonic acid present in these waters.
Sunlight penetrates the low depth turbid water systems like lakes and river
banks and supports the photosynthetic activity of the phytoplankton consisting
of different types of algae such as the blue greens, greens and the diatoms.
In India, power stations located at Dhuvaran, Tarapur and Trombay on the
west coast and Ennore, Kalpakkam and Tuticorin on the east coast make use of
sea water for cooling the power plant condensers and process water heat
exchangers(3).
The conventional and the widely practised method for controlling biofouling
is through the chlorination of the coolant water(4,s). Since large volumes are
involved in once through systems, no other method appears to be economically
viable. At the same time this imposes the need for handling bulk quantities of
hazardous chlorine. mostly in the form of pressurised gas cylinders round the
clock. Residual chlorine present in water from a cQoling tower basin could be
detrimental to fresh water ec<,system when the blowdown water is drained into
the environment. It has been observed that residual chlorine present in the
combined form and as chlorinated organics is detrimental to fish, invertebrates
and algae in natural water. The effect is a function of the size of the organisms,
the period of exposure, the water quality, (e.g. pH) temperature and the nature
of the chlorine species. Hence there is a need to regulate the release of chlorine
content in the effluents(6,6.). Environmental concerns have led to the lowering
of the allowable discharge limits to less than 0.3 mg/l or even 0.2 mg/1 of
chlorine at the condenser outfall. Such discharges are permitted for not more
than 2 to 3 hrs in a day. For continuous chlorination, the discharge limits are set
much lower at 0.05 mg/I.
When chlorine gas is added to water, hypochlorous (HOCI) and hydrochloric
(HCl) acids are formed.
el
2
+ H
2
0 -+ Hel + HOCI (5.1)
The oxidising property and the disinfecting action of chlorine is due to HOel.
Hypochlorous acid dissociates to give hydrogen and hypochlorite (Oel) ions
Treatment of Natural Waters for Industrial Cooling 41
depending on temperature and pH of the water; the dissociation is considerable
above a pH of 6.5 (Fig 5.1). The OCI- is not as effective as HOCI(4). Chlorine
also reacts with ammonia present in water producing chloramines, which possess
a disinfecting property, 300 times less than that of HOCI. Chlorine reacts with
nitrogenous compounds like proteins, and other organic matter forming
chlorinated compounds or oxidised products. Chlorine present as HOCI and
OCI- is termed free residual chlorine and that existing in the f:-rm of chloramines
etc., is termed combined residuals. The current practice consists of intermittent
chlorination upto 1 mg/l of free residual chlorine for 20-30 minutes, two to
three times a day. In order to get the free residual chlorine, it is necessary to
know the chlorine demand of the water, that amount of chlorine consumed
by the organics and inorganics, (e.g., present in water before free residual
chlorine is detectable in water.
100
0
80
20

40
ci
80
Z

S!
III
40
60 &
>
t
..:
20
80!
0
100
4 5 6 7 8 9 10 11
pH
Fig. 5.1. Dissosiation of HOCI and HOBr as a function of pH(15)
It has been suggested that death of bacterial cells results from a chemical
reaction of HOCI or a chlorine compound with an enzyme system essential for
metabolic activity. The difference between various disinfectants is attributed to
their ability to penetrate the cell. The effectiveness of HOC I as compared to
other forms of chlorine species could be due to its small molecular size and
electrical neutrality which allows it to penetrate the cell wall. The lesser
bactericidal effect of OCI- could be due to its negative charge, which may impede
its penetration into the cell. Chloramines have comparatively slow diffusion
through tne cell wall, however, these are of importance in water chlorination
due to their persistence in water for a longer period of time as compared to
HOCI.
From this, it is obvious that chlorination is quit,. an effective antifoulant
measure in fresh water systems, where the pH is in the range of 6 to 7, while in
slightly alkaline waters (8 pH), it is less effective. The question that needs an
answer is the universal observation that chlorination of seawater, which has a
pH of 8.2, is still effective in controlling marine biofouling. Herein comes the
role of dissolved bromide in sea water.
The presence of 68 mgll of bromide in seawater, results in a complex
chemistry of chlorinated seawater(6). This is because chlorine (HOCI) releases
42
Water Chemistry
HOBr from bromide. Hence at the pH of seawater, chlorination leads to the
formation of hypochlorous acid, OCI' ion, HOBr and OBr' ion, plus the
bromamines, which co-exist with chloramines. Hence total residual chlorine in
seawater always refers to a mixture of HOCI, HOBr, OCI', OBr', chloramines
and bromamines.
The dissociation of HOBr to form H+ and OBr' (hypobromite ion) is also
pH dependent; with the equilibrium shifting to a higher pH value. Upto 8.0 to
8.2 pH, 90% of bromine is in the form of HOBr and the percentage drops to
10% only, at 9.5 pH (Fig. 5,1). HOBr is a superior biocide as compared to
HOCI. Consenquently, the chlorination of seawater which leads to HOBr, is a
successful method of controling marine biofouling(7). At a coastal power station
this practice should be optimised depending upon the nature of the fouling
community and the chlorine demand of the seawater in the intake area. The
chlorine demand varies somewhat with the season and the sea currents and
needs to be analytically determined at regular intervals so that the total chlorine
dose needed can be evaluated.
As briefly mentioned aboye, HOCI reacts with both inorganic and organic
nitrogenous compounds present in natural waters (a major fraction of the chlorine
demand). Examples of such compounds are ammonia, nitrates, amino acids,
proteins and humic acid. While the reaction of HOCI with ammonia is
comparatively fast, that with organics is slower and depends upon the contract
time. The formation of chloramines, stepwise is a follows.
HOCI + NH3 -+ NH
2
CI + H
2
0
HOCI +- Nf!2CI -+ NHCI
2
+ H
2
0
HOCI + NHtt2 :-+ NCI
3
,+ H
2
0
(5.2)
(5.3)
(5.4) ,
Similar equations can for organic nitrogen compounds. The
reaction between chlorine and organic nitrogen is relatively slow. The product
of chlorine demand and contact time is a characteristic of the water under
examination and is given by,
D= K t
n
(5.5)
In Eq.S.S, D is the final chlorine demand (initial chlorine dose - final residual
chlorine) in mgll, K is the chlorine demand in mgll at the end of one hour
(initial chlorine dose - (minus) chlorine residual at the end of one hour), t is the
contact time in hours and n is the slope of the curve that is obtained on plotting
the experimentally determined chlorine demand at different time intervals vs.
contact time in hours(4,6,8).
A significant development following chlorination of natural waters for
industrial use, is its reactions with the ever increasing' number of man made
chemicals of undetermined toxicity discharged into the aquatic environment.
The majority of the reaction products are chi oro-organics phenols,
aromatic acids etc.). The cumulative effect of the potentially carcinogenic chloro-
organics is a matter of concern. Thus, in once-through systems, lot of care is to be
exercised in regulating the chlorination practice so that the discharged water contains
as little total residual chlorine as possible.
Treatment of Natural Waters for Industrial Cooling 43
Turning to the biological aspects of chlorination, the general of
chlorine as a bactericidal agent is universally accepted. Work on algae indicated
that while the effect of chlorine is algistatic, that of bromine is algicidal. Reduced
marine productivity in chlorinated seawater has been observed.
Similarly reduced carbon uptake (using C-14) and depression of photosynthesis
were noted. Branacles are one of the common macrofouiants and their response
to chlorine has been well studied. Eighty percent average mortality of Balanus
larve was recorded after five minutes exposure to seawater at a chlorine level
of 2.5 mg/I of tOlal chlorine. Marine mussels, typified by Mytilus edulis, Mytilus
virdi and Mytilus californicus, are the most important of the fouling organisms
that restrict the cooling water flow. Macrofouling by branacles and mussels
have been the focus of many investigations, including studies at Bombay and
Kalpakkam, India(!I·12). The time to achieve a 100 percent kill has been related
to the temperature and residual chlorine level through a generalised regression
equation. It has been realised, of late, that instead of intermittent moderate
chlorination (2.5 to 3 mgll of free residual chlodne), practised once in eight
hours, a continuous chlorination level of (0.2 to 0.4 mgll of free residual
chlorine) appears to be more effective in combating mussel fouling. Chlorine
interferes with the process or thread of filament formation by the mussel larve,
that is vital to the growth of these organisms.
5.2 OPERATIONAL PRACTICE OF CHLORINATION IN
POWER STATIONS· USE OF BROMINE
The Central Electricity Generating Board (CEGB) U.K., carried out a systematic
study on various antifouling methodi-used in cooling water circuits. They found
that chlorination is the most economical method for combating all biogrowth
in power station circulating water systems(13). According to the CEGB, c.ode
for chlorination is as given below:
(a) Unless local pollution of seawater is severe it should be assumed
that marine fouling is likely.
(b) A thorough census of fouling organisms must be carried out before
the erection of a power station.
(c) Chlorination plant must be ready before water is admitted to the
circulating water culverts. Chlorine injection must be such that
residual chlorine is distributed uniformly throughout the intake water.
(d) Residual chlorine of 0.2 ppm must be maintained at the condenser
outlet.
The Tarapur Atomic Power Plant consumes 2500 - 3000 kg. of chlorine
everyday. The duration of chlorination is 15-20 minutes in each shift of eight
hours with 2-3 mg/l of residual chlorine at the condenser water box. There are
four bays at the intake. Each bay is subjected to a shock dose of chlorine that
results in 2 to 3 mg/l residual chlorine for I hr.lweek.
While all the seawater cooling systems are once-through, a number of fresh
water cooling systems are not. In fact it is becoming the norm to use cooling
towers to dissipate heat into the atmospheric environment. Thus. they are
44 Water Chemistry
recirculating systems, where most of the cooling water is recycled between the
cooling tower basin and the heat exchangers or condensers. Fresh make up water
is added only to compensate for the evaportion losses from the cooling tower
and the blow down is discharged into the aquatic environment, so that a balanced
chemical conditioning is maintained in the recirculating cooling water. Biofouling
is again a problem area in these systems in which chlorination is invariably used
to Since, it is a recirculating system, once in a while additional
biocides can also be used without economic penalty.
Micro organisms, dead or alive, form slime, which acts as material for
cementing particles together. It is, therefore, essential that tt.ey are dispersed in
water using surface active agents. Dispersed biological matter also makes the
chlorination programme effective, by allowing chlorine to interact easily with
the binding material. It has been found, for example, that algae and bacteria can
be flocculated using cationic polymer. Biocides used in water treatment
programmes are mostly cationic surface active agents. Recently it has been
established that chlorination and the use of low molecular weight cationic
polymers alone can control biofouling of cooling water systems, and the use of
biocides can be eliminated.
In fresh water cooling systems,the trend is towards a programme of chemical
conditionirrg of the circulating water, whose pH is maintained towards the alkaline
side. Under such conditions, as seen earlier, chlorination loses its efficacy and
research was focussed on the use of alternative biocides. Keeping the experience
with seawater in mind, the application of bromine (in the form of bromide or
C?ther bromine cOqlpo\.tnds) as a substitute tor chlorine is coming more and more
into use(IS). Bromine chemistry offers reduced corrosion and environmental
hazard. The efficacy of HOBr as a biocide over that of HOCI has been well
established facilitating dose reduction. Rapid decay of bromine and its compounds
sllch as bromamines, minimises the environmental impact ofthe biocide on the
receiving aquatic eco-system. In addition to HOBr, bromine is available in
different chemical forms which can be added as a biocide. One such compound
is bromochloro dimethyl hydantion (BCDMH) which is commercially available.
At about 2 mg/l equivalent of chlorine, BCDMH and HOBr are about 100 times
more effective than HOCl towards pseudomona in alkaline cooling waters.
Brominated propionamides like, 2,2-dibromo - :3 - nitrilo propionamide are
extremely potent broad spectrum microbiocides. The compound is an oxidising
type microbiocide and is unstable with increasing pH and temperature. Thus,
the cooling water dosed with this chemical can easily be detoxified before being.
discharged into the natural aquatic environment.
Equally effective are the bromamines. In addition, the reaction leading to
the formation ofbromamines can be made reversible by lowering the pH. Thus
they are less persistant than the corresponding chloramines. Electrochemi .. >J
measurements with copper alloy condenser tubes such as Cu : Ni = 90 : 10
showed that in the presence HOBr, their oxidative corrosion is much less than
in the presence of HOCI, especially around pH 7.S • 8.2. It is shown that
manganese fouling of 304 stainless steel (SS) condenser tubing is arrested on
switching over to bromine based biocides(IS). In case, the required bromine
biocides are not available, recourse carl be taken to adding a few mg/1
Treatment of Natural Waters for Industrial Cooling 45
(5 mgll) of sodium bromide to the recirculating cooling water (pH about 8 or
more) and carrying out chlorination as usual. As in seawater chlorination, the
chlorine will release bromine in the form of HOBr as an effective biocide.
Manufacturers of cooling water chemicals offer a number of proprietory
pjpcides, These are recommended to be used once a week, while chlorination is
suspended for that day. Their effectiveness depends upon site specific studies
and no generalisation can be made. Tin - organic biocides made a major entry
into the markel, but of late, environmental considerations have imposed servre
constraints on their large scale application. Methylene bis-thiocyanate is an<'ther
biocide that is effective against. algae, fungi and bacteria. The compound is
made use of in combination with a dispersant to enhance its penetration of
algal and bacterial slime layers.
5.3 MATERIALS IN A COOLING WATER CIRCUIT
Before considering the chemical treatment and conditioning of cooling water,
it would be appropriate to look briefly at the materials with which such treated
water comes into contact. From the early stages, brass was used to serve as the
material for the condenser and heat exchanger tubes. Admirality brass or Naval
brass is used for fresh water systems, while aluminium (AI) brass is the preferred
material for seawater systems. Subsequently cupronickels were developed and
the 90-10 alloy found wide applications in seawater systems. The 70 - 10 allo),
is better suited, but is not much used in view of its high cost. II' all these copper
based alloys, the release of cupric ions due to corrosion is considered to be a
good antibiofouling measure, in view of the toxicity of copper to such organisms.
When the need for total leak proof condensers arose, titanium (Ti) came into
use as the tube material. However, it has no resistance to biofouling. Another
equally good alloy is stainless steel, especially some of the new stainless steels
that were developed with this specific application in mind. Again stainless steel
has no in-built resistance to biofouling. In most cases the tube sheet is of carbon
steel, sometimes overlaid with materials like stainless steel and titanium.
For seawater applications employing either Cu-Ni or Ti' or even SS, there is
no chemical treatment for erosion and corrosion prevention. However, with Al
brass being a widely used material, a chemical treatment was found that is
effective against such types of attack.
Leakages in condensers, where water with a high salt content is used for
cooling, have almost always given rise to serious effects in the operation of
power stations(l6). However, immediate damage bears no relation to the possible
consequential damage. In extreme cases, on the spot intrusion of cooling water
containing sodium chloride leads to equipment breakdowns such as a tube burst
in the boiler or breakages of turbine parts in areas having contact with wet
stream. A prolonged search for leak dt'tcction and fixing becomes necessary.
The major part of the damage to condensers was substantively due to the
corrosion of the condenser tubes. When copper alloyed tubes were used, the
damage was caused by local corrosive attack on the tubing. The resistance to
corrossion of copper alloyed tube materials in braekish or seawater is said to be
due to the formation of a natural covering film of cuprous oxide. If the thickness
of this film is inadequate in aggressive cooling waters, it is necessary to add
46 Water Chemistry
agents which will create additional prote,ctive layers which are sufficiently strong
and adhere over the internal tube surfaces.
5.4 FERROUS SULPHATE INJECTION
The use of ferrous sulphate as an inhibitor of the corrosion of aluminium brass
was first described by Bostwick(l7). He produced detailed statistical data relating
to the addition of ferrous sulphate versus the number of tube failures(18.1f). By
way of explanation, Bostwick envisaged the iron additive acting as compensation
for the loss of 'natural' iron which had been available from the water boxes
prior to installation of cathodic protection. Ferrous sulphate dosing is now widely
practised, but there is still no agreement on the mechanism of protection. One
way to look at this situation is by considering the principle of Point of Zero
Charge (PZC) of the original oxide layers and its interaction with iron hydrous
oxides having a different PZC. Iron may also act as a cathodic inhibitor or can
be incorporated into a cuprous oxide (Cu
2
0) film, by a mechanism similar to
that found when iron or nickel are incorporated from cupro-nickel alloys. This
gives It a greater pllssivity. Other workers believe that a relatively thick film of
hydrated ferric oxide if formed which reduces the erosive action of seawater
and enables a protective film to form on the brass itself. This view implies that
the iron film is effective in the commissioning stage of condenser operation and
that there after iron neither contributes to the passivation action nor is necessary.
There may then be a possibility of reducing or discountinuing iron additions to
the cooling water once service conditions are well established. However, this
has not been realised in practice at all.
Of the many conceivable and proposed measures, the presence of ferrous
oxide layers has proved most efficient in many respects. It is basically of no
consequence whether these oxide layers are consciously produced, for example,
by ferrous sulphate (FeS04) injection or by making use of sacrificial anodes, or
whether uncontrollably formtd, for example, via the corrosion of steel tubes in
the cooling water feed lines. The main thing is that conditions of uniform
distribution, good adhesion and reconstitution ofthe'film are maintained.
With regard to development oflayers via ferrous sulphate injection, several
procedures have proved successsful for continuous operation :
Injection of 1 mgll Fe
1
+ in cooling water for the duration of one
hourday. '
Injection of the same concentration twice per day, but for half an
hour at a time.
Continuous injection to values in the 10 /lg/l range.
What concentrations and sequences are finally chosen will depend on the
organic matter and sulphide content in the cooling water; especially during back
washing of the condensers. Small quantities will be chosen as far as possible
because of the formation of slime.
The injection of concentrated FeS0
4
solution (21 percent FeS04' 20°C)
should be effected shortly before entry of cooling seawater into the heat
exchangers or condensers, since longer dwell times result in premature oxidation
which from flaking Fe (III) compounds. In the case oflarge size condensers, an
Treatment of Natural Waters for Industrial Cooling 47
additional injection into the return water boxes can be advantageous.
The incorporation of iron takes place through negatively or positively charged
colloids of hydrated iron oxides, either under the influence of the electric field
of the Cu
2
0 covering film with a positive Zeta potential, or by electrolytic
precipitation on the cathode surface of the epitactic layer. It is therefore not
expedient to inject FeS0
4
directly into pickled tubes, i.e., tubes deprived of
their own natural covering film.
Depending on the injection method, brown uniform layers of varying
structure are formed on ,the inner surfaces of the tubes after some weeks. The
thickness of these layers is 7S microns. On continuous cleaning with sponge
rubber balls or brushes, glossy reddish-brown films with a thickness of only a
very few microns appear. The thickness and roughness of the films increases
proportionally to the length of the cleaning interval. Automatic cleaning methods
lead to a consolidation and of the external covering layers.
There are difference of opinion with regard to the cleaning intervals for
condenser tubes having ferrous sulphate injectiC'n. Whilst some aim for a firmly
adhering and consolidated external protective layer with continuous cleaning,
others are of the opinion that, on account of the formation of natural oxide
films, a cleaning period of only one hour at a time is acceptable. There is also a
body of opinion against the sponge ball cleaning after the treatment with ferrous
sulphate.
After a longer injection period, the layers show up as two lamellae on the
metallographic picture. Over the natural Cu
2
0 covering film is a homogeneous,
closely meshed layer of ferrous oxide, the crystalline content of which consists
of gamma-FeO OH. In isolated cases, FeCu0
2
has also been radiographically
diagnosed. According to the results obtained by electron microscopy this hybrid
oxide seems to occur as a thin intermediate layer to which adhesion-enhancing
properties are ascribed.
Ferrous sulphate treatment has been successfu)'y applied not only to brand
new tubes, but also to condensers that were in service for sO.me years and which
were damaged by pitting and erosive corrosion. It is desirable to inject ferrous
sulphate the operating period and at an increased level and frequency
after a shut down maintenance. This ia due to the tendency of the layers to split
on drying and peel off in some places.
Electrochemical characteristics of the corrossion of Ni-Resist type 2 alloy
in seawater, dosed with ferrous sulphate have been investigated(lO). The alloy
underwent a uniform cathodicafly controlled corrosion and no alteration in the
stress corrosion cracking suceptibility of the alloy was observed. Electrochemical
measurements have shown that on Cu:Ni (90: 10), the protection offered is
meager (very thin layer) and hence it is not worthwhile to practise !his treatment.
The procedure has been also advocated for Ti and SS tubes, but has not found
acceptance.
5.5 COOLING WATER TREATMENT
Cooling water treatment of a power station or a heavy chemical industry is to
be organised from the very inception(14). Unless the required site specific water
quality assessment is carried out well ahead of time and suitable chemical
48
Water Chemistry
treatment procedures evolved, problems such as reduced flow in heat exchanger
tubes. failure of equipment etc. would certainly crop up during operation of the
plant (Fig.5.2). Thus the most important part of the study is togather data on
water quality, over a two year period.
Cooling
Tower
" /"

Makeup ............. /'
Water __ -"'::"/:.....JI-----7J
Heat
E)(changer
Fig. S.2 Important Problem Areas in Cooling Water System(l)
As discussed in detail earlier, in once-through cooling, very little chemical
treatment is made use for economic reasons. Of more interest are the
recirculating systems with or without a cooling tower. The open recirculating
cooling water systems invariably have a cooling tower from which water is lost
due to evaporation and mechanical dispersal due to the sprays in the tower.
This will result in concentration of impurities and intentionally added chemicals
in the cooling tower water. In order to maintain an appropriate level of the
chemicals, a part of the water is blown down from. the tower. The combined
loss due to evaporation, mechanical factors and blowdowil is made up by adding
the requisite quality of fresh water.
In view of the concentration of impurities in the cooling tower due to
evaporation losses, the circulating water contains greater levels of both cations
and anions as compared to the make up water. The ratio is known as the
concentration cycle. One can take any pair of ions in both streams to arrive at
the concentration cycle. It is usual to take chloride ion ratios as chloride
deposition is the least. The cooling towers usually operate with concentration
cycle in the range of 2 to 3.
The preliminary steps in the treatment of raw water consists of,
(a) Contr01 of biofouling by chlorination, and
(b) Removal of suspended solids.
The first step has already been dealt with. The suspended solids are removed
usually with the help of a flocculator, by adding the necessary coagulants(ll).
The process, known as clarification, makes use of alum or ferric sulphate. The
hydroxides of the trivalent ions, neutralise the surface charge of the suspended
Treatment a/Natural Waters/or Industrial Cooling 49
particles and facilitate their agglomeration. An important problem in flocculation,
is the generation of sludge, which is bulky due to a high content of water. This
has to be dewatered and disposed of. Another problem is the carryover of the
finely divided hydroxide flocs into the clarified effulent. Such problems, arising
out of the lise of inorganic coagulants alone, has been overcome to a large
extent by the use of organic polyelectrolytes in conjunction with them. Thes.e
are water soluble, long chain polymers with attached active groups and having
molecular weights in the range of 10
7
• The ionisation of the active group confers
a charge on the bulky molecule as a whole. Based on the sign of the charge,
these are classified as cationic or anionic polyelectrolytes. Also available arC!
non-ionic or so called neutral polyelectrolytes. Based on site specific
experimentation, a polyelectrolyte or a combination thereof is selected. These
compounds help in neutralisation of the surface charges of the suspended fine
particles by the inorganic coagulants. This results in the formation ofmicroflocs
and subsequenttly in r.lacroflocs. It was sec.n that the use of polyelectrolytes
reduced the volume of sludge by as much as 75 percent allowing it to be readily
dewatered. The carry over problem is thus minimised. Although organic in nature,
the use of polyelectrolytes does not add to the organic fouling of the treated
water. Lesser quantities of inorganic coagulants have been found to be adequate.
The dissolved chemical constituents present in the cooling water could result
in(l) :
(a) Interaction with materials of contruction leading to corrosion,
(b) Reactions such as precipitation among themselves that could lead to
scale formation (such reactions depend upon concentration,
temperature etc.) and
(c) Acting as nutlients to the biological species present in the system,
thus aggravating the problem ofbiofouling.
The constituents present in water fall broadly under four categories:
(a) Suspended impurities like clay, silica, organic maiter etc.
(b) Dissolved impurities, such as Ca
2
+, Mg2+, Na+, NH/, He0
3
·, Cl·,
C03·2,S04·2, silica, besides traces of iron, N0
3
·, and soluble organic
matter, (e.g., humic substances).
(c) Micro-organisms such as algae, different types of bacteria (sulphate
reducers, iron bacteria, etc.) and fungi.
(d) Dissolved gases like 02' CO
2
, NH
3
, H
2
S, etc.
In general scale forming salts have inverse solubility characteristics and tend
to get precipitated when saturation is reached due to local changes. These include
temperature, concentration due to evaporation, presence of ions which cause
precipitation etc. Calcium. magnesium, carbonate. sulphate, phosphate and
sometimes silica contribute to this effect. Based cn thermal conductivity, the
loss of heat transfer due to scaling has been estimated as. Si0
2
: 0.2 to 0.5.
CaC0
3
: 0.5 to 1.0 and CaS0
4
: 1.0 to 2.0 (in k.callm.h.oC)
Constituents like carbonate. sulphate, phosphate and organic compounds
from cooling tower serve as nutrients for the micro-organisms. The presence of
50
Water Chemistry
ammonia or nitrate also contributes to the metabolic activity and can change
the water chemistry of the system considerably.
Dissolved C O ~ in the water, which Jepends very much .:>n the temperature
and pH of the water, is an extremely significant, factor in chemical reactions
involving precipitation of calcium and magnesium salts as scales. Dissolved
°
2
, and CO
2
contribute to the increased corrosion of system surfaces.
Amongst the added chemicals, that contribute to scaling in cooling water
systems is the degradation of metaphosphates to orthophosphates.
In general it is very difficult to predict in isolation the part played by the
dissolved constituents in promoting corrosion, biofouling and scale formation.
Sometimes one of the reactions can aggravate the other processes.
5.5.1 Deposit Formation and Control
In a cooling water system, an efficient transfer of heat from process fluid to
cooling water is possible, when deposition on heat exchanger surfaces is
minimised(l,14). Presence of sparingly soluble salts (e.g. CaS0
4
) having inverse
solubility, results in scaling (Table 5.1). Corrosion of constructio'n materials
leads to the deposition of corrosion products (mainly different forms of iron
oxides) on heat exchanger surfaces. Deposit of dead bacteria, algae, etc., also
impair heat transfer. A cooling water treatment programme should effectively
control the above mentioned deposition processes.
Table 5.1 Solubility Trends among Scale Forming Calcium Salts.
Approximate solubilities, mg/1.
Temperature CaS0
4
CaS0
4
CaS0
4
CaC0
3
°c
anhyrous 0.5 H
2
O 2H
2
O
0 High V. High 1775 90
40 2800 High 2050 50
100 750 22{)0 1700 15
Crystallization of scale forming salts precedes the deposition step. Formation
of crystals takes place initially by nucleation followed by crystal growth.
Nucleation in a cooling water system occurs either in solution or on rough
surfaces, once the water is supersaturated with any scale forming salts, e.g.,
CaC0
3
• Crystals grow either in solution and subsequently get deposited or grow
on the surface itself. Deposition can be controlled during the crystal growth
stage by use of surface active agents. These chemicals may increase the time of
nucleation but cannot prevent it.
As noted earlier, surface active agents such as polyelectrolytes are classified
as cationic, anionic and nonionic depending on the functional groups possessed
by them. As a consequence of the absorption of surface active polymers on the
suspended particles, floes are formed which get deposited very loosely on the
surfaces. It is also possible that the surface active agents occupy lattice sites of
the growing crystals resulting in the formation of distorted crystals having large
internal stresses .. These modified cryst .. ls do not adhere to the surface on which
they are first deposited.
Treatment of Natural Waters for Industrial Cooling 51
The effectiveness of the surface active agents is not the same for all types of
deposit forming compounds. The vari'ous surface active agents should be
screened for their effectiveness for the different deposits encountered in the
cooling water system. Sometimes the final deposit may result through an
intermediate compound, e.g. Mg (OH)2' The inhibitor chosen should be more
effective for the intermediate compound than for the final product.
S.S.2 Scaling Indices
As against the principles of cooling water chemistry discussed so far, let us see
how the treatment programmes have evolved in practice. The most common
scale pJ;esent in cooling water systems is calcium carbonate, derived from the
decomposition of calcium bicarbonate that is normally present in natural waters.
Thus it is obvious that when the circulating water has higher levels of calcium
hardness and bicarbonate alkalinity, this problem becomes acute. Since the
solubility of calcium carbonate shows a decrease with increase in temperature,
the inner surface of the heat exchanger will be prone to scale formation. To
predict the scale forming tendency of a cooling water with respect to calcium
carbonate several teChniques are employed, the foremost of which are the
Langlier (or saturation) index, the Ryznar (or stability) indeX: and the Puckorus
(or modified stability) index(14). It is required to calculate pH of saturation (pHs)
for calcium carbonate. The calculation being involved, nomograms have been
developed for the use as ready reckoners. The Langlier equation is formulated
with pH of saturation (pHs) as,
pHs = (pK2 - pKs) + pCa + p Alk (5.6)
Where pCa and pAlk are the negative logarithms of their respective
concentrations (as in pH with respect of hydrogen ions). pK2 and pKs are the
second dissociation constant and the solubility product constant of calcium
carbonate respectively. The Langlier Index is then defined as,
LSI = pH actual - pHs
(5.7)
and can have a positive or negative value. The former indicates a tendency for
scaling while lateer signifies a tendency for corrosion by the cooling water.
The Ryznar Stability Illdex is given by
RSI = 2 pHs - pH actual (5.8)
Under this classification, a value of 6 for RSI indicates stable water, i.e. no
scaling or corrosion, values less than 6 would lead to scaling, while above 6
would result in scale dissolution, i.e. corrosion. The Puckorious Modified
Stability Index is formulated as
PSI = 2pHs - pHc
(5.9)
Where pHc is the equilibrium pH based on total alkalinity. Usually the former
two indices are made lise of for on site evaluation of the scaling and corrosive
tendency of natural cooling waters. Since temperature gradients are site and
design specific, a variable in the operator's control is pH, which is often adjusted
to keep the cooling water in a slightly scale forming condition, rather than on
the slightly corrosive side. This was an early way of cooling water treatment;
modern treatment programmes -depend upon inhibition of scaling as well as
52
Water Chemistry
corrosion by chemical additives. However, both Langlier and Ryznar indices
still serve as initial guidefines for 'evolving a proper chemical tteatment, as
v;ell as spot checks later.
5.5.3 Chemical Additives
Chlorination being verj' effective in the pH range of 6 to 7, coupled with the
need for reducing the bicarbonate alkalinity, acid addition is a common practice.
Concentrated sulphuric acid is used for this purpose and addition is usually
done in the cooling tower basin. Although there is a constant flow of water
movement in the basin, it is possible that mixing of the acid may not be uniform,
particularly if the slopes in the cooling tower basin are not proper or altered by
sedimentary deposits at selective locations. Such a situation could lead to
acidulated water directly getting into the heat exchanger tubes. Adequate controls
need to be exercised by measuring pH at different locations of the cooling tower
basin especially at the basin's outlets. It must also be mentioned that handling
of concentrated sulphuric acid is a hazard at all times, and more so during night
shifts. The workers have to be given training in safety consciouness and
remedies for treatment of acid burns must be available on hand. Since
chlorination is effective at a lower pH, acid addition should precede chlorination
when practised on an intermittant basis, i.e .• once a shift.
Addition of sulphuric acid to the cooling water automatically raises the
It:vel of sulphate. Depending upon the calcium, level of sulphate to be
guarded against, given the fact that its solubility decreases with decrease in pH
and increase in temperature .. Fortunately, calcium carbonate is more insol'lble
than calcium sulphate under SUGh conditions and thus will be deposited first. A
useful guideline is to see that the product of ionic concentrations of calcium
and sulphate does not exceed 5 x 10
5

There are two aspects for any cooling water treatment by chemical addition.
One is the need to prevent scale formations and other types of fouling, the
other is to prevent or inhibit corrosion of the system materials. These will be
considered separately. .
As will be seen later, inorganic phosphates have been widely used as
,-orrosion inhibitors. Consequently when considering prevention of scaling, in
addition to calcium carbonate and calcium sulphate. the possibility of calcium
phosphate scal'!s also needs to be considered. The other hardness ion,
magnesium, figures occa"ionally as scales in combination with silicate. In high
silica waters, the scales could contain silica (Si0
2
) itself or in the presence of
Mg appear as magnesium hydroxy silicate.
A good way to minimise' scale formation is to add chemicals that will keep
tne sC'lle forming constitutetlts in solution. For Ca and Mg, polyamino-
po)ycarboxylic acids such as ethylene diamine tetracacetie acid on its di sodium
salt (EDTA) and polYll),eric _phosphatl!s itke sodium hexameta phosphate have
been made use of. At present polyacrylates, copolymers of sulphuric and acrylic
- acids, polyelectro)ytes etc. in proprietary combinations
are available and are widely used for the inhibitation of
To keep Ca in solution a little Jess than 5 mg/l a polyacrylate with molec':llar
weight in the range of 1000 ·is sufficient. Both carbonate and sulphate scaling is
Treatment of Natural Waters for Industrial Cooling 53
prevented. Inorganic polyphosphates have been effectively replaced by organic
phosphates and phosphate esters. The former class are quite effective for Ca
scale control. The frequently used among them are amino methylene phosphoni-::
acid (AMP) and I-hydroxy-ethylidine 1. I-diphosphonic acid (HEDP). As seen
earlier. since AMP contains aminonitrogen. chlorine could attack it and destroy
its effectiveness. Thus AMP addition to the cooling tower basin or any injection
point has to be done out of phase with chlorination. Since HEDP does not have
this disadvantage. it is preferred over AMP. Both these phosphonates have a
tendency to dissolve copper from circuit materials. Thus when these are added
to prevent scaling. it is necessary to add an inhibitor to minimise copper
corrosion. The phosphonates are also taken up by the iron corrosion product
that is always present in the system. thus reducing their effectiveness.
The principle behind scale control by crystal modification was discussed
earIier(14). Sulphonated polystyrenes and polymalac acids which are water
soluble polymers. have been used for this purpose. At a concentration level of
0.5 to 2 mg!l they are very effective in modifying the cubic form of calcium
carbonate to spherical sludge particles. These polymers are also effective again.>t
calcium sulphate and phosphate. The sludge so formed can be conveniently
removed.
As the cooling tower is exposed to the environment the wind borne
particulates get trapped. Due to the absence of a clarifier or its malfunction.
some mud or silts will also get into the tower basin. The basin more or less acts
as a trap for all sorts of insolubles and fine sediments are.usually formed. There
is always a chance of these getting into the heat exchanger tubes and causing
fouling. Periodic clean up of the basin. provision of a side stream filter. use of
dispersing chemicals and removal of sludge are some of the techniques employed
for overcoming the problem. In many plants. the location of the cooling tower
is such that exhaust gases or those gases arising out of plant leaks get dissolved
in the cooling tower spray and thus alter its chemistry. A typical example is a
fertiliser plant. where the ambient atmosphere around the cooling tower could
contain ammonia and sulphur dioxide. Changing local wind direction would
result in these gases being blown into the cooling tower and there are many
examples. where pH of the cooling water gets altered as a result. The wooden
planks in the cooling tower are subject to biodeterioration. One of earlier
practices was to spray an aqueous solution of sodium pentachlorophenate on
such surfaces.
In Chapter No.4. the general aspects of corrosion have been considered and
the characteristics and causes of different types of corrosion described. To
recapitulate briefly. the anodic reaction. in the case of iron is.
Feo --+ Fe
2
+ + 2e -
while the cathodic reaction is represented by
2e - + 2H+ --+ H2
(5.10)
(5.11 )
If one breaks or inhibits either. or both the path ways. corrosion will be
minimised(14). Thus one can have anodic inhibitors and cathodic inhibitors with
which the cooling water system can be dosed. Best known among the former
are chromate and orthophosphate. while zinc and polyphosphate are well known
54
Water Chemistry
cathodic inhibitors. When both are used in combination such as chromate - Zn,
the treatment is known as dinodic. Among the anodic inhibitors, chromate was
widely used untill recently. It is very effective over a wide pH range and gives
excellent protection to mild steel at concentration levels of 300 to 500 mg/l.
However, with restrictions on chromate discharge into the environment
throughthe blowdown route becoming mandatory, such high concentrations
could no longer be employed. Thus a low chromate treatment, in fact a dinodic
treatment has come into vogue. In this practice, the pH is adjusted between 6 to 7
and chromate (20 - 25 mg/I), polyphosphate (10 - 20 mg/I) and zinc (I - 3 mg/I)
are added. This combination is one of the best availahle, but still suffers from
the disadvantage that the limit of discharge of hel.'avalent chromium into the
environment is 0.5 mg/1. Efforts have been made to evolve a blowdown
treatment process that either reduces chromate to trivalent chromium or recovers
chromate by ion exchange. The later is preferred due to various reasons.
In view of the above difficulties, the chromate treament is gradually going
out of use. A number of non-chromate treatments have been evolved(ll). These
are extensions of the scale inhibition techniques discussed earlier.
Polyphosphates and aminomethylene phosphonate figure in this treatment. The
idea is to inhibit corrosion by the formation of a fine scale in alkaline
conditions(pH 7 to 8.5), but at the samt time to control excessive scaling by
use of chemicals AMP, total phosphate levels can be upto 15 mg/I in the
case of polyphosphates and I to 2 mg/l of zn is also added as a cathodic inhibitor,
while the possibility of Mg silicate scale is minimised by adding an acrylic
polymer. Proprietary formulations ate available in the market. It has to be
emphasised that cooHng water treatment In the alkaline region is much more
delicate than the procedure in the 6-7 pH range and needs better chemical control.
Programmable chemical addition anl
1
frequent monitoring of chemical
parameters are required.
Among other corrosion inhibitors mention has to be made of nitrates and
orthosilicates on the anodic side and molybdates and polysilicates on the cathodic
side. In fact chromate and polysilicate in combination offer excellent protection
10 steel, copper and aluminium components of the 'cooling water circuit.
Polyphosphate and zinc offer equivalent protection to steel only.
In conclusion, a water treatment programme has to effectively counter
biofouling, scaling and corrosion. A variety of procedures are available Clnd
many of these are site specific and dependent upon the water quality. Since
ninety percent of the industrial usage of water is for cooling,this segment of
water treatment has special importance and can in no case be neglected.
REFERENCES
I. Ven'{8!.:swarlu K.S., B. Venkataramani and A.K.Sriraman, (1983), Chemical Trt:atment
for Cooling Waters, Proc.ofworkshop on Water Chemistry in Thermal Power
StatIOns. Central Board of Irrigation and Power, New Delhi, 9-12.
2. Viswanathan R. and K.S.Venkateswarlu, (1982), Programme to Control Biofouling
at Madras Atomic Power Project, Bull.Radiatlon Protection,S, 21-22.
3. Venk, \warlu K.S, (1981), Water Chemistry in Thermal Power Stations, Proc. J 19th
AlIlIll<ll Research Session, Central Board of Irrigation and Power, New Delhi, \-8.
4. While 'J.e., (J 972), Hand Book of Chlorination, Van Nostrand Reinhold, New york.
5. White G.C., (1975), Current Chlodrination and Dechlorination Pratices in the
Treatment of Potable Water, Waste Water and Cooling Water. proc. of the
Treatment of Natural Waters for Industrial Coolmg 55
Em "onmentallmpact of Water Chlorrnatlon. ed Jolley R L • Oak Ridge, 1-7
6 Da\ IS W P 'lnd D P Middaugh. (1975). A Review of Impact of Chlorination Processes
Upon Marine Ecosystem. Proc Env"onmental Impact of Water Chlorrnatlon, ed.
Jolley R L . Oak Ridge. p 299
6a K Sand R Vlswanathan. (1982). Environmental Aspects Concerning
the Large Scale of ChlOrine to Combat Blofouhng and references theretn, Proc.
InternatIOnal Conference on Coal F"ed PO\<l er Plants and the Aquatic EnVironment.
Copenhagen August. 1982
7 K S • (1990). Marine BlOfoultng and Its Chemical Control 10 Power
Industry. Chemlcul Business February - March (1990). pp 39-41
8 STlTdman. A K and R Sea Water chlOrination. Ind J Tech.
I
9 Karande A A . (\ 989). Manne B lofnultng the Need for an Integrated
Apporach. Proc 5pecIGIIsts Meettng on Martne BlOdeterroratlOn \<IlIh reference to
plant coo Illig s)stems BARC. J 8
J 0 Nair K V K . (J 989). Manne BlOfouhng and Alhed Problems 10 the Condenser Coohng
Systems of MAPS. Ibid. 92-103
II Holmes N J . (1969). The SuppressIOn fouhng by ChloTlnauon. 5)mposlum
VII Manne BlOlog\ ISSlled as a report b\ C"ntral EleclrtclI), Gelleratlllg Board.
UK.CEGB RD/LIM 269
12 Whitehouse J W. (1975). Chi on nation of Coohn.; Water A review of Literature on
the Effects of ChloTlne on Aquattc Orgamsm. CEGB (UK). RD/LlM/496
13 Coughlan J and J W Whltehcuse. (1077). Aspects of ChlOrine UtlhlatlOn 10 the
United Ktngdom. Chesapeake SCiellce 18. 102
14 S D and P R (19,;4). Coohng Water Treatment for Control of
Scahnll. Fouhng. COHoslOn. PO" er June. 1984. s-I to g-24 and lh.ereln
15 Fellers B D • E L r iock dnd J C Conley. (1988). Bromine Replaces ChlOrine In Coohng
Water Treatment. Power, June. 1988. 15-18
16 Papmarcos J . (1973). Tube DeSign Dm.ctlons. Power Engtneertng. July.
1973
17 BostWick TW. (1961), CorrosIOn. 17. 12-19
18 Borth R F a'nd H J Pryor. (1968). The Protection of Copper by Ferrous Sulp ... ate
AdditIOns, CorrodlOn 5:ll'lIce. 8. 149
19 Pearson C • (1972). Role of Iron In the Inhibition of CorrosIOn of Marine Heat
Exchangers A Re\ lew. Brlllsh CorrosIOn Journal. 7.61
20 Daud M B , G Venkateswaran and K S Venkdteswarlu. (1990). "Electrochenucal
CorrosIOn Charactenstlcs of NI-Reslstant type 2 In Sea Water Contatntng
Sulphate" Brlllsh CorroslGn Journal. 25(4), 3J3-307
21 Venkateswarlu K Sand B Venkataraman:. (1979), Recent Trends 10 Industrial Water
Treatment, ChemIcal Age of IlIdIG. 30.1089-! 098
22 Boffardl B P and G W Schweitzer. (1980). tn the Cht'mlstf) of Alkahn"
CoollIIg Water Treatment Calgon Coq:or?,lon. Pittsburgh. Pcnn-15230 USA Also
see Matena/s Performance. 19(12).44
23 Peters C Rand W R Holhngshad. A Ne .... Ge'leratlOn of Coolmg Water Treatment
Calgon Corporation. Pmsburgh Penn.-15230. USA
24 DubIO L • (198D). The Effect of Compounds and on
CaCO, Crystal Morphology. Annual Meetlllg of the Nallonal Assoc.atlOn of CorrOSIO,.
ElIgllleers. March, 1980
GENERA..L REFERENCES
I Handbook of Industrial Water COlldlllonlllg (1980).
Betz LaboratoTies Inc Pa. USA
2 The Na/co ",ater Handbook (1979)
McGraw-HIli Book Co . New York. NY.USA
3 Pmlclples of IndustrialWarer Trearmellt (1977).
Drew Chcnmal Co Boonton, N J USA
6
DEMINERALISATION BY ION EXCHANGE
The purity of water that is fed to a steam generating system is of utmost
importance, since by its very nature a boiler concentrates impurities. Hence the
lower the lewel of impurities, i.e .• dissolved solids. the better. Of course, this
applies equally rigorously to suspended solids and to an extent to dissolved
gases, especially carbon dioxide and oxygen.Thus, every unit of an electricity
generating jr'dustry installs, as part of its equipment, a water purification
system, more commonly known as a Oimineralisation(OM) Plant(1). Raw water
after proper pretreatment steps such as f1oculation, clarification, chlorination
etc. is the source for the OM plant(l). The process of demineralisation( getting
water free of all its dissolved cations and anions) squarely rests on ion
exchange. In fact water purification is the largest single application of the -ion
exchange technique. Synthetic ion exchange resins have become available over
the last fifty years. At present a variety of resins serve the needs of industries
as diverse as power generation to purification of life saving drugs.
Use of semi permeable membrances by the reverse osmosis technique for
water purification has become important. Since the last two decades drinking
water is being produced by this method.
As noted in an earlier chapter, drinking water contains dissolved salts, with
permissible levels being specified. Obviously, this' water is not fully
demineralised. However, if the raw water available to a power plant has a salt
content. higher than normally expected, it might be economically advantageous
to have the Reverse Osmoss(RO) plant precede the OM plant. This will reduce
the load on the latter and enhance the useful service life of the costly resins. But
this would mean, two plants based on different priniciples and techniques.
Reverse Osmosis is also a very useful technique in waste water treatment,
especially in the treatment of low level radioactive effluents.
Demineralisation by Ion Exchange 57
In this chapter, the application of ion exchange for water purification is
discussed, while reverse osmosis is dealt with later on under Desalination.
6.1 ION EXCHANGE RESINS
Natural zeolites of the type [Min (AI0
2
)b cH
2
0] are known to possess ion
exchange properties. In fact, some of these materials under the trade name
ofPermutit, were beiTlg used for water softening. Steam lvcomotives fill up such
softened water at railway stations to avoid scale formation in their boiler
internals. By softening is meant thal hardness causing cations such as Ca
2
+ and
Mg2+ are replaced by Na+ in the water under treatment. The synthetic ion
exchange resins developed during the thirties and forties are based on water
insoluble organic pnlymer matrices, with exchangeable sites(l). They are
essentially solid electrolytes and rt"ersibly exchange their mobile ions with ions
of like charge from the surrounding liquid medium. Divinyl benzene crosslinked
with styrene forms the matrix for strong acid cation exchange r.esins and strong
and weak base anion exchange resins. Divinyl benzene crosslinked with acrylic
or methyl acrylic acid forms the matrix for the weak acid cation exchange resins.
The terms "strong" and "weak" have the same connotation as in the case of
simple acids and bases. For example, while HCI is a strong acid, propionic acid
is a weak acid. Similarity, while NaOH is a strong base, ammonium hydroxide
is a weak base. It is the nature of the dissociating functional group in the resin
that is indicated by these terms.
The strong acid cation exchangers are produced by the sulphonation of the
polymer skeleton. The sui phonic acid group, .S03 gets fixed on to the matrix
while H+ ions are retained as mobile exchangeable ions. The anion exchange
resins are produced by chloromethylation followed by amination ofthe polymer
matrix. This leads either to the formation of quarternary or tertiary ammoniacal
nitrogen in the polymer matrix. Since tetracovalent nitrogen is always +ve, the
former would contain N+ in the matrix and is neutralised by a mobile anion such
as OH- or CI-. The resin that has tertiary ammonical nitrogen needs protonation
in the acid medium to act as an anion exchanger(l).
I
-CH-
©
I
SO;'W
Strong acid
cation
exchanger
f
-CH-

CH
2
I
(CH
3
)3W.C1-
Strong base
anion
exchanger
f
-CH-

CH
2
I
(CH3)2N.WCI-
Strong base
anion

Secondary and primary ammonium resins are also available. These are weak base
anion exchangers that can only function in an acidic medium. In the weak
58
Water Chemistry
acid cation exchange resins, the functional group is usually -COOH in place of
-S03H, in an acrylic -DVB matrix.
6.2 ION EXCHANGE PROCESS
The exchange eqilibria can be illustrated by the following reactions, taking
commonly present ions in natural waters as examples:
-RSOJ. H+ + Na+ <=> -RSOj'. Na+ + H+
-R4 W OH- + CI- ~ -R4W,Cl + OH-
(6.1)
(6.2)
H+ + OH- 7 H
2
0 (6.3)
Since the dissociation constant of water is very small and as the reaction of
H+ with OH- is extremely fast, reaction 6.3 goes to completion instantaneously,
which in turn acts as the driving force to push reactions in 6.1 and 6.2 in a fast
forward direction. When all the exchange sites that originally held H+ or OH-
ions are occupied b'y Na+ or a" (or any other cations or anions) respectively the
resin is said to be exhausted. The resin can then be regenerated by equilibration
with a suitable acid or a base.
-RSOj" . Na+ + HCI <=> -RS0
3
-. H+ + NaCI
-R4 N+.CI-+ NaOH <=> -R4N+. OH- + NaCI
(6.4)
(6.S)
The reactions in equations 6.1, 6.2, 6.4 and 6.S being equilibrium processes,
can be moved in the forward direction. As a result, the ionic impurities in water
are exchanged and retained in the resins. Thus when ordinary water, say tap
water, is passed through a bed ofa cation exchanger, all the cationic impurities
such as Na+, Ca++, Mg++ are exchanged for the hydrogen ions of the resin.
Obviously, the effluentwill be acidic. When this is passed next through an anion
exchanger, all the anionic-impurities such as CI-, N0
3
- and sulphate are held by
the exchanger, releasing OH- in turn. The hydrogen and hydroxyl ions-9(>mbine
to form water molecules and the effluent becomes neutral water again. The total
equivalents of cationic impurities are balanced by the total equivalents of anionic
impurities in 'natural waters. Thus, in principle, the ion exchange capacity is
exhausted in both the resin columns to the same extent. But in practice, it is
somewhat different, because of the presence of bicarbonate and carbonate ions
in natural waters. When water is pass sed through the cation resin, we have seen
that it becomes acidic. The hydrogen ions interact with these anions and the
resultant carbonic acid so formed decomposes into water and carbon dioxide.
H+ + HCO)" ~ H
2
C0
3
~ H
2
0 + CO
2
t (6.6)
Thus, a part of the anioic load is removed in the gas form reducing the load
on the anion resin bed. This causes a lot of bubble formation, almost like
frothing. It is necessary to degas this effluent, usually by blowing air through
it before it is led into the anion resin columns.
Since ion exchange is an electrostatic(ionic) phenomenon, it is to be expected
that multivalent ions rather, than monovalent ions, in the aqueous phase will be
preferred by the resin phase. Thus there is a selectivity series. For strong acid and
strong base resins, the selectivity for the ions commonly present in water is.
Deminerallsation bi' Ion Exchange
59
Fe
s
", > Ca
2
+ > Mgl+ > Na+ and Sulphate> chloride>Bicarbonate.
The strong acid and strong base resins function over the entire pH range of
tbe medium. The weak acid cation exchange and the weak base anion exchange
resin. function b ~ s t in basic and acidic pH ranges respectively.As a corollary,
strong anions such as sulphate and chloride are most preferred by the weak base
anion exchangers. This has led to an important application in water treatment,
whereby ions like sulphate and chloride are first removed by a weak base anion (
exchanger(since the medium at that point is gcing to be acidic as seen earlier)
and tbe so-called weak anions such as silicate are taken up in a second column
contaming a strong base anion exchanger.
6.3 PROPERTIES OF10NeEXCHANGE RESINS
A reference was made earlier to ion exchange capacity and its exhaustion. The
capacity is theoretically defined as the number of exchangeable sites present for
one mole of the resin. In practice it is expressed as milliequivalents per
gram(meq/gm) of the dry resin. Because the resins are always made use of in
a wet condition, the capacity is always less than the value in the dry state. For
strong acid cation resins, the capacity in the dry state could in principle reach
5.0 meq/gm. The capacity of the weak acid cation resin is much higher than this,
while that of anion exchange resins in general is somewhat lower than 5.0 meq/
gm. The capacity in the wet state is determined experimentally and it is usually
of the order of 65 percent of its value in the dry state(3). t, '
Another important property of the ion exchange resins' is the degree of
cross linking, which more or less corresponds to the percentage ofthe crosslinking
agent, viz., divinyl benezene present in the resin. Commercially available resins
have a range of crosslin king from 2 to 12. It is obvious that the greater the cross
linking, the greater will be the mechanical strength of the resin and hence its
swelling behaviour.It also determines the pore or the channel size.
Other physical characteristics of the commercial ion exchangers are ,density,
effective bead size, unifonnity co-efficient and the percentage of whole beads in the
material(3). For .S03H type resins, the apparent wet density is about 0.85 glml, while
for the -COOH type it is about 0.7 glm!. For anion resins, the apparent wet density
is again around 0.7 glm!. A good sample o f t h ~ resin contains not less than 70 percent
of whole beads, their unifonnity coefficient being 1.7(max.).
Some of the relevant properties of the standard resins are given in Table 6.1.
When the resin is in use, it experiences different cycles of treatment over
prolonged periods. For example a cation exchange resin would be cycling
between the -H form and the -Na form, while an anion exchanger would cycle
between -OH form and -CI form. This leads to a periodic swelling and
contraction of the resin beads, at least once in 24 hours. This is known as the
osmotic shock. Resistance to osmotic shock(resin beads should not crumble) is
a very important criterion for judging resin performance. Resins with low cross
linking experience this shock more than those with a high cross linking;
however, the latter are brittle. Sulphonated resins are more resistant to osmotic
shock than aminated resins (CER > AER).
60
Water Chemistry
Table 6.1 Characteristics of Standard Ion Exchange Resins(4)
Type and Bead Moisture Total Max.
functional size content exchange recommended Swelling

(mm) (%) ca2acitx (eg/l) Tem2' (oC)
(%)
SAC 0.45 4.4 1.9 120
Na+_H+
_S03H to 0.6 to 4.8 ( 7 )
SBA 0.38 4.2 1.4 60
CI-_OH-
_N(CH
3
)3 to 0.45 to 4.8 ( 19 )
WAC 0.33 4.3 3.5 120
H+
-
Na+
_COOH to 0.50 to 5.3 ( 10 )
WBA 0.36 4.0 1.9 100
OH-_CI-
NHOH to 0.46 to 4.5 ( 10)
In the table the abbreviations stand for,
,
SAC: Strong Acid Cation Exchanger,
SBA: Strong Base Anion Exchanger,
WAC: Weak Acid Cation Exchanger,
WBA: Weak Base Anion Exchanger.
There are two. types of strongly basic anion exchangers, Type I and Type II.
Both have quarternary ammonium groups as the active exchange sites. In Type
I, the groups attached to the nitrogeJ.1 are usually alkyl groups, while in Type II,
one of the groups is an alkanol thus,
/CH)
-N_, _CH)
---CH
)
Type • I

-N __ CH)
'CH
2
0H
Type - II
Usually Type II resins are used in water purification, since they are cheap.
However, they do not effectively remove silica, and are also susceptible to organic
fouling(l). .
Two varieties of ion exchange resins are commercially available for water
purification. They are classified on the basis of their porosity, (a) the gel or the
microporous type and (b) the macroreticular or macroporous type(3). The former
are clear, transparent and glassy in appearance. As their name implies, the pores
have a small diameter. The beads are spherical with a diameter ranging from
0.1 to 1.0 nm. The pores tend to get clogged with organics, which are relatively
large molecules. The macroporous resins on the oth<..r hand have pores whose
diameter is of the order of several thousand angstroms with large surface
areas( -100 m2/g).The macroporus resins are opaque in appearance and exhibit
a good resistance to osmotic shock. Large size neutral molecules such as org .. nics
can easily pass through them and hence flows are not reduced in service. These
organics subsequently decompose in the boiler.
6.4 DEMINERALISATION OF NATURAL WATERS
The feed to a demineralisation plant i<; clarified raw water, free from chlorine
Demineralisation by Ion Exchange 61
and nearly purified of organic and bilolgical rl1ateriai. In principle, what one
needs from that point would be a cation exchange column,(ofien referred to as
bed) a de gasser where air is usually blown through the effluent to drive off
carbon dioxide and an anion exchange bed, with facilities for regeneration of the
spent resins(4). In practice, it was realised that the water effluent from the anion
exchanger outlet was not pure enough; its specific conductivity ranges from
about 10 to 20 ).1S/cm, with the pH being in the alkaline range(upto 9.0). Hence
it becomes necessary to add one more bed of ion exchangers, called a mixed bed
wherein, as the name implies, a mixture of cation and anion exchangers are in
place. This additional bed improves the water purity and one can get water
whose specific conductivity is less than 0.5 ).1S/cm with a pH between 6.5 to 7.5.
Silica is reduced to less than 0.02 mg/l, with the total electrolytes being less than
0.1 mg/I.
It has been more or less established by experience that the cation exchange
part of the demineralisation process does not pose many problems. The
performance of a DM plant really depends upon the performance of the anion
exchanger and that of the mixed resin bed. From the input water side, the organic
content plays a significant part in the efficiency of the anion exchange. In several
countries, the current practice is to have two anion exchange beds. The first
contains a ~ e a k base anion(WBA) exchanger, while the second is made up of
a sttrong base anion(SBA) exchanger. The former has a better affinity for
chloride, nitrate and sulphate. Its bed volume, height etc. are to be determined
from what is known as negative M alkalinity, which represents the total
equivalents of these three anions. If this value is greater than that of bicarbonate,
in the raw water, it is essential to have a WBA column. The SBA bed which
follows it will then effectively pick up silica and the effluent from this anion
exchange bed will have a lowest specific conductivity and reduced silica slip.
6.4.1 Organic Load vs. Anion Exchange
For several years, water technologists all over the world have been preoccupied
by the problem of the fouling of strong base anion exchangers. Some of the
conclusions available in literature are(l), .
(a) In type I strong base anion resins, the fixation of organic matter
depends upon the dried matter content of the resin.
(b) Macroporous exchangers of the corresponding variety do not show
specially high fixation of organic matter I1S compared to gel type
resins.
(c) The removal of organic matter over a period of time is far from
complete and leads to partial, but irreversible fouling of the resin.
Hence type I strong base anion exchangers are not well suited for the
treatment of water having a high organic load. This conclusion is all
the more true if the raw water contains detergents even at low
concentrations of I mg/I.
(d) On the other hand, when type II strong base anion exchangers are
used, the quality of water from anion bed outlet has sh()wn a distinct
improvement for about the same conditions of organic and detergent
fouling.
62 Water Chemistry
(e) Investigations have indicated that condensation exchange resins(weak
base type) perform well in water containing a high percentage of
or.ganic matter.
(f) M'acroporous polystyrene weak base anion exchangers have their
own limitations and have been shown to be fouled up by water heavily
charged with organic matter.
(g) Experience shows that the presence of a weak base anion exchanger
with a reasonably dry solid content will protect the strong base
exchange resin column that follows it.
6.4.2 Mixed Beds(MBs)
In order to acheive the required quality of DM water as make up for the high
pressure boilers, a mixed bed of cation and anion exchange resins becomes
essential. The mixed bed is to be used as a final polishing unit and should be
operated with higher levels of regeneration. The plant should produce an
effluent that is essentially neutral. The cause of the poor quality of the water
coming out of the mixed bed Is contact with the sulphuric acid, which is
employed for regenerating the cation resin with some of the anion resin in the
bed. A strongly basic anion resin picks up acid in the form of the bisulphate ion
which is easily hydrolysed later resulting in the leakage of acid into the treated
water. This difficulty can be eliminated by using hydrochloric acid as the cation
resin regenerent. The strongly basic anion resins take up Hel as the chloride and
the chloride form of the resin is not suspectible to hydrolysis which could lead
to acid formation and its leakage.
6.4.3 Regeneration Technique
It is customary to effect regeneratiofl by passing the regenerant through the bed
of ion exchange resins in the same direction as the raw water being treated(1,l).
This is known as 'co-current' regeneration. It has been shown theoretically, all
well as in actual practice. that if the co-current regeneration is effected
(downward flow), the bottom layers of the exhausted columns are poorly
regenerated. unless a very large amount of regenerant-acid or alkali is used. On
the other hand, if the regeneration !s effected counter-current, that is. in the
direction opposite to that selected for the exchange cycle, the bottom
layers of the resins are more efficiently regenerated. This process results in
reducing the leakage of sodium to very low levels in the case of cation
exchanger and of silica in the case of anion exchanger during the exchange
cycle. Apart from increased regeneration efficiency. economy in regeneration
(in terms of consumption of chemicals) can be acheived by this technique.
With a strong acid cation exchange resin in service. when the diffusion
process has reached equilibrium, it is known that the relative concentration of
Na+ in the resin and in the liquid phase are not identical and their concentration
ratio or coefficient is a characteristic of the resin. Sodium
leakage,(Na)\ is expressed in terms of this distribution coefficient, K and the
ratio R of H+ in the last layers of the resin bed to its total capacity. thus,
S
(Na)1 = KR
1---
lOO-R
(6.7)
where S represents the total Na. From eq. 6.7. it is evident that if R is close
Demineralisation by Ion Exchange 6J
to 100, the last layers are that much nearer to a state of complete regeneration.
This is however achieved by counter current regeneration.
Water of very good quality can be obtained With counter-current regeneration,
whereas co-current systems require a finishing column, tv give the same result.
With counter-current regeneration system, the quality of the treated water is not
influenced by the nature of the influent water and by the regeneration rate; the
factor with maximum effect on water quality being the selected sodium leakage
rate at which the cycle is stopped.
It has been demonstrated that the performance of type II resin can be
improved by the counter- current regeneration. Silica leakage from type II resin
can be made to be on par with that of type I resins, if regeneration is made
counter-current.
Following the idea of counter-current regeneration, extensive studies have
been made on using the fluidised bed technique for demberalisation. In this
process the raw water to be treated is passed upwards and regeneration is
carried out by a downward flow of the regenerant.
Regeneration of a mixed bed has been a challenge for a long time. For an efficient
in-situ regeneration of the resins, the separation of the anion and cation resin should
be perfect and clean, which cannot usually acheived in practice. Due to improper
seperation during regeneration, a small layer of cation exchange resin at the interface
between the two resin phases is converted into the sodium form during the
regeneration of the upper layer of anion exchange resin. Also a part of the cation
exchange resin is present in the anion exchange resin bed and gets converted to the
sodium form.(Fig.6.1). This improper regeneration results in reduced operational
capacity (Na-slip) oftbe mixed beds cycle after cycle .
......... -_.-
RIOH
NaR

HR
MIXED BED
AFTER REGENERATION
. . -.
••••••• :. t:lR/R'OH

• •• •
• • • •• HR/R'OH
••• ••
MIXED BED
AFTER MIXING
Fig. 6.1 Sodium Contamination in Mixed Bed Regeneration (Scbematic)
This problem has been ingeniously overcome by introducing a layer ofin(!t
resin with carefully selected buoyancy properties, so that it acts as buffer layer
to seperate the two zones of active resins when the regeneration and rinse down
cycles are operating (Fig.6.2). This involves a careful selection of the density
of the inert material and control of the density of the cation and anion 'exchange
resins. The inert material is an organic polymer(for example, polystyrene) which
possesses no ion exchange properties and is physically and chemically inert to
most solvents and reagents, particularly to those normally used for regene.r:ation
purposes(2) .
64
Raw
water
Water Chemistry
+Re;!enerant
in
Mixed bed --W;mRm!l6!l
Anion
exchange
resin
EXHAUSTtON
Inert Regenerdnt
resin out

exchange
resin
REGENERATION
Fig. 6.2 Schematic Diagram of 3-Resin Mixed Bed System
Economy in the production of deionised water can be achieved by the use of
stratified beds which consist of superimposed layers of resins of the same polarity.
One of them is weak acid or base, while the other is a strong acid or base. During
regeneration, the weak acid resin, which is lighter than the strong acid resin is
placed at the top of the bed (Fig.6.3). The counter-current regenerant flow will then
pass upwards through the bed, encountering first the strong acid resin. followed by
weak acid resin. Thus the former is thoroughly regenerated(I).
EXHAUSTION
Raw water
Treated
water
REGENERATION
Regenerant
in
Regenerant
out
Weak
a:idic lbasic
resin
Strongly
acdiclbasc
resin
Fig. 6.3 Schematic Diagram of Stratified Bed
Demineralisation by Ion Exchange 65
In comparision with a single exchanger(weak or strong) regenerated by
counter-current flow. stratified beds have a higher operating capacity per
installed litre. Less resin is therefore required to treat the same volume of water.
and the efficiency of the process is improved in terms of less regenerant
consumption.
The ratio of weak acid( carboxylic) resin volume to total bed volume in the
case of a stratified system will be larger, the shoner the cycle time and the higher
the alkalinitynOS and total hardness/alkalinity ratios. The performance of
stratified beds also depends on a good seoeration between the two exchangers.
This means that the flow pattern within the column should be optimum in order
to have a clear seperation between the two resins during regeneration which
necessitates a careful se!ection of the particle size of the two resins.
In the case of anion exchangers, type II resin can be used as a strong base
exchanger. The SiOiTOS ratio ",ust be less than 20 percent, otherwise the low
regeneration rates used entail a risk of fouling by silica. For a good seperation
between the two resins, the particle size range must be carefully selected.
It has been mentioned that a high level of regeneration of the polishing mixed
bed is desirable in order to ensure the highest possible quality of water. To
acheive this the so called thoroughfare system of regeneration can be used. This
system involves passing the regenerant required for the pre('eding cation or
anion units, firstly through the coresponding resins in the mixed bed. The
quantity of the anion resin in the basic demineralised unit will be at least five to
ten times the quantity of the corresponding resins in the mixed bed. As such the
regeneration level in the mixed bed will be correspondingly higher without any
additional consumption ofregenerants. In addition, temperature is also important
when removal of silica from mixed resin bed is considered. At regeneration
levels greater than 100 gm of NaOH per litre, the influence of temperature is
pronounced. It is important to remove as much silica from mixed resin as
possible, since silica in the treated water is dependent upon the amount of silica
left in the mixed bed after regeneration. When this type of regeneration is used
with either acid or alkali, it is implicit that the mixed b ~ d be regenerated at the
same time as the preceding cation or anion exchange column. The quantity of
water passing through a mixed bed unit per regeneration being known, it is
possible to calculate the permissible amount of silica and other solids in the
treated water, that can be taken care of by the mixed bed during normal
operation, from the preceding units.
Resin fouling is a major irritant in OM plants(5). One often comes across fouling
of the cation exchanger by iron, maqganese and copper. These impurities,
particularly, iron, comes along with regenerant chemicals. For example, commercial
hydrochloric acid usually contains iron. Thus, it has become a practice to specify
tbe iron and chlorine contents off-rCI used for regeneration. Once in way the cation
exchanger is also fouled up by precipitates such as calcium sulphate. As
mentioned earlier. the anion e"changers are fouled up by organics in addition to
colloidal silica. Both resins are fouled up by oil.grease. microbes, silt and clay
. which get in ,due to improper pretreatment procedures. To overcome the different
fouling problems. cleaning up of the resin beds is required. The sequential
procedure includes, backwashing, acid wash (10 percent inhibited hydrochloric
66 Water Chemistry
acid), 15 percent NaCI solution mixed with 5 percent NaOH, or 15 percent
NaCI solution mixed with 5 percent sodium hypochlorite (to give about 3 percent
wtlv of free chlorine) and 0.5% solution of formaldehyde. the solution or
solutions to be used for overcoming the problem of fouling depend upon the
nature of fouling. In each case appropriate test procedures are available to judge
the efficacy of the treatment.
Some special problems are also in the mechanics of
demineralisation. In counter current flow units, it is most essential to maintain
the compactness of the resin bed at all times during regeneration and preferably
during the service regime also. Any disturbance of the cation bed always leads
to an unacceptable leakage of sodium. Counter current flow units should be
operated in such a way that sodium and silica end points for cation and anion
units are not excecded. It is also essential that the feed to the DM plant after
pretreatment be free from any residual chlorin_" introduced earlier(6).
In modern power stations. where the operation of the high presssure boiler
and turbine requires the highest quality feed water, it is becoming a standard
practice to include the polishing of the steam condensate(partly or even fully)
by ion exchange resins(7.8), This is specially necessary, if the steam condenser is
cooled by or sea water, since condenser leaks result in an unacceptable
level of impurity intrusions. Condensate polishing is strongly advised, if the
salinity of the cooling water exceeds 2000 mg/l. Since large quantity of
condensate to be polished, the purification system operates under a
pressure much greater than that of the usual demineralisation plant. Thus. in
order to withstand the pressure and flow, attrition strength of the resin bead
becomes an important criterion. Particle size and grading are also important to
reduce pressure drops. In some condensate processing systems, very fine size
resins(25 micron diameter) 'ire used as precoat materials on pressurised filter
media before the deep bed polisher. The precoat filters are non-regenerable. If
the condensate is near neutral, experience has shown that it is possible to acheive
and maintain feed water conductivity below 0.07 and total metals around
2-3 However, if the condt'nsate, contains alkafising additives such as
ammonia. hydrazine or morpholine, the condensate polishing becomes a very
complicated process, due to the relative affinity of ammonium type of cations as
compared to say that of sodium for the resin sites. As a result, it is difficult to
achieve a conductivity value as low as that mentioned above.
6.5 QUALITY OF DM WATER
One can take a specific conductivity of 0.1 as the basis for the water
and can be sure that a very low concentration of electrolytes are present
(theoritical conductivity of water at 20
0
C being 0.05 However, due to
ion slip in the OM plant, specific conductivities higher than 0.1 are often
observed at the outlet of mixed bed filters. These slips do not have much influence
on the feed water conductivity in condensate recycling power plants whose
requirements of make up water are below I percent of the hourly steam output.
On the other h"nd the conductivity of the OM water for industtrial steam
generation plants with a large quantity of make up water is an exceptionally
important parameter. Increased electrolyte input in this case invariably leads to
Demineralisation by Ion Exchange
67
damage, particularly in once-through boilers and superheaters.
It has often been said that the performance of a demineralisation plant is
crucial to the over all water chemistry in a thermal power station. This emphasis
is due partly to the installation of a number of once-through boilers in advanced
countries and partly to the increasing requirements of steam purity for high
pressure turbines. Power stations in India have been making attempts to improve
the performance of DM plants. One way to assess this is to monitor critical
chemical parameters of the mixed bed output water. Table 6.2 presents data of
some case studies carried out by the author in this context.
Table 6.2 Comparison of Mixed Bed, Performance(9)
S. Chemical A B C D
No. Parameters J M S J M S J M S J M S
1. Input
Sp. Conductivity 4.3 7.3 7.5 30 40 40 8.8 8.5 6.2 4.8 13.0 4.0

2. Output
Sp. Conductivity 0.15 0.15 0.19 0.25 0.25 0.5 0.40 0.44 0.36 0.43 0.42 0.40
J.1SIcm
3. Output pH 6.8 6.8 6.9 7.0 7.0 7.0 6.7 6.8 6.8 6.8 6.8 6.9
S.No. 1 represents the Sp. conductivjty at tile anion exchanger outlet.
A,D,C &: D represent the power stations under study.
I,M &: S represent January, May and September in the year of.study.
It is usual for DM plant manufactures to claim a specification that the specific
conductivity of the output water from the mixed bed is less than 0.2 J,1S/cm. It
is evident from Table 6.2 that only in case A and to some extent in case B is this
specification met. There is much room for improve,ment in performance in cases
C and D. On the other hand, in case B, the anion exchanger effluent (S.No.l)
shows a high value of conductivity, twice that of the specifications usually given
for that parameter. Investigation revealed that at B, the anion bed was
contaminated with some cation exchanger leading to the higher value. Despite
this, the MB performance is not far from optimum, indicating that MB
regeneration is being carried out in an efficient manner.
REFERENCES
1. Venkateswarulu K.S., (1982), Boiler DM Water Makeup Consumption and Quality.
Proc. Indo- German Seminar on Performance of Thermal Power Plants. Central
Board of Irrigation and Power,New Delhi, Vol.1. KVI-I to KVI-4.
2. Venkateswarlu K.S. and B. Venkatatamani, (1979), Recent Trends in Industrial
Water Treatment, Chemical Age of India, 30, 1089-1098.
3. Gokhale A.S., P.K. Mathur and K.S.Venkateswarly, (1987), Ion Exchange Resins
for Water Purification: Properties and Characterisation, Bhabha Atomic Research
Centre Report, BARC-1364.
4, Nair B.K.S., (1983), of Water: Principles, Production and Quality
Control, Proc. Workshop on Water Chemistry in Thermal Power Stations. Central
Board of Irrigallon& Power, New Delhi, 13-20.
5. Natarajan R., (1983), Trouble Shooting in demineralising Plants, Ibid.. 57-66.
68 Water Chemistry
6. Jha J., (1983), "Case Histories and Trouble Shooting in Water Chemistry at Thermal
Power Statio;,," Ibid .. 47-56.
7. Nandwani T.B .. (1983), .. Condensatc Polishing." Ibid .. 67-79.
8,. Burcau of Indian Standards ( 1987), Guide for Condensate Polishing (Power Plant),
New Dclhi. IS:/11970-1!J87.
9. Venkatcswariu K.S., (1985). From Raw Water to Pure Steam: Problems in Therml\l
Power Stations, Corrosion and Maintenance. 8, 187-192.
7
WATER CHEMISTRY IN FOSSIL FUEL FIRED STEAM
GENERATING UNITS
7.1 WATER SIDE CORROSION AND DEPOSITION
PROBLEMS
For a world in need of energy, the use of water to generate steam for running
turbines of power plants is a most important activity. Whether the steam
generated is from burning fossil fuels or from nuclear heat, or whether it is to be
directly employed for steam cracking of naptha in fertiliser plants, the steam
quality is of utmost importance. This has been realized during the last 10 to 15
years, in a full measure all over the world. If one has to meet this requirement,
there is no alternative to a well considered and integrated water treatment
programme at all steam utilities. For securing better therinal efficiencies, high
temperatures and pressures are employed in the steam water circuit, the latter
comprising of feed water, boiler water, steam and condensate in contact with
surfaces of different materials. The words boiler and stellm generator are
synonimous, though the former term finds a larger usage in fossil fuel fired
power plants, while the latter term is frequently used in the nuclear power sector.
In fossil fuel fired boilers, the boiler tubes are usually of carbon steel. In the
case of nuclear steam generators, stainless steel 304,Monel-400, Incoloy-800
are employed as tube materials. In view of what was said in Chapter 4 and also
because of t"le chemical incompatibility of copper with respect to carbon steel
under the conditions of a steam-water circuit, there is a marked tendency to
eliminate copper alloys from the feed train. Condenser tube materials used include
brasses, cupronickels, stainless steel titanium. The steam turbine makes
use of a variety of alloy steels.
A block diagram of the water and steam circuit is shown in Fig. 7.1.
70
SUPERHEATER
ECONOMISER
CONDENSER
Water Chemistry
CONDENSATE
STORAGE
CONDENSATE
POLISHER
(OPTIONAL)
I
I
I
I I
1. ______ ..1
Fig. 7.1 A Simplified Circuit In a Power Plant
In high pressure boilers that make use of fossil fuels, the failure of boiler
tubes due to internal corrosion and external 'hot' corrosion, is of concern. The
subject matter in this book deals with the former rather than with the latter
which is metallurgical in nature. Boiler tube failures result in reduced availability
and reliability of the steam generating unit and impose an economic penalty. In
India, the Central Board of Irrigation and Power conducted a five year research
programme on water chemistry and boiler tube failures in thermal power stations
across the country and published their findings in two reports*(I,2).
Protection against internal corrosion by the boiler water is primarily provided
by the thin magnetite (Fep4) film formed on the tube surfaces during the early
stages of operation. As long as the adherent film is there, corrosion is prevented
or greatly minimised. If the film is damaged, internal corrosion starts again.
The corrosion of carbon steel is minimal in the pH range of 8.5 to 10.5(3). The
corrosion rate increases more rapidly with decrease in pH from 8.0, than with
increase in pH from 11.0. Consequently, the efforts are directed towards
* As the Expert Coordinalor for the study on water chemistry. the au,hor was responsible for
Coordinating al\ the technical work "arried out. This chapter is partly based on that experience.
Water Chemistry in Fossil Fuel Fired Steam Generating Units 71
maintaining boiler water pH around 9 to 9.5. The actual range depends upon
the nature ()f other constructional materials in the circuit, specially copper alloys.
In all ferrous systems, which is the modem practice the pH is maintained around
10.0 ± 0.5. When the pH is excessively high or low, the magnetite layer is partly
destroyed and internal corrosion starts.
Under high pH conditions, excess OH, in the form of NaOH, gets concentrated
in the pores resulting in metal wastage, wall thinning of the boiler tube at that
point; finally leading to tube rupture(4). This type of attack is often called caustic
gauging and the resulting failure is known as ductile failure. Tube thinning is a
characteristic of this class and could be detected earlier through ultrasonic in-
service inspection. A more frequent type of failure of boiler tubes is due to
internal corrosion that occurs in the low pH region. The hydrogen produced in
corrosion process gets trapped in the film and diffuses into the metal. There it
combines with carbon present in boiler steels and generates methane. The
combined pressure exerted by hydrogen and methane within the metal results in
grain boundary fracture. This results in tube failure, which may occur explosively,
throwing out bits of metal. Ultrasonic inspection might not reveal the trouble-
lipot early enough to effect a tube replacement.
The cause of pH fluctuations can be traced to leakage in the power plant
condenser, resulting in contamination by raw water, cooling tower water or sea
water depending upon the location. The internal deposits resulting therein cause
tube failures.
The internal deposits being poor thermal conductors, can also lead to'over
heating of boiler tubes at the spots where such deposits exceed a certain
thickness.!n other words, the heat transfer from the fire side through the tube to
the boiler water is reduced at such spots which becomes over heated.
Consequently blisters appear on the boiler tube, which ultimately burst. This
type of failure takes place not only with boiler tubes but also with tubes of the
superheater and reheater( in units where they exist). To avoid deposit formation
in these sections,it is essential that the attemperator or desuperheating spray
water be of high quality. The deposit analysis usually shows oxides of Fe, Cu,
Ni and Zn which originate from the components bearing these metals in the
preboiler section. The causative factors are pH and dissolved oxygen, the latter
being more significant than the former(5). As the preboiler section operates at
relatively low pressure, air ingress is often the cause of an increase in dissolved
oxygen in the feed water. This can be controlled (to values less than 5mg/l) by
dosing with hydrazine. This will also help in minimising pitting corrosion, which
frequently occurs close to the welds due to internal stresses at such points.
While talking of water side corrosion, the influence of the chloride ion has
to be considered. Of the various alloys present in the system, stainless stocls are
most susceptible to chloride attack, through stress corrosion cracking, specially
in tbe presence of dissolved oxygen. Fortunately, the extent of stainless steel
surfaces exposed to feed and boiler water and condensate fn a fossil fuel power
plant is limited. However, just like NaOH, NaCI would also concentrate in the
crevices of a boiler. In general, chloride being a corrosion promoter, it is
monitored and kept under control through blowdown. With increasing p r e s s u r e ~
the vapour phase carryover of sodium chlonde into the turbine and deposition
72
Water Chemistry
on the turbine blades is a matter of serious concern, as is the behaviour of
silica.Thus sodium chloride and silica are to be looked at from a different view
point, viz. the turbine. The only way to control them in the steam fed to the
turbine is to control them in the feed and boiler water<6). It may also be mentioned
that stress corrosion cracking is a serious prqblem on the water side of nuclear
powered boiling water reactors where stainless is used extensively.
7.2 CHEMICAL TREATMENT OF WATER FOR
INDUSTRIAL AND POWER PLANT BOILERS
Boiler water chemical conditioning and its control is aimed at:
(a) Avoiding internal boiler tube corrosion.
(b) Preventing deposit formation on heat transfer surfaces.
(c) Ensuring the quality of steam acceptable to the turbine.
Boiler water chemical treatment and its control have evolved over the decades
and the process is related to the increasing temperatures and pressures obtained
in boilers, as well as to changes in the boiler design itself. Recirculation drum
type boilers with blowdown facilities were the first to appear on the scene.
There were designs over a period for increasing pressure. The water
quality changed as a result of this. At a later date, once-through
boilers or steam generators came up. In these there is no drum to hold boiler
water with a higher content of dissolved solids than feed water nor is there a
blowdown facility to regulate the chemistry. This group of boilers require almost
zero TDS in feed water.
. After the steam loses most of its energy in driving a high pressure turbine, it
is condensed and the condensate forms the main bulk of feed water to the boiler,
after being reheated and repressurised. The high purity DM water serves only
as a make-up to take care of losses( or more the boiler blowdown). A
very large number of utilities use the condensate without further purification.
However, with the increasing technical requirement of a minimum amount of
dissolved solids as practicable for feed water, condensate polishing by mixed
bed demineralisers has come into vogue.
7.2.1 Low and Medium Pressure Boiler Water Treatment.
Low and medium pressure boilers find extensive use in the chemical industry,
serving as a source for ·both process heat and steam. Low pressure boilers are
by convention those operating upto 15 to 20 kglcm
2
(-300 psig). Above this
working pressure, but below 64 kglcm
2
(- 900 psig) are the group of medium
pressure boilers.During the last 30 years the design of the boilers has undergone
improvements in all directions, necessitating a superior quality of feed water.The
boilers operate at high heat transfer rates and have evaporation capacities in
the range of 10,000 kg/h. The two problems faced under such conditions are
scaling und corrosi_on. The required feed water quality is not attainable by the
conventional base exchange softening plant as the water has to be completely
soft and clear. In addition to scaling, these boiler internals are also susceptible
to corrosion by dissolved carbon dioxide and oxygcn(7).
Water Chemistry in Fossil Fuel Fired Steam Generating Units 73
The boiler water quality in the boiler drum as specified for low pressure
boilers is given in Table 7.1.
Table 7.1 Water Quality Specifications for Low Pressure Boilers(7)
Total dissolved solids
Total alkalinity
pH
Total hardness
Sulphite
Phosphate
Less than 3000 mgll
20% of the TDS
(Less than 600 mgll as CaC0
3
)
10 to 10.5
Less than 5mgll as CaC0
3
30 - 50 mg/l
30 - 50 mgll
Sulphite is added for deoxygenation,while phosphate is a corrosion inhibitor.
Since the boiler is an evaporator, that too at very high rates (as compared to
a cooling tower), it is possible to maintain the above boiler water quality only
by a process of feed and bleed. The bleed is known as blowdl'>Wn and is possible
only in the case of drum type boilers. The quantity of boiler water to be blown
down can be calculated from the quality of feed water (that acts as a diluent)
and the equilibrium quality of boiler water ,that needs to be maintained despite
evaporation. The formula applied is,
B(lnMJlh).ExS(lnMJlh) (7.1)
c-s
Where B is the blowdown rate, E is the rate of evaporation, S is the amount
of dissolved and suspended solids in mgll and C is the maximum permissible
aruount of dissolved and suspended solids in mgll in the drain. In fact, it is
highly desirable that the amount dissolved or suspended solids in Sand C be
close to zero.
It is obvious from the above discussion that the amount of blowdown (in
terms of a percentage) will be inversely related to the qUQlity of feed water.
Sincp. blowdown means loss of heat and improvement in feed water quality is
more expensive, a balance is struck on the basis of cost effectiveness. As a rule
of thumb one can say that if the blowdown can be maintained at below 10 percent,
preferabley at S percent, a normal base exchange softening system for feed water
along with chemical conditioning is sufficient. If the blowdown works out to be
greater than 10 percent it is necessary to install a more elaborate feed water
purification system.
Since alkalinity is a controlling parameter and an excess of it would lead to
scaling, one aspect of the boiler water treatment for low and medium pressures
is to control alkalinity. Earlier practices included acid dosing (as in the cooling
water treatment) and lime soda softening. However. the increasing quality
requirements have supplanted these procedures and the use of ion exchange
resins in one way or another has become the common practice(7,8). Two cases in
raw water quality may be distinguished:
(a) Alkalinity in raw water is high and the total hardness less than the
alkalinity,
74
Water Chemistry
(b) Alkalinity in raw water is high and the total hardness more than the
alkalinity, as well as most of the hardness is permanent.
In the first situation, the dealkalisation is carried out by the use of a weak acid
cation exchange resin in the hydrogen form. As mentioned earlier, these resins
have -COOH as their functional group. The cations tesponsible for hardaess viz.,
Ca++ and Mg++ are e:tchanged and replaced by H+ in the water under treatment.
The carbonic acid formed, such circumstances is removed through a degasser. This
method of treatment leaves the levels of sodium, chloride and sulphate uneffected
in the water. The total dissolved solids content is reduced by a factor corresponding
to the removal of Ca and Mg carbonates and the product water is of low hardness
and low alkalinity. The exhausted resin is regenerated by one to four percent of
mineral acids like hydrochloric or sulphuric acid.
In the second case it becomes necessary to achieve partial demineralisation
as well as softening. This is usually realised through the use of two streams
(independent and parallel) of ion exchange columns. One contains a strong
acid cation exchanger in the bydrogen form, while the other is loaded with a
strong acid cation exchanger in the sodium form. Ca++ and Mg++ get exchanged
in both the columns, while H+ .and Na+ are released from the two columns
respectively. Both streams are mixed and led through a degasser. By this process
the total solids are reduced to an extent equivalent to the alkalinity in raw water,
which is a l ~ o softened. The resins are regenerated by the usual procedures. As
an alternative, the soft water from the sodium form of the cation resin is fed to
a stror.g base anion exchanger in the chloride form. There would be no cation
bed in the hydrogen form. The bicar;bonate and carbonate ions are replaced by
chloride. The advantage lies in the regenerant, viz. sodium chloride rather than
acid. The effluents are easy to handle, environmentally speaking(8,9).
The degasser used to remove carbon dioxide in the ion exchange set-up, saturates
the water stream with dissolved oxygen. Since this accelerates corrosion, it needs
to be eliminated in the water circuit. This can be done either by the use of a thermal
deacrator or by chemical dosing with a reductant, such as sodium sulphite. In the
former case, the temperature of the water is raised and sprayed through a tower, so
that most of the dissolved oxygen is given off. This i.s 'an efficient method, but
energy input is needed. On the other hand, in chemical addition, the sulphite gets
oxidised to sulphate leading to a low level of dissolved oxygen. This procedure
while being simple, does contribute to the total dissolved solids.
As mentioned earlier, the medium or intermediate pressure boilen are those
that operate between 300 to 900 psig (20 to 64 kg/cm
2
). The guideline values
for the chemical quality of boiler water are given in Table 7.2.
Table 7.2 Water Quality Limits (Max.) of Medium Pressure Boilers(lO)
Chemical Working Pressure in kglcm
2
Parameters 20 40 64
Sp. Conductivity + lu/cm 10,000 5000 2500
P value ++ mval/kg 12 6 3
Silica mglkg 70 30 10
Phosehate m ~ k &
10 -20 15 15
+ Sp. Conductivity measured at 25°C after neutralisation with HCI with phenolphthalein as
indicator.
++ 1 mvallkg of value = 40 "lg of CaC0
3
/l or 0.04 gm NaOH/l.
Water Chemistry in Fossil Fuel Fired Steam Generating Units 75
Working curves that relate the admissible levels of conductivity, silica and
p-alkalinity to the working pressure are available in literature. The very fact
that the p-alkakinity is allowed to be present in the boiler water means that
NaOH is added and the system is under alkaline operation. This chemical regime
has been evolved to minimise the corrosion of iron and other ferrous alloys' in
the boiler circuit that come into contact with water. A sudden switch over to
polymer based treatment is not advisable without proper precautions like a heavy
blowdown. In fact, the sulphonated and the carbonxylated polymer along with a
copolymer are being recommended for sludge conditioning in boilers upto
900 psig or even a little higher. In low pressure boilers, a programme of using
chelants like nitrilo tri acetic acid (NTA) and ethylene diamine tetra acetic acid
(EDTA) to keep Ca and to some extent Mg, Fe and Cu in solution has been
proposed. At the required residuals of the chelants. scale and sludge problems
are minimised. There are other advantages as well, but monitoring of the chelant
concentrations in boiler water is difficult. Alternatively polymers have also gained
attention as sludge dispersants. Early dispersants include potato peels, saw dust,
tanin, lignin etc. Subsequently synthetic polymers have been used to distort
crystal growth, reminiscent of cooling water treatment. New polymers t:19,t
incorporate sulphonic and carboxyiic functional groups are proving bettel than
the earlier straight chain polymers such as polymethyl
The best aqueous environment in which boiler steel can form and maintain a
protective oxide layer that protects the metallic surface from further corrosion,
is realised by maintaining a controlled degree of alkalinity with sodium hydroxide,
aided by the presence of sodium orthophosphate. While problems crop up with
such a type of control in high pressure systems, for boilers in the medium or
intermediate pressure range, this treatment offers enough protection against
corrosion,provided dissolved oxygen is controlled. As seen earlier, hydrazine is
a better dissolved oxygen scavenger than sodium sulphite and is widely used in
high pressure systems. Medium pressure boilers have also. started to make use
of hydrazine to control dissolved oxygen. However, as fears surfaced of hydrazine
being a possible carcinogenic agent, a number of substitutes for hydrazine have
come into the market. Among these are hydroquinone, carbohydrazide, diethyl
hydxylamine, methyl ethyl ketoxime and erythorbic acid. The last one has FDA
approval, which allows its application in the food processing industry where
steam comes in contact with food products.
7.2.2 High Pressure Boiler Water Treatment
All the boilers or steam generators operating above 64 kg/cm2 (900 psi g) come
under the category of high pressure boilers. They are of two types, a) Drum
type recirculating and (b) Once- through. Apart from steam, there are three
varieties of water in the steam water circuit. These are boiler water (which
boils), condensate water and feed water (condensate+makeup water). The
blowdown is from the drum, in other words its composition corresponds to
boiler water at the time. Makeup water is the high purity water that comes from
the demineralisation plant and as the name implies will take care of the losses
due to blowdown and aflY other leaks. We are now in a position to consider
76
Water Chemistry
different facets of water conditioning in the steam water circuit of high pressure
boilers.
Prior to 1950, there were two types of chemical conditioning for boiler water
in recirculation type boilers. The first one was based on the presence of free
caustic so that the boiler water is in the pH range of 10 to 11. As it is not
advisable to have such a pH value in the presence of copper alloys in the circuit,
a pH range of 9.5 to 10.0 was considered a!=ceptable. In addition,a few mgn of
residual phosphate as trisodium phosphate was also addeti to the boiler water.
This would be of use, if any hardness salts enter the feed train due to condenser
tube leaks or contamination of makeup water. As operating pressure increased,
this treatment was found to lead to two corrosion problems, namely 'caustic
embrittlement' and 'caustic gauging' of the boiler internals(4).
Fifty years ago 'caustic embrittlement' was a major problem. This type of
attack was due to concentration of alkali in certain locations of the boilers. It
was commonly found in areas around the riveted seams of boiler drums and in
the highly stressed areas where tubes were rolled into the drum. Flashing of
steam in and around the sensitive areas produced localised high concentrations
of NaOH in the adjoining crevices. A number of inhibitors were tried and found
unsatisfactory. On the design and fabricaton side, improvements were made
such as welding boiler drums and the eiimination of 'cold' work practices.
'Caustic gauging' persists in modern high pressure boilers, where sodium
salts are used in one or other form. It is normally a pitting phenomenon and
occurs underneath the deposits of boiler tube internal surfaces. Metal wastage
can be very rapid once caustic gauging starts. Due to high concentration factors,
NaOH is built up under the porous oxide deposit. This points to the need for
very close control and monitoringJlf.Na+ and OH- in the boiler water. In boilers
operating at pressures greater than 160 kglcm
2
(2300 psig) is the boiler water
contains more than 3 mgll of caustic, its solubility in steam is such as to exceed
the primary target.
To combat the two corrosion problems mentione above, a different concept
called the co-ordinated phosphate-pH control came into vogue forty years ago(I1).
Simply put, in this type of boiler water treatment, there is sufficient phosphate
to prevent the formation of 'free caustic', thus reducing the risk of 'caustic
embrittlement and gauging'. As this method continues to be in wide use even
today, the process and the mechanism will be discussed in some detail. The
value of pH in boiler water is maintained by phosphate. The observed pH has
to be less than what would have been attained, if an equivalent of Na
3
P0
4
alone
was present in the water. A lower pH value ensures the absence of free alkali.
The relevant data are given in Table 7.3.
Table 7.3 Referanee Data for Conventional Coordinated Phosphate Treatment
pH Value
10.05
10.35
10.65
10.90
11.00
Working curves are available in Iiterature(11).
10
20
40
80
100
Water Chemistry in fossil Fuel Fired Steam Generating Units 77
Chemical control is maintained by adding trisodium phosphate mixed with
Na
2
HP0
4
and NaH
2
P0
4
and not by itself. The addition of trisodium phosphate
alone will produce OH- due to a reversed hydrolysis reaction(I1),
PO 3- + H 0 <=> OH- + HPO-2
424
(7.2)
The degree to which this reaction proceeds depends upon the pH of the
solution at equilibrium. It stands to reason that with increasing pH (excess of
OH-) or increase in HPOi- concentration, the reaction proceeds in the backward
direction due to the mass action effect. Since the question of increase in pH
does not arise, as in fact, the whole exercise is to remove free OH- from boiler
water, the only course open is to add HPOi- in the form ofNa
2
HP0
4
to the
system. In the theoretical formulations, the question of the hydrolysis ofHPOi-
is also to be looked into. This is represented by,
HPOi- + H
2
0 <=> OH- + H
2
P0
4
- (7.3)
Table 7.4 gives the percentage of the three species of phosphate as a function
of pH at 25°C.
Table 7.4 pH vs. Percentage of Different Species of Phosphate
pH Percentage of
H
2
P04- HPOi-
6 93 7
7 40 60
8 14 86
9 3 97
10 100
11 95
12 70
13 17
5
80
83
It is seen from Table 7.4, that in the pH range of9 to 11 or more specifically
9.5 to 10.5, the phosphate in solution is exclusively present as the monobasic
ion, HPO i-It is this pH range that is specified in many boilers. It is also observed
from, Table 7.4, that the best way of chemical control is to add a mixture of
trisodium phosphate and monosodium dihydrogen phosphat,e. When boiler water
pH fluctuates, the ratio of these two salts is so adjusted as to bring the pH into
the desired range. For example, when pH drops due to condenser tube leaks,
the rate of conversion of the trisodium salt to the monosodium salt is increased
and vice versa in case of pH rise.
In the higher pressure range of boilers (175 kg/cm
2
) chemical control by
using data given in Table 7.3 results in high phosphate values leading·to the
distribution of the solute between boiler water and steam. Hence, a lower level
of phosphate is desirable and the data given in Table 7.5 is to be used.
The guidelines are the Same as in Table 7.3-Coordinated phosphate pH control
Is desirable where the makeup water is from the demineraliser plant. Alkaline
buffers other than phosphate in boiler water disturb the phosphate -pH
relationship. Since many utilities use ammonium hydroxide as a pH
78 Water Chemistry
Table 7.5 ;Reference Data for Low Level Coordinated Phosphate Treatment for
High Pressure Boilen
Phosphate- mgll pH (25°C)
1.0 9.15
2.0 9.30
4.0 9.60
6.0 9.80
10.0 10.02
15.0 10.20
20.0 10.30
24.0 10.40
30.0 10.50
• As a mixture of Na
3
P0
4
+ Na
2
HPO.
regulating agent, the presence of chloride in boiler water will lead to the buffer
NH"OH - NH
4
Cl. Its interference in measured pH values after phosphate (tri
and mono mixture) addition is to be carefully evaluated, specially in high pressure
boilers (where transport of NH
4
CI into the steam introduces a further
complication). Thus one important conclusion is that chloride in boiler water is
undesirable.
A variation of the coordinated phosphate pH control is known as the
congruent pH-phosphate control, which employs a mixture of phosphates as
mentioned earlier. The 'free caustic' condition in boiler water is understood not
only in terms of its possible concentration but also on the basis that free hydroxide
serves no useful purpose in high pressure boilers, where hardness salts(Ca and
Mg) are rigorously excluded.
A phenemenon encountered in phosphate treatment of boiler water is its
hide-out(ll). The solubility of trisodium phosphate increases with temperature
upto 120°C, to a value of around 94 gms/lOOgms of water. It then decreases
gradually upto 210°C to a value of60 gm/IOOgm and falls sharply thereafter. At
230°C it is only 20gmliOOgm of water. The hide-out is due to this retrograde
solubility (Table7.6).
Table 7.6 Solubility of Trisodium Phosphate as a Function of Temperature
Temp.oC Solubility
(gm/IOO gm H
2
O)
38 20
65 45
93 70
120 94
150 82
177 65
204 60
232 18
260 7
Water Chemistry in Fos .. tl Fuel Fired Steam Generating Units 79
Utility and laboratory studies indicate that the compound which crystallises
out under hide-out conditions has a sodium to phosphate ratio of less than 3: 1.
Under operating conditions, this may result in free hydroxide, which is
undesirable. When the plant load is reduced, the phosphate is redissolved with a
reduction in boiler water pH. Thus phosphate menitoring during load changes
is very important for high pressure boilers, to ascertain the extent of hide-out
and its implications.
There have been suggestions to make use of potassium phJsphate, since it
has a much higher solubility than the sodium salt at high temperatures. Although
this has been tried(6), there is reluctance to use the potass;um salt as evidence
shows that gauging type corrosion is more with KOH,than with NaOH. It must
be mentioned that sodium phosphate hide-out (crystallisation) can occur on the
surfaces of boiler tubes, even if they are in a clean condition, leading to elevation
of the tube temperatures. While phosphate hide-out is not desirrable, a number
of utilities have operated under cyclic hide out without much damage to boiler
tubes, To maintain the corrosion of the boiler at a very low rate the feed water
is also specially chemically conditioned by hydrazine dosing, to reduce
oxygen to less than 1 0 and maintain its pH in the alkaline range.
While alkalinity is a major factor to be properly controlled in the water steam
circuit, it is equally important to control dissolved oxygen to avoid pitting
corrosion. It is clear that the phosphate regime has no influence on the dissolved
oxygen. With increasing boiler pressures and the introduction of once-through
boilers, control of dissolved oxygen and alkalinity by volatile chemicals like
hydrazine and ammonium hydroxide or morpholine has beell considered(12). The
advantage of such an All Volatile Treatment (AVT) is that the reagents being
volatile, will also go into the steam phase and get condensed along with it. Thus
they give protection to the turbine and condenser surfaces in addition to the
boiler internals (See Chapter 4). However the alkalinity that can be reached
with ammonia and morpholine is lower and chemical control limits for pH are
9.5 to 10.5 or more usually 9.8 to 10.0 in boiler water.
At high temperatures hydrazine also decomposes to ammonia and hydrogen.
Thus the amount of hydrazine to be dosed depends not only on its scavenging
action for oxygen, but also on its rate of decomposition under operating
conditions. The characteristics and behaviour of ammonia, morpholine and
hydrazine were considered in detail in Chapter 4.
A disadvantage of the AVT is the lack of buffering capacity. Consequently,
during condenser tube leaks, the alkalinity drops quickly, specially if the
condenser cooling water is brackish or seawater. Under such circumstances, it
has been suggested that the chemical treatment be switched to coordinated
phosphate addition. After the tube leak is plugged, the phosphate can be blown
down and the treatment reverted to AVT. Condensate polishing will give some
lead time to operators under the above circumstances. In fact, in once-through
boilers that operate only under AVT, condensate polishing is mandatory, even if
fresh water is used for tondenser cooling.
While morpho line is a component of A VT, specially in nuclear power stations,
80
Water Chemistry
ammonia continues to be made use of in several fossil fuel fired stations and in
once-through steam generators. In addition, there are other candidates for
alkalinity control such as cyclohexylamine (CHA)and methoxypropylamine
(MPA). It is quite possible that MPA would playa leading role in AVT in the
years to come. Combination of amines is also being practised in the condensate
system. In addition, the use of filming amines such as octadecyl amine is on the
.increase. These amines have both hydrophobic as well as hydrophilic groups.
The monQmolecular film formed on the oxide surface inhibits b t ~ h low pH and
oxygen attack but does not protect the pitted surfaces. For optimising protection,
a combination of neutralising amines (for alkalinity control/neutralisation of CO
2
in the boiler due to decomposition of organics), filming amines and oxygen
scavengers are highly recommended. These are commercially available as blends
under different trade names.
7.2.3 Chemical Regimes for Feed Water, Boiler Water and Condensate
Against the above background let us consider the optimum chemical regimes
envisaged by different utilities, manufacturers etc. for feed and boiler water
and condensate in high pressure steam generating units. At the outset it should
be mentioned that the earlier approach was to specify these chemical targets
mainly based on corrosion control in the preboiler, boiler and condenser sections.
In other w0rds the specifications have been evolved mostly with respect to the
water si1e corrosion. During the last decade, it has been amply realised that this
is not an appropriate approach. The current praQtice is to look at cycle chemistry
from the stram side(lJ). In high pressure turbines, the steam side corrosion and
deposition problems have been found to be much more important than the water
side corrosion in the other sections of the unit, as failures in turbine components
impose a greater economic penalty and unit unavailability. Hence the steam purity
has become the guiding principle. To achieve that type of purity, the quality of
feed and boiler water has to be upgraded. This of course will automatically ensure
that water side corrosion is minimised. Steam side problems are dealt with in
the next chapter.
A study of the literature reveals that every organization basically agrees that
the important parameters in feed water, are pH and dissolved oxygen. In fact,
the Central Electricity Generating Board (CEGB), UK(14), considers dissolved
oxygen as a primary target and specifies that at the economiser inlet, oxygen
should not exceed 5J.1g/1. Combustion Engineering (CE), USA, agrees with this
low Iimit(J). CEGB further specifies that at the condensate extraction pump
discharge (CEPD), oxygen should be less than 151lg/1. Electric P.ower Research
Institute (EPRI), USA, advises that oxygen at the deaerator outlet be less than
7J.1g/l, while at CEPD, it should be less than 20 J.1g/l(1S). For 200/210 MWe sets
in India, it is generally agreed that oxygen at the economiser inlet be less than
7 J.1g/1. These figures are based on the de aeration capability of modern plants
and are supplemented by the addition of hydrazine as oxygen scavenger. During
operation about 10 to 30 mg/l (an average of 20 mg/l) of residual hydrazine
would be able to keep oxygen within the specified limits. Since this measure is
to control the concentration of iron, copper and nickel ::orrosion products a
limit is sel by CEGB, in this respect also as a primary target. At the economizer
Water Chemistry in Fossil Fuel Fired Steam Generating Units 81
inlet these should not exceed a combined level of20 CE and ASME agree
with this limit, but specify only Fe and Cu (10 each). Recently EPRI (based
on steam purity consideration) reduced the Cu limit to 2 From the above
resume, it is evident that oxygen and its control is a very important chemical
function in operating power plants.
In view of the importance attached to corrosion of Fe and Cu components,
pH is another important specification of the feed water chemical reigme. For
systems having both Fe and Cu, the pH range (at 25°C) specified by EPRI is 8.8
to 9.3, at the economiser inlet, while for all ferrous systems, it is 9.0 to 9.6. The
concentration of the alkalising agents and the specific conductivity should be
consistent with this pH range. On the other hand, to make surt: that no other
soluble impurities are getting into the boiler, the cation conductivity of feed
water at the economiser inlet should be less than 0.2 (EPRI).
Silica has not been included as a primary target in feed water either by CEGB
or EPRI. Combustion Engineering mentions a limit of20 for total silica. In
case condensate polishing is utilised, at the polisher outlet, silica should not
exceed 10 (EPRI). This is the same limit as for makeup water.
As mentioned earlier, feed water is a mix of condensate (with or without
polishing) and a relatively small amount of treated makeup water from the DM
plant. Thus their chemical regimes are equally important. The EPRI guidelines
arc summarised in Table 7.7.
It is noteworthy that pH has not been specified. With both sodium and chloride
being at low levels, it is assumed that the pH will be in the neutral range of 6.8
to 7.2.
Table 7.7 EPRI Guidelines for Makeup Water aDd Condensate(U.13)
Chemical
parameter
Sodium
Sodium
(if condensate
polishing available)
Chloride
Sulphate
Silica
TOC
Dis. '0
2
Sp. conductivity
Cation conductivity stcm
Cation conductivity
(if condensate
polishing available)
Makeup
water

5
3
3
10
300
0.1
Condensate
pump discharge

5
10
200
20
0.2
0.3
,.
82 Water Chemistry
With the respect to boiler water of the drum type unit,CEGB, UK, makes a
clear distinction between units employing NaOH or NaOWPhosphate or A VT.
In case caustic soda alone is employed as the alkalising agent, its level is made
dependent upon the level of chloride impurity as NaCl. The chloride specification
shows a decrease from less than 6 mgll to less than 2 mgll with increase in
pressure from 900 to 2350 psi (or 64 to 162 kg/cm
2
). NaOH should be 1.S times
that ofNaCI, with a minimum of 5 mgll at 64 kglcm
2
, which is to be reduced to
a minimum of 2 mgll at 162 kglcrp2. For the coordinated P,hosphate treatment
also, the chloride levels are the same as with free caustic treatment. However,
for AVT, the chloride level must be less than 0.2 mgll by weight, as NaCI for all
pressures. CEGB has separate specifications for the high pressure- high heat
flux boilers (162 kg/cm
2
) cooled by seawater, as given in Table 7.8.
Table 7.8 CEGB SpecificatioDs for Higb Pressure (162 Kg/cm
1
) - Higb Heat
Flux Boilers Cooled by Sea Water(J4)
In Boiler Water Units . Primary targets
Chloride mgtl by wt as NaCI Less than 0.5
Caustic Soda mgll by wt as NaOH 1.5 x NaCI with min.
NaOH of 0.5 mgtl
pH
at 25°C 9.8 % 0.2
Sp. Conductivity
~ s/cm at 25°C Less than 20
Cation conductivity ~ s/cm at 25°C less than 6
Silica
mgll by wt. as sial 0.2
For 200/210 MWe units in India operating upto a pressure of 160 bar (i.e.
comparable to the operating pressures given above by CEGB) the boiler water
chemistry specifications appear to be slightly different(16). The pH is mentioned
as 9.0 to 9.5, (lower than CEGB value). Free caustic is not permitted at all. This
is because of the fact, that mere caustic'addition is no longer practised. Phosphate
is given a.s 2 to 4 mgll, while silica and chloride should be less than 300 and
SO ~ g t l respectively.
As expected in boiler water in drum type units with or without reheat, the
sodium limits are very stringent, since sodium compounds (as hydroxide or
chloride) are major boiler tube and turbine blade corrodents. In the 64 to
162 kg/cm
2
pressure range, sodium concentration is specified as 5 to 2 mg/l.
The same specifications hold for chloride as well, while that of silica are from 3
to 0.3 mgtl. Sodium to phosphate molar ratio is in the range of 2.3 to 2.8.
Working curves have been developed by EPRI for different chemical
contaminants vs. pressure so that any situation can be monitored and analysed
for target values. Action levels have been prescribed so that when contaminants
exceed target values beyond these'levels, corrective action, such as increasing
blowdown and reducing pO\L'er can be taken within specified time limits.
Since the guidelines set by EPRI in 1986(15) have been evolved through a long
process of consultation between experts, utilities and vendors, in the author's opinion,
they should be gh.., , enough weightage. If others differ from these guidelines, the
underlying arguments for the variation must be clearly spelt out.
Water Chemistry in Fossil Fuel Fired Steam Generating Units 83
A study on the feed water and boiler water characteristics of seven thermal
power stations in India,spread over a realistic time span revealed the following
features(l7). At a seawater cooled power station, the specific conductivity of
the feed water was above I J1 s/cm for most of the time, occasionally going as
high as 3 J1s/cm. This was due to condenser tube leaks. In only two out of the
other six stations, where the condensers are cooled by river or dam water, the
feed water conductivity was lower (0.3 to 0.4 J1s/cm), while in two others it
was about IJ1s/cm. What was surprising was that at the remaining two stations,
the feed water conductivity was higher than at the seawater cooled location,
although their condensers were being cooled by fresh water. On comparing the
above observed values with the specifications discussed earlier, it was obvious
that considerable improvement was needed. For example, at the sea water cooled
station, replacement of the AI- Brass by Cu-Ni tuDes, improved the feed water
conductivity through a better leak-proof situation.
Since feed water is a mix of condensate and makeup, its characteristics were
also studied. The problem of high feed water conductivity in the last two stations
was traced to condensate contamination and remedial action in terms of cleaning
and corrosion protection was initiated.
Other characteristics of feed water studied were the pH (maintained between
8.S to 9.0), silica (10 to 20 J1g1I) and chloride (not detectable, except at the sea
water .cooled locations).
The concentration factor between feed and boiler water was also studied in
terms of the ratio of the respective specific conductivities. The ratio varied
from about 10 to 70. It was reasoned that the lower level was due to excessive
blowdown, whilst the higher "level was a result of feed water contamination.
Phosphate treatment was in v o ~ u e in all stations.
The above discussion along with the examples, clearly demollstrYas the need
to monitor the chemical parameters of different components of water as found
in the steam generating system and understand the reasons for normal or abnormal
varations,only then can corrective action be initiated(18).
It is evident that for once-through boilers, without a drum and blowdown
facility, the chemical regime will be much more stringent. The question of caustic
and phosphate treatment does not arise at all and OTs depend upon AVT only,with
ammonia (in most cases) or morpholine as the alkalising agent and hydrazine as
the dissolved oxygen scavenger. Condensate polishing is mandatory and the
alkali sing agents create special problems in terms of resin selectivity at times of
condenser leakage. The type of chemical treatment for feed and boiler water is
often referred to as 'Zero Solids Treatment'. At present, the only once-through
boiler or steam geneator in India, is the one attached to the Fast Breeder Test
Reactor at Kalpakkam. Operational experience on the ammonia cycle is very
limited. The specifications for once-through boilers as stated by CEGB(l4) are
given in Table 7.9.
84
Water Chemistry
Table 7.9 CECB Primary Targets for Once-Through BoUers(14)
Parameter Limit Sampling Points
Cation conductivity
01 slcm at 25°C)
pH at 25°C
Dissolved 02 (J.lgll)
Sodium
(mgll by wt. as Na)
Silica
(mgll by wt. as Si0
2
)
Total Fe, Cu and Ni
(mgll by wt. as
Fe + Cu + Ni)
0.1
9.0 - 9.3
15
Condensate polishing
plant outlet
After chemical dosing at the
condensate polishing
pl"nt outlet
Final stage extraction
pump discharge.
5 Boiler inlet.
5
20
10
(3 as Cu)
Condensate polishing
plant outlet.
Condensate polishing
plant outlet.
Economiser inlet or
boiler feed pump
discharge.
In conclusion, it needs to be emphasised, that with increasing pressure of
the operating units, the chemical conditioning procedures have undergone a
change, both in character and rigour. Currently, the chemical targets in the water
phase are derived from the chemical control requirements of the steam phase,
which will be discussed in the next chapter.
REFERENCES
1. CBIP( 1988), "Investigation on Water Chemistry, Material Compatibility and Related
Problems in Steam-Water Cycles of Thermal Power Stations". A project Completion
Report, July 1988. Central Board of Irrigation & Power, New Delhi. India.
2. CBIP (1988), "Investigation on Boiler Tube Failures in Thermal Power Stations: A
Project Completion Report, August, /988. Central/Board of Irrigation & Power,
New Delhi, India.
3. Gabrielli F., F.R. Henry, R.C. Keistead, J.A. Ray and W.R. Sylvesta, (1978). Prevent
Corrosion and Deposition Problems in High Pressure Boilers. Power, July 1978,85-
92.
4. Venkateswarlu K.S., (1979). Corrosion in Power Industry. Corrosion & Maintenance,
4,257-259.
5. Venkateswarlu K.S., (1988), Deoxygenation : An Essential Ingredient in Steam
Generating Indqstry, Chemical Business. February.
6. Venkateswarlu K.S., (1984), Chemical Treatment of High Pressure Boiler Water to
Ensure Steam Quality Requirements, Corrosion and Maintenance, 7. 177-182.
7. Deshpande K.V., (1992). Feed Water Tr:atment for Low Pressure Boilers. All India
Convention on Industrial Water Treatment and Conservation. National Centre for
Technical Development. Bombay, Nov. 1992. pp. H.l to H.3.
8. Mhetre S.N., (1992), Low Pressure Water Treatment: Cost Economics of Dealkalisers
vs. Softners, Ibid., pp.OO.1 to 00.15.
9. Deshpande K.V., (1992), Dealkalisation for Small and Medium Pressure Boilers,lbid .•
pp.I.l to 1.5.
10. VGB, FRG, (1972), Indicative Data for Water for Industrial Use, Vd TUV. Edition.
April 1972,164-173.
II. Klein H.A., (1962). Use of Coordinated Phosphate Treatment to Prevent Caustic
Corrosion in High Pressure Boilers. Combustion, October 1962. 1 to 8.
Water Chemistry in Fossil Fuel Fired Steam Generating Units 85
12. Strauss S.D .• (l!)86). Advances in Chemical Water Treatment Improves Reliability
of Steam Generating Systems. Power. October 1986. 15-20 and references therein.
13. Strauss S.D .• (1988). Water Treatment Control and Instrumentation. Power (Special
Section) May 1988. W.l-W.30 and references therein.
14. CEGB. Generation Operation Memorandum 72 (1973). Chemical Control of Boiler
Feed Water. Boiler Water and Saturated Steam for Drum-type and Once-through
Boilers. Central Electricity Generating Board. U.K .• September.1973. 5-25.
IS. Aschoff A.F .• Y.H. Lee. D.M. Sopocy. and O. Jonas (1986). Interim Consensus
Guidelines on Fossil Plant Cycle Chemistry. Electric Power Re.search Institute.
EPRI CS 4629. June 1986.
16. Gopal R .• (1983). Water Chemistry and its Control in Feed and Boiler Water. Proc.
Wor/cshop on Water Chemistry itt Thermal Power Stations. 39-46. Central Board of
Irrigation and Power. New Delhi. India.
17. Venkateswarlu K.S .• (1985). From Raw-Water to Pure Steam: Problems in Thermal
Power Stations. CorrosioR and Maintenance. 187-192.
18. Straiss S.D .• (1990). Water-Chemistry Improvements Enhance Steam-System
Reliability. Special Report Power (International Edition). Dec. 1990.27-32.
8
STEAM QUALITY REQUIREMENTS FOR HIGH
PRESSURE
Steam purity is an important criterion that has received considerable attention
from industries in developed nations. The relative distribution of contaminants
between boiler water and steam is a function of .emperature and pressure. At
pressures in the 105 kg/cm2 (1500 psig) range or below. the steam solubility or
vapourous carryover of the soluble contaminants. except that of silica. can be
ignored at concentrations which are usually encountered in boiler water. In this
range of temperatures and pressures, the salt content of the steam is essentially
due to moisture entrainment of the steam. The solvation property of steam
increases as the critical point and single fluid phase is approached. For very
high pressure recirculating boilers 193 kg/cm2 (- 2750 psig), SO to 90 percent
of boiler water soluble contaminants (mostly the sodium salts) are transferred
to the steam phase and get deposited in the turbine with decrease in ste&m
pressure. In supercritical pressure boilers copper transport and redeposition in
the turbine is also a serious problem. The purity of inlet steam to the high pressure
turbines is specified by leading manufacturers to be: Conductivity less than 0.3
micro siemens/cm with sodium and chloride less than 5 Jlg/l* (Table 8.l).
Manufacturers and the organisations of electrical utilities give specifications
for high pressure steam that differ slightly. Those listed in Table 8.1 illustrate
the stringent requirements for the purity of HP steam. During the last few years,
the tendency is to further tighten these specifications under normal operation.
For example, MIs General Electric, USA puts the limit for sodium at 3 Jlgn and
cation conductivity at 0.2 j.ls/cm, while MIs Allis Chalmers, USA gives a limit
of 1 Jlg/l for copper. EPRI guidelines, on the other hand, are those evolved
through comprehensive discussions(l).
* Ilgll may be taken as equivalent to ppb.at such low levels
Steam Quality Requirements for High Pressure Turbines 87
Table 8.1 High Pressure Steam Quality Specifications(1·S)
Impurities in Normal
HP steam operation
Sodium 6
Chloride 5
Dis. 02
10
Silica 10
Cu 2
Fe 20
Cation conductivity 0.3
Limiting condItions of
operations
24 hrs.
10 to 20
10 to 20
30 to 100
20 to 50
0.5 to 1.0
2 weeks
5 to 10
5 to 10
10 to 30
10 to 20
0.3 to 0.5
In all drum type boilers, means are provided in the drum to seperate the
steam generated in the boiler·tubes from water. The required efficiency of this
seperation depends to a great extent on the use to which the steam is put e.g to
drive a turbine or crack naphtha and whether it is to be superheated or not.
Thus one has, 'saturated steam' and 'super heated steam'. In the former case,
0.25 to 0.5 percent of moisture can be tolerated. If the steam is to be super
heated, the seperation efficiency should be such that the moisture content is
well below 0.2 percent. This is to prevent the moisture carryover of soluble
impurities into the steam phase. All this is apart from mechanical carryover of
impurities(Z).
Detailed studies have shown that reliable performance of high pressure steam
turbines depends on the selection of its constructional materials, the stresses to
which the components and parts of the system are subjected to during operation
and chemical environment, which is high quality steam. While design and
availability of improved materials have reduced the contribution of the first two
causative factors, the control of steam chemistry/has not been achieved to the
same extent. In fact steam quality has become a varying parameter in otherwise
comparable high pressure turbines. As a result of this, a n\lmber of problems
have been experienced. To mention only a few, lower quality steam leads to
deposit formation in crevices and the consequent loss of thermodynamic
efficiency as well as corrosion and erosion of the turbine parts. The variations
in steam quality are partly due to lack of stringent control on feed and boiler
water quality due to a lack of sufficient appreciation of the basic chemistry
involved in the high pressure steam-water cycle(3). As noted !n the previous
chapter, the feed and boiler water chemistry specificatiQns are arrived at by
working backwards from steam quality requirements. This has-led to better steam
quality. At the same time considerable progress has been made in understanding
the steam chemistry as it passes through the turbine(from high to intermediate
to low pressures).
As steam expands in the turbine, different impurities present in steam start
separating out and get deposited in the turbine as the solubility of most
compounds in dry steam decreases with pressure. One can see this from solubility
data represented on P, T coordinates or a Mollier diagram (Chapter 4), where
the coordinates are entropy vs. enthalpy. From this it is deduced that the presence
88 Water Chemistry
of just 10 J.l.gll ofNaOH is sufficient for the formation of an 80 percent solution
ofNaOH in the intermediate pressure range(·I). It is evident that seperation of
concentrated solution ofNaOH would adversely effect the turbine parts due to
stress corrosion cracking. This would mean that NaOH in dry steam at high
pressures ought to be much less. The same is true for NaCl.
Solubililty data ofNaOH and NaCI in steam illustrate this point very clearly(4).
At 330°C and 1067 psia pressure, the solubility ofNaOH in steam is 750 J.l.g/l
(in terms of Na), which decreases sharply to 540 J.l.g/I, when the pressure is
reduced to 1052 psia at a temperature of 316°C. In the case ofNael, when the
pressure is reduced from 1176 to 1063 psia, the solubility sharply decreases
from 680 to 360 J.l.g/l (again in terms ofNa) over a narrow temperature range
(327.7°C to 325.5°C).
Chemical impurities such as NaOH or corrosion product oxides enter the
steam phase from the water phase due to their differential solubility between
the two phases. The so-called 'Ray Diagram' of the carry over coefficients from
water into the steam phase given by Martinova of the Moscow Power Institute,
is widely used to appreciate this aspect of steam chemistry (See Chapter 4). As
the density difference between the liquid and" vapour phase diminishes and the
critical point is approached with dielectric constant of steam on the increse, the
transport of materials to the vapour phase steadily increases. Just how clean the
steam entering the turbine should be and the mechanisms involved in stress
corrosion cracking are still not fully appreciated. An extensively reported study
in this context, is the failure of a turbine at Hinkly Point 'A' power station,
wherein it was shown that concentrated caustic solutions were deposited in this
turbine. For very high pressure ( 190-200 kglcm
2
drum pressure) recirculation
boilers, the vapour transport of sodium salt may approach 80 percent of the
total solids carried. Besides sodium hydroxide, sodium carbonate, sodium
phosphate and iron oxides are known to get deposited on all tje three states
(HP, IP and LP) of the turbine internals. On the other hand, oxides of copper
a ~ d sodium sulphate are preferentially deposited in the HP and IPstages, while
silica & sodium chloride get preferentially deposited from the steam phase in
the IPand LP sections(2).
Even though the impurity levels in the feed and boiler water are kept relatively
low, the concentration of such impurities in the steam phase within the turbine
results in a host of problems. Without such concentration mechanisms, the
construction materials can tolerate steam with low levels of impurities. However,
the concentration processes operate via deposit formation from super heated
steam, evaporation and drying as well as adsorption or inotganic ion exchange
on the metal oxide surfaces. It has been shown that iron oxide films concentrate
impurities by a factor of 10 to 100 and this might alter the composition of the
steam/water phase close to oxide interface. It is known that "dissociative
hydrolysis" of sodium chloride into HCI and NaOH at the hillb temperature
oxide surfaces results in the products as such being present in the IP and LP
sections of the steam turbines. Chemical analysis of the compounds in steam
turbines has shown a wide variety and range of compounds such as potassium
trisodium aluminium silicate, calcium aluminium hydroxy sulphate, sodium
aluminium molybdenum silicate etc., (which represent some of the highly complex
Steam Quality Requirements for High Pressure Turbines 89
compounds present) on the oxide surfaces in steam turbines, in addition to simple
compounds such as sodium chloride, ferric sulphate etc(3). It has been emphasised
by Westinghouse Electric Corporation that, .. Impurity concentration in dry steam
should be below its solubility anywhere in the dry regions of the system (turbine)".
Table 8.2 lists some of the failures in turbine components and the suspected
causes behind such events.
Table 8.2 Turbine Part Failures-US Industry Experlence(5)
Failure
HP Turbine bolts (steel)
HP Discs (Ni Cr Mo)
HP Blade (Springs)
HP Inner cylinder (Cr MoV)
LP Blades (SS)
LP Blades (12 Cr hardened)
Probable Cause
High Na in steam
High caustic in steam
- do-
High NaOH, NaCI in steam
Organic acids in steam
Inorganic acids in steam
After a detailed study, electrical utilities in USA and other advanced countries
have realised that an improvement of steam purity is needed in several operating
units inspite of the existence of well established boiler water specifications(5,6).
The philosophy behind the recommendations(l) as given in Table 8.1, for
superheated/reheat steam is,
(a) The steam quality should be achievable,
(b) The specified limits should be measurable.
The most important cationic and anionic limits are for sodium and chloride.
For normal operations, the sodium level has been specified to be less than
5 J.1g/l, low enough to guarantee that no deposition takes place of sodium
hydroxide, sodium chloride or any other compound any where in the turbine.
Analytical methods currently available are able to determine sodium in quantities
" less than 5 J.1g/1.
The corresponding limit for chloride ior has also been specified to be less
than 5 J.1g11. On-line chloride analysels using solid state electrodes are available
for such measurements. Ion chromatography with ready to use cartridges for
concentrating chloride in spot samples is also on the anvil.
If due to some reason or other, these limits of sodium and chloride are
exceeded during normal operation, some limiting conditions on operation have
been suggested. Sodium and chloride should not each exceed a limit of 20 J.1g/l
in one calender year or in one operating year, in any 24 hour operating period at
full power. On the other hand, for a two week operating period at full power,
these impurities in steam might range from 5 to 10 J.1gll in one calender or
operating year.
Measurement of the conductivity of the steam condensate after passing
through a cation exchanger, is also used as an important specification. Cation
conductivity rather than the total conductivity measurement, will avoid
interference due to the presence of ammonia, but will reflect the presence of
carbon dioxide. The best way to measure cation conductivity is to remove carbon
dioxide by blowing pure dry nitrogen. Under such conditions, the conductivity
90 Water Chemistry
of the steam condensate must be less than 0.3 J'S/cm during normal operation.
The limiting conditions are 0.5 to 1.0 J'S/cm for 24 hrs, and 0.3 to 0.5 J'S/cm
for two weeks in a calendar or an operating year. "
A 20 J'g/1limit for silica in steam has been in vogue for quite some time.
However, as a result of the silica hide out phenomenon and in view of the complex
silicate formation in turbine deposits, this '"limit has been lowered to 10 J'g/1 for
reheat units. During adverse operating conditions it can range from 20 to 50
J'g/l during a 24 hour period and can be in the range of 10 to 20 J'g11 during a
two week period. Since the distribution of silica between steam and boiler water
depends upon pressure, as well as on the pH of the boiler water, it is desirable
to follow the guidelines, given in Table 8.3.
Table 8.3 Maximum Permissible Concentration or Silica in Boiler Water, iCthe
Target or 10 J.1g11 of Silica in Steam is to be Met
Boiler Pressure
kglcm
2
60
90
120
150
18()
Boiler water silica in mgll (max.)
pH 9 pH 10
4.7 5.5
1.6 1.9
0.6
0.2)
0.10
0.7
0.28
0.12
Dissolved oxygen is yet another impurity that has been specified to be less
than 10 mg/l during normal operations. The limits under adverse conditions
were given earlier in Table 8.1.
EPRI guidelines prescribe Action Levels, when the specification limits are
exceeded duriAg normal operations(l).
Action level 1 is 2 weeks (14 days), same as noted earlier.
Action level 2 is 48 hrs., twice that noted earlier.
Action level 3 is 8 hrs, after which the persistence of abnormality
cannot be tolerated for more than 1 hr and calls for an immediate shut
down.
As far as reheat steam is concerned, EPRI guidelines are as given in Table
8.4. It may be noted that EPRI introduced a new chemical parameter, viz.,
sulphate, whose limits are as tight as that of chloride. While sodium and cation
conductivity are to be monitored on-line (continuous), chloride and silica are to
be sampled once a shift, while sulphate can be measured once a day.
table 8.4 Guidelines for Reheat Steam(l)
Parameter Unit Normal ""AI A2 A3
Sodium
J.1g11
5 5 10 20
Chloride J.1g11 3 3-6 6-12 12
Silica J.1g11 10 10·20 20-40 40
Sulpl1ate J.1g/1 3 3·6 6-12 12
Degassed cation J.1s/cm 0.3 0.3·0.55 0.55-1.0 1.0
conductivity
Steam Quality for High Pressure Turbines 91
The author's experience(7) with thermal power stations in India indicates
that sufficient attention is not being paid to the chemical monitoring and control
of steam chemistry. One of the lacunae noticed was the quality of attemperating
water. Unless this is well controlled, there is every likelihood of impurity ingress
into the high pressure steam. In fact, because of this type of situation, CEGB,
UK requires the sampling of saturated steam, so that the extent of contamination
can be monitored. Similarly, EPRI recommends the monitoring of sodium and
silica in saturated steam. It is generally recognised that saturated steam is the
most complex fluid to be sampled(1). This is primarily due to the differences in
density between steam and entrained water droplets.
Coming to the consideration of industrial turbines as distinct from utility
turbines, a recent survey indicated that blade deposits dominate the problem
area followed by pitting, and corrosion induced cracking(6). The pattern
resembles that found in utility turbines. Most of the industrial turbines require
an improvement in steam purity. The Mollier diagram has also been applied in
these cases to deduce the level of impurities that could be tolerated in steam.
The following procedure is recommended for using this diagram.
(a) Steam expansion lines are to be drawn for different types of operation
of an individual turbine. By different types, it is meant, whether the
turbine is to be operated at low or high load etc.
(b) The solubilities of major chemical impurities ill" superheated steam are
determined at the points where these lines cross the saturation line.
(c) The solubility value at the cross point is the impurity limit. However,
this is specific to the turbine under consideration.
The recommended steam purity limits for industrial turbines using non-reheat
steam are given in Table 8.5. It is obvious that the above limits are less stringent
than for high pressure steam (superheat/reheat) in utility turbines. It is only to
be expected, that with decrease in pressure, one can tolerate a higher level of
impurity.
Table 8.S Steam Purity Limits in 1\Jrbines(6)
Industry Temp. Pressure Inlet chemical parameters Cation
°c
kg/cm2(psig)
(llglI ) conductivity
Na Cl Si TOC Ils/cm
Pulp/paper 400 33.5(475) 15 10 30 150 0.5
Oil 450 63.4(900) 20 12 40 200 0.7
Waste Heat 315 38.7(550) 40 25 80 200 1.5
Non-reheat units
.REFERENCES
la. Strauss S.D .• (1988). Water Treatment Control and Instrumentation. Power. May
(Special Section) 1988. W-I to W-30.
lb. Aschoff A.F .• Y.H.Lu, D.M. Sopocy, and O. Jonas, (1986), Interim Consensus
Guidelines on Fossil Plant Cycle Chemistry, EPRI CS-4629, June 1986.
2. Prabhakara Rao A., (1983), Sampling and Analysis of Water/Steam in Power Plants,
Proc. Workshop on Water Chemistry in Thermal Power Stations, 25-38. Central Board
of Irrigation & Power, New Delhi, India.
92 Water Chemistry
3a. Venkateswatlu K.S., (1980), Steam Quality Requirements for High Pressure Turbines.
All India Conference on Boiler Water Treatment, Institute of Energy Management,
Bombay, October 1980,1-1 to 1-6.
3b. Venkateswarlu K.S, (1981), Water and Steam Quality for Maintenance of Generation
Efficiency. All India Conference on Water Chemistry for Industrial and TherfTIQl Power
Station Boilers. Indian Institute of Plant Engineers, New Delhi, April 1981, G-1I1 to
G-III1.
4. Gould G.C., P.W. Potter and F.J. Pocock. (1978). Activities of the International
Association for the Properties of Steam, American Power Conferences. April 1978,
Chicago.
S. 10nu 0., W.T. Lindsay, and N.A. Evans, (1979), Turbine Steam Purity, 9th
International Conference on Properties of Steam. Germany, 1979.
6. lonas 0., (1989), Developing Steam Purity Limits for Industrial Turbines, Power.
May 1989.78-83.
7a. Venkateswarlu K.S., (I98S), From Raw Water to Pure Steam: Problems in Thermal
Power Stations. Corrosion and Maintenance. 8, 187-192.
7b. Venkat:swarlu K.S., (1992), 'Update on Steam-Water Chemistry in Power Plants',
All India Convention on Industrial Water Treatment and Conservalioll, National
Centre for Technical Development, Bombay, November 1992, P.I-P.S.
9
SPECIAL PROBLEMS OF WATER CHEMISTRY
AND MATERIAL COMPATIBILITY IN NUCLEAR
POWER STATIONS
At present and in the foreseeable future, the deployment of nuclear power is
through water cooled nuclear power reactors(1,l). In nuclear power plants, both
light and heavy water, H
2
0ID
2
0 is made use of as a moderator and coolant. As
a moderator, the hydrogen or deuterium atoms of the water molecule, reduce
the velocities of neutrons generated-in fission to thermal energies (0.025 ev)
which makes the chain reaction feasible. A sQlid like graphite can also act as a
moderator or one can dispense with the moderator altogether as in fast reactors,
wherein the fission chain reaction is sustained by fast neutrons (-1 Mev).
However, since the ultimate aim is to generate steam that drives a turbille, the
use of high temperature-high pressure water cannot be avoided in any type of
nuclear power plant. As far as this part of the operation' is concerned in which a
steam generator, a turbine and a condenser are the major components, the
problems of water chemistry and material compatibility are essentially the same
as in thermal power stations(3). The nuclear steam generator tube integrity is
however, much more critical than the fossil fuel fired boiler tube integrity, as
any rupture in the former would lead to radio-active contamination of the steam
water circuit. Consequently, superior materials like stainless steel and high nickel
a ~ l o y tubes are used in nuclear steam generators.
The all important issue in the safe operation of nuclear power reactors is the
accidental release of radioactive fission products from the core and generation
of activated corrosion products in the primary water coolant that flows through
the reactor core and their redeposition(4). It is equally important that during
normal operation and maintenance, the occupational exposure of workers,
The author was associated with the Coordinated Research Programmes of the International
Atomic Energy Agency on Reactor Water Chemistry and the material in this chapter is
partly based on that experience.
94
Water Chemistry
operators and supervisiors, be kept to a minimum i.e. lower than the radiation
exposure dose limits, prescribed by International Commission for Radiological
Protection and national regule.tory agencies.
Water cooled nuclear reactors can be broadly divided into two groups: boiling
water reactors and pressurised water reactors. The boiling waterreactors (BWRs)
developed in USA, make use of a pressure vessel, lined with stainless steel in whlch
the nuclear fuel elements, in the form of a core of a particular geometrical
configuration reside. The fuel elements consist of an array of fuel rods (7x7 or 8x8).
The fuel rods are made of zircaloy tubes filled with low enriched uranium dioxide
(V02) pellets and sealed at both ends. The core is surrounded by water, which acts
both as a neutron moderator and as the name implies, a boiling (- 270°C) coolant.
The steam-moisture mixture is passed through moisture or steam seperators and
the steam is then fed directly to a turbine. In some of the BWR versions, part of
the reactor water is fed to a secondary steam generator and the steam which is
generated at low pressure is fed to an appopriate stage of the turQille. The exhaust
steam after condensing to water is purified through the use of deep bed
demineralisers and fed back to the reactor through feed water heaters. The
Tarapur Atomic Power Station is an example of this type(s,sa).
, "
Jhe boiling water reactors developed in the former Soviet Union, use graphite
b l o ~ k s is the moderator in which pressure tubes are embedded vertically. The
fuel elements reside in the pressure tubes, leaving sufficient space for coolant
water to flow through them and boil. The steam generated is collected and fed
to a turbine as in western BWRs. The Chernobyl nuclear power station is an
example of this type ofBWR and is known as RBMK(6).
The other group of water moderated and cooled reactors are known as
pressurised water reactors (PWRS). Here again the arrangement is the same as
in western BWRs, except that the water is not allowed to boil by the application
of higher pressure. The high pressure coolant is fed to a steam generator on its
tube side. Steam is generated on the shell side and the rest of the circuit is the
same as in a thermal power station. While this type of.plant is called PWR in
western countries, in Russia and other states of the former Soviet Union and in
eastern Europe, it is known as VVER (6). At present in the nuclear power industry
PWRIVVER is the dominant reactor. The nuclear core is again made up of low
enriched U0
2
pellets encased in zircaloy tubes, which are smaller in diameter
than in BWRs.
A third gruop of water reactors has been developed by Canada and are known
as CANDU reactors. The Indian nuclear power programme is based on this
type of reactor, which have been described as Pressurised Heavy Water Reactors
(PHWRs)(S). A!':8entina. Rumania and S.Korea are the other countries interested
in this type of power plant(6).
CANDUlPHWR makes use ofzircaloy pressure tubes as fuel channels which
are horizontally fixed in a vessel ca,lled calandria. This is filled with heavy
water which acts as a moderator at about SOoC. A little pressure is applied to
maintain the required circulation. The fuel is made up of natural U0
2
pellets
clad in zircaloy. The fuel pin clusters or bundles are of much smaller length,
than those in BWRs and PWRs. Usually 12 bundles are loaded into each of the
Water Chemistry and Material Compatibility
95
fuel channels, through which heavy water at high temperature (-275°C) and
pressure flows as the heat transport fluid,. without boiling. The outlets of all the
fuel channels are combined and this hot heavy water then goes through the tube
side of a steam generator. Light water is used on the shell side to generate
steam which is then fed to a turbine.
A class of reactors developed in the UK, makes use of as the
moderator and Carbon dioxidelHelium as the coolant. Ultimately the coolant
gases generate steam. These reactors are the mainstay of the UK nuclear power
industry.
In fast reactors where there is no moderatot:and the fuel is of highly enriched
Uranium and Plutonium, the heat of the compact core is removed by molten
sodium, which in turn is used as the heat source in a steam generator, either of
a recirculating or once through type.
Against the above background, special problems of water chemistry and
material compatibility are further discussed. The major issue of concern is
radioactivity. The low level magnetite transport in the heat transfer circuit, which
is of no consequence in thermal power stations, results in the activation, transport
and redeposition of corrosion products in nuclear power plants(7,1). The principal
offender is Cobalt-60 (Co-60), a strong gamma-ray (y-ray) emitter with a half
life of -5.3 years. The deposition of this nuclide on out of core surfaces, along
with Co-58 and other radioactive products makes maintenance a serious problem.
Skilled maintenance personnel can work at their tasks for only a short period at
a time. The radiation exposure limits are such that a welding repair in a thermal
power station which takes about an hour of a skilled technician's time might
require as many as six welders of equivalent skill on the coolant circuit in a
nuclear power station shortly after shut down. In nuclear industry this has come
to be known as the ¥an-Rem problem. Considerable effort of water chemistry
control in nuclear power stations is focussed on to this issue('). Minimising the
Man-Rem problem is taken up from the stage of design and materials selection
itself. The number of valves and joints is minimised to reduce repair work and
materials with as Iowa Cobalt content as practicable are selected for reducing
the radiation dose. Apart from design and material selection, this problem is
largely tackled in the primary system by a strict water chemistry control.
Maintenance of steady pH in a narrow range effectively controls mass transport
during the operating cycle of a nuclear power station.
An equally important issue is the chemistry under accident conditions(lO).
Unlike in thermal power stations, the core can heat up very fast. In the Three
Mile Island nuclear power station, unit 2 (TMI-2) and in the Chernobyl nuclear
power station, unit 4 (CN-4), such a sharp and fast rise in clad temperature led
to its chemical interaction with water. The highly exothermic reaction resulted
in the production of hydrogen.
Zr + 2H
z
O ZrOz + 2H
z
(9.1)
The hydrogen generated in massive quantities can lead to an explosion
(muffied in the case ofTMI-2 and violent in the case ofChernobyl-4) and spread
ofradioactivity(II). The major concern even in minor accidents is the release of
radioactive iodine and caesium (both fission products). Their chemical forms
and hence their dispersal depends strongly on the water chemistry prevalent in
96
Water Chemistry
that particular situation.
Another problem of serious concern is the rupture of a steam generator tube
in PWRs and PHWRs. It is almost impossible to retube such a steam generator
which will he radioactive due to the deposition of corrosion products on the
tube side. The stress corrosion cracking of l..ainless steel pipin6 in BWRs is
also a matter of serious concern.
A problem of water chemistry that is special to water moderated and water
cooled reactors is the radiolysis of water(l2). This leads to the production of
hydrogen and oxygen, which gives rise to two issues. One aspect would be to
ensure that the mixture does not explode. The other concern relates to the
increased dissolved oxygen content of v.ater that would result in enhanced
corrosion. If the water is heavy water as in PHWR, the additional problem of
recovery of D
z
(a costly isotope) has to be tackled.
Because of radiolysis, oxygen and pH control additives such as hydrazine,
ammonia 01' morpholine may not be added to the primary coolant system during
operation. However, VVERs do add ammonia as seen later on. A chemical
additive which is not required in thermal power stations is boric acid. This
chemical (B
2
0
3
dissolvrd in HzO or DzO) is widely employed in PWR/VVER/
PHWR as a neutron absorbing (control) material. The ion exchange purification
has to be dovetailed into the maintenance of the required concentration of boric
acip in the moderator at any given time. There is no addition of boric acid in a
BWR.
Thus the main objectives of reactor water chemistry are,
(a) Reduction in the aggressive action of high temperature water towards
the structural materials (stainless steel,carboll steel, zircoloy and high
nickel alloys like Monel, Inconel etc.) to condition the chemistry
environment such that the mass transport is minimal and in a specific
direction, so that activity build up on out-of-core surfaces can be
kept to a minimum.
(b) Achievement of the lowest possible radiation exposure
by minimising the ingress of incore impurities and out-of-core
radioactivity build up.
(c) Prevention of the release of radioactivity into the environment.
(d) Prevention of fuel element surface fouling that could adversely affect
heat transfer and corrosion.
(e) Containment of radiolysis products.
Radioactive corrosion products may be generated either directly or indirectly.
In the first instance, corrosion would result in the release of neutron activation
products from in-core structural materials. In the second case, corrosion products
from out-of-core surfaces that get deposited on the incore surfaces, undergo
neutron activation and get resuspended into the coolant(l3). Since the bulk
corrosion product is magnetite, Fe
3
0
4
, the other corrosion product oxides may
be free (e.g.Co
Z
0
3
) or mixed ferrites such as NiFe
z
0
4
or CoFe
2
0
4
• The radio-
activity is due to 60CO, sSCo, SICr, s4Mn and s9Fe. Apart from S8CO, the others
are generated due to thermal neutron activation of the corresponding inactive
isotopes of these elements. S8Co is generated by fast neutron activation of s8Ni.
Cobalt is a low level (ppm level) componen' of stainless steels, nickel alloys
Water Chemistry and Material Compatibility 97
such as Monel-400 and Inconel-600, as welt as a high level (55 percent)
constituent in hard facing materials such as stellite alloys. Whiie the former
group of alloys are extensively used, stellite is used only sparingly with relatively
low incore surface area. As mentioned earlier the principal concern is 6OCO,
followed by 5SCO. Radioactive and non-radipactive corrosion products may be
transported in the coollUlt both as truely soluble species, as well as inertial
(> 1 J..I.m)or colloidal «I J..I.m) particulate species·. Particulate matter is
conventionally defined as that retained by a 0.45 J..I.m microporous filter
membrane. Material that is not retained and which goes through the membrane
is often classified as ·soluble'. Therefore, the soluble fraction will also contain
some colloidal particulates in addition to the truely 'soluble' species. It has
been suggested that most of the non-filterable 6OCO circulating in a PHWR coolant
is colloidal in nature. A contrary view is that true soluble Co transport is dominant
when the crud levels are low. It is also often assumed that iron, nickel and
chromium species behave in the same way as the cobalt species, with respect to
nucleation and precipitation. this however, is not borne out by experience. The
behaviour of substituted ferrites is somewhat different from that of magnetite.
It is desirable that all such variations be reflected in the evolution of any model
for corrosion product transport(l4, 15).
A simplified diagram of the processes described above is shown in Fig.9.1.
Out of core
A
a. Corrosion of
system surface
!
I
I
I
I
I
b. Formation of ~
corrosion products I
Soluble. Colloidal I
Particulate species !
J
BB
I
I
~ - - - - - - - - - - - - - - ~ I
REACTOR CORE !
Out of core
B
1. Neutron flux zone
I a. Corrosion of
2. Source offission and ~ system
corrosion products I surface
3. Neutron activation of I c. Deposition of
corrosion product' I corrosion
4. Soluble and colloidal - ~ . prod. as films.
corrosion products flow I d. Deposition
through getting activated I and
S. Particulate corrosion
products deposit and reside
in-core for a while. get
activated and get released
by exfoliation and/or by
resuspention
AA
incorporation
of fission and
activated
corrosion
products.
COOLANT FLOW CANDUIPHWR
Fig. 9.1. Corrosion and Deposition Process In Water Cooled Nuclear Power
Reactor
(Processes in AA and BB are same as indicated in A and B respectively.)
'" Reactor coolant water chemistry literature wideHy refers to this as 'crud'. The term
appears to have originated in Canada and is reported to be an acronym for Canadian
Reactor Unidentified Deposit. It is insoluble and hence. is composed of both inertial as
well as collodial particulates.
98
Water Chemistry
From the above discussion, it is apparent that in the reactor coolant circuit,
a 'source term' and a 'recipient term' coexist which will ultimately result in the
transport and deposition of radio nuclides. These two terms are inter-dependent.
Any change in operational chemistry that affects the corrosion rate has an
immediate impact on the 'recipient tel,n' and a delayed efrect on 'source term'.
Consequently, control of corrosion will lead to the control of the entire activity
transport process. The regimes in the primary heat transport system of water
cooled reactors have been devised to meet this requirement, viz.,minimising
corrosion with a consequential reduction of material transport through the core.
In the harsh environment of the reactor core, both hydrodynamic and radiation
field wise the fuel cladding material, viz.,ziracaloy experiences the worst conditions.
Fortunately, the corrosion resistance of zircaloys (zircaloy-2 and 4)is very
good(16,17,17.) and the neutron absorption cross section of Zr is very low.
Consequently,radioactivation and the deposition of radioactive 9SZr on out of core
surfaces is not a matter (If concern. However, what is of significance is the
integrity of the thin fuel tubes, as welI as the relatively thick pressure tubes in
PHWRs. Development of pin holes or minor cracks in the fuel tube will lead to
the release of fission products (like iodine and caesium) to the coolant, which is
not acceptable. In fact, when one speaks of fuel performance in nuclear reactors,
one is actually discussing the Zr clad integrity. It was found that this is affected
more from 'inside attack' than from the outer coolant. Internal hydriding, stress
corrosion cracking due to pellet clad mechanical interaction coupled with the
chemical interaction between fission product iodine and Zr are some of the
reasons ascribed to clad failure both in BWRs and PWRs/PHWRs(
18
1. Hydrogen
embrittlement of zircaloy is another problem that has received considerable
attention. The failure of a pressure tube in one of the reactors at the Pickering
Nuclear Generating Station, Canada is suspected to be partly due to hydrogen
percolation into zircaloy pressure tube under special stress conditions.
A wide variety of analytical techniques have been applied in chemical
laboratories of nuclear power stations to monitor and control water chemistry.
The International Atomic Energy Agency, has colIected relevant information
from different cvtlntries and tabulated the same for easy reference
l19l

In boiling water reactors, the dominant material is stainless steel (304, 304L
etc.) besides zircaloy. Not only is the pressure vessel lined with SS, but the
primary piping is also of this material (steam lines are of carbon steel). The
coolant chemistry in BWR adopts a hands-off policy, with no chemical addition,
using as pure water as possible(s.a). Thus condensate polishing is mandatory.
The main chemical characteristics of the feed water and the boiling reactor water
are more or less the same. Differences are essentially due to the concentration
factor. The specifications(61 for water quality in BWRs are given in Table 9.1.
As the reactor oxygen level IS an equilibrium value depending on the reactor
operating power, one has no control over this parameter. Hence, BWRs impose
a severe restriction on chloride. This is to avoid the stress corrosion cracking
(SCC) of stainless steel. Pipe rupture accidents due to (SSe) have been
experienced in BWRs.
Wat" Chemistry and Material Compatibility 99
Table 9.1 Feed and Reactor Water Specifications for BWRs(6)
Chemical Units GE VGS RBMK
2arameter FW RW FW RW FW RW
Sp. Conductivity
J.l.S/cm 0.1 1.0 0.15 1.0 0.1 1.0
pH a 25°C 6.8 7.2 6.5 8.5
Chloride
J.l.g/l
NS 200 NS 200 4 l00(CI+F)
Oxygen
J.l.g/l
NS • NS •
NS NS NS NS
Silica J.l.g/l NS 4000 NS 4000 NS 1000
Iron
J.l.g/l
13 NS 25 NS 60 200
C022er J.l.g/l
2 NS 3 NS 2 50
NS: Not Specified
• Though not specified. feed water dissolved oxygen is not expected to exceed 14 1Lg/1 in
Tarapur. In reactor water an equilibrium level of - 400 1Lg/1 would be prevalent due to
radiolysis and stripping.
The see propensity of austenitic stainless steel in relation to chloride and
dissolved oxygen in water has been thoroughly studied(lO.ll) and the inter-
relationship is shown in Fig.9.2.
100
100
2\
\
\
\
0
1
2
1
'."'IWR! o· NO ,.AILURE
FGURES tlEMJ'M tfJM8ER a: SP£CIMlNS
2
2
\'
\
"
3
n,wS
1
.2
2

.2
2
1) 3'
"'-
",

!J"'"-- _
,z
-2

10
CHLORIDE mgtl
100
03
01
1000
Fig.9.2 Stress Corrosion Cracking of Stainless Steel-Influence-Chloride and
Dissolved Oxygen(lO) ,
One way to reduce dissloved oxygen in a radiation environment is to promote
the radiation induced back reaction. This can be achieved by the injection of
hydrogen into the coolent water. Production of oxygen can be through
a chain reaction which rapidly eliminates OH. H0
2
and H
2
0
2
• the precursors of
t1101ecular oxv!!en,
100
H2 + OH HzO + H

H + H0
2
H
2
0
2
H + H
Z
02 H
2
0 + OH
Water Chemistry
(9.2)
(9.3)
(9.4)
(9.5)
Eventually, the chain reaction will lead to the reconversion of the stable
radiolysis products, H
z
0
2
, 02 and H2 back to water. Laboratory as well as large
scale demonstration experimems have shown this to be feasible, even in a boiling
(consequent stripping of hydrogen) condition of the coolant. This type of
chemistry cO!1trol, called Hydrogen Water Chemistry(2J), is gradually being
introduced in BWRs (though not at Tarapur, India).
Reactor water purification is the key to adequate cooiant chemistry control
in BWRs. The normal clean up flow is about 2 percent of the feed water flow at
full power. The primary coolant, diverted to the purification plant is at a high
temperature and pressure. It is usual to reduce the temperature, but purify at a
relatively high pressure so as to maintain the desired high purification flow rate
through mixed bed demineralisers, preceded by cellulose and/or Powdex* precoat
filters. A decontamination factor not less than lOis acheived. Full flow
condensate polishing is mandatory, as stated earlier, for BWRs, using deep mixed
bed ion exchange resins.
The primary coolant chemistry of PWRIVVER is more complicated than
that of BWRs(6). A specific feature of the chemistry is the presence of boric
acid over a wide range of concentrations, to control reactivity. The variations
could be from 0 to 1200 mg!l measured in terms of boron. A boron level upto
400mg!l could be encountered under shut down conditions. At operating
temperatures (270°C-to 320°C), an alkaline pH condition is to be maintained
to minimise the corrosion. The presence -of boric acid makes it aU the more
necessary to add an alkltli. Here, PWRs differ from VVERs in the nature of the
alkalising agent. While PWRs make use of lithium hydroxide, (as 7LiOH), VVERs
employ a mixture ofKOH and NH
4
0H. Since the mixture is a of a
strong and a weak base, a sort of buffering action prevails. A pH (300°C) value
of 6.9 to 7.4 has been found to be optimum. Since this range of pH calmot be
directly measured in a reactor system at 300°C, a set of calculations based on
room temperature pH measurement of boric acid-LiOH ,mixtures is made use
of. A coordinated boron to Li ratio has been evolved to acheive pH (300°C) of
6.9 to 7.4 throughout the cycle. Similarly in VVERs a pH (260°C) of 7.1 is
acheived by adjusting the boron to potassium ratio. Considering that a part of
the rractor water is constantly purified by ion exchange, one can see the
difficulties involveu in maintaining such constant ratios over prolonged periods.
In PWRs, a low level of dissolved oxygen is maintained by injecting hydrogen.
On the other hand, in VVERs, in-situ radiolysis of ammonia generates the
hydrogen required to keep the level of oxygen low.
The chemical specifications for the reactor coolant water in PWRs and
VVERs are given in Tables 9.2 and 9.3(6).
• POWDEX is a brand name for cation &. anion exchange resins made in very fine particle
size. These resins mixed with binders in a slurry and cast over porous surface, serve as
precoat filters.
Water Chemistry and Material Compatibility 101
Table 9.2 PWR Reactor Water Quality Specifications(')
Chemical Unit Value Remarks
Parameters
pH at 25°C 4.2 - 10.5 Depends upon H
3
B0
3
and 7LiOH concentration
pH at 300°C 6.9-7.4
Boric acid as boron mgll 0- 1200
7LiOH as 7Li
mgll 0.7 - 2.2
Sp. Conductivity J.1S/cm 1 - 40 As for pH at 25°C
at 25°C
Hydrogen cm
3
/kg 25 - 35
(at STP)
Oxygen J.1g11 5 During power operation
with H2 as above
Chloride
J.1g11 150
Fluoride

150
Table 9.3 VVER - 400 Reactor Water Quality Specifications(6)
Chemical
Parameters
pH at 25°C
KOH as K+
H
3
B0
3
NH3
Hydrogen
Unit
mglkg
glkg
mglkg
cm3/kg
(at STP)
Value
6.0
2 to 16.5
o to 8.0
5
30 to 60
Remarks
In-situ equilibrium
values
Water chemistry on the steam generating side of PWR/VVER is the same as
in fossil fuel fired power stations(9). Coordinated phosphate.or AVT is employed.
In early designs of drum type steam generators, the tubes were of a high nickel
alloy, Inconel-600. Stainless steel has also been used as the tube material. Based
on long term experience, the present trend is towards the use of a
relatively low nickel alloy, with additional content of Cr. Inconel-690 is a tube
material that is showing great promise.
In several cases, the nuclear heat transport system is coupled to a once-
through steam generator, with zero solids treatment and condensate polishing.
The nuclear industry has been conditioned over the years to have dissolved
oxygen at levels less than 10 !lg/l in the feed water to the steam generators.
However an accident in December, 1986 in a nuclear power plant opearated by
the Virginia Power Company, USA has revived arguments against such low
levels. A portion of the carbon steel section of the feed water piping experienced
severe tPinning from the inside, which escaped in-service inspection. The pipe
line suffered a guillotine failure. Water (non-radioactive,as it is in the secondary
circuit) flashed to steam. Due to the configuration in that section of the piping
turbulence was the main culprit. In the initial stages of the investigation although
102 Water Chemistry
the low level of dissolved oxygen was blamed for not providing enough of the
protective magnetite layer, a full investigation, showed this to be unsubstantiated.
The reason for this is that just as on the primary side, dissolved oxygen is to be
rigorously controlled on the secondary side as
The history of PWR steam generator corrosion is a good example of all the
major problems in any steam raising circuit(9). The study led to an understanding
of the complexity of the water-steam system at high temperatures vs material
compatibility. Phosphate chemistry works well at relatively low temperatures.
Temperature increase leads to phosphate hide-out, which results in alkaline stress
corrosion and phosphate induced thinning where local boiling temperatures are
aroung 280°C. Removal of phosphate, without rigorous removal of chloride,
produces excessive corrosion of carbon steel causing tube denting in the baffle
plate region. This situation gets further aggravated, if copper alloys and a higher
level of dissolved oxygen are present. It could even lead to tube pitting. On the
other hand, the advantages of A VT are off set by its inability to provide buffering
action in the event of condenser tube leaks, especially if the condenser is cooled
by sea water. A VT is also not really compatible with the presence of copper
alloys and poses problems in condensate polishing. A boiler water treatment
that is being tried out in conjuction With A VT is the addition ofboric acid,which
is a very weak acid at high temperatures. Its action in reducing corrosion damage
results from the incorporation of boron in the thin corrosion films, making
them more protective.
The water chemistry in CANDU/PHWR group of reactors(S.6) is in some
ways simpler than that ofPWR/VVER. However, the use of heavy water as the
coolant and moderator imposes special restrictions on operations, sampling and
analysis as the presence of the radioactive isotope, tritium(3H) poses an additional
inhalation hazard and spillage of the expensive heavy water has to be avoided.
As mentioned earlier, Canada and India are the countries where these reactors
are tl,e base for nuclear power. All these units are of the pressure tube type,

emplo) mg zircaloy-2 clad natural uranium dioxide fuel and using heavy water
as the moderator as well as the coolant. The latter is in seperate circulating
systems that operate under different conditions of temperatrue, pressure and
chemistry. The primary heat transport system is comprised of multi metal
surfaces, the major components being carbon steel,zircaloy-2 and Monel-400
or Incaloy-800. The objective b\!hind coolant system chemistry is the same as in
all other nuclear power reactors,viz.,to minimise the out of core radiation fields
by minimising the processes of corrosion and erosion of the heat transfer
surfaces(8,H). A prerequisite for achievir.g this objective is, "Hot Conditioning,"
of the primary heat transport system during its light water commissioning stage.
After cleaning and de greasing the system surfaces, water maintained at pH 10
(by LiOH) and deoxygenated (by hydrazine) is circulated in the system in the
temperature range of 220°C-240°C for about 10 days. Such a procedure results
in the formation of a thin protective layer of magnetite (Fe304) especially on
carbon steel surfaces(5). This minimise's further corrosion of the structural
materials and acts as a check on crud inventory. The steady state crud
concentration values /lave been observed to be -0.0 I mg/l, with some transient
values during up and cool do .... n operations. The integrity of the magnetite
Water Chemistry and Material Compatibility 103
film is due to a well regulated coolant chemistry and consequently results in a
low level of the activity transport. This contributes to low out of core radiation
fields(4).
As compared to PWRs or VVERs, the advantage of PHWRs stems from
their different moderator system in which boron is added rather than to the
coolant. This simplifies the coolant chemistry and in general permits a higher
operating pH which is mostly kept constant at 10.2 ± 0.2 (as measured at 25°C)
by the addition ofLiOH. The specific conductivity of the coolant normally ranges
between 15 to 30 j.ls/cm. A pH of 10.2 at 25°C due to LiOH addition alone
means apH of7.4 at 270°C - 280°C which is generally the operating temperature
in PHWRs. In terms of magnetite solubility the pH and the temperature regimes
ensure that the solubility of magnetite is almost minimum. Actually it is a little
towards the right hand side of the minimum in the solubility vs. pH (280°C)
curve for Fe
3
0
4
(Fig.4.4). With a positive temperature coefficient, the magnetite
solubility increases in the coolant channel from the inlet to the outlet, thus
reducing the chance of deposition on the fuel clad surface. It may be mentioned
that the adsorption of Co (II) on magnetite is maximum and constant in the pH
range. This would mean that the Co adsorbed by the magnetite layer on the fuel
clad surfaces has a chance to get activated. On the other hand,with the solubility
gradient of magnetite in a fuel channel, Co(II) is expected to be in the suspended
or soluble form in the coolant. In short, the operating pH takes care of the
integrity of the magnetite film formed during hot conditioning/normal operation.
It also keeps the magnetite solubility in the appopritate direction and ensures a
lower residence time for Co (II) in the core(14).
Another chemical control that is strictly adhered to is that of dissolved oxygen
in the coolant. In a closed system, water radiolysis leads to generation of hydroxyl
radicals which end up as dissolved oxygen. The Primary Heat Transport (PHT)
system in earlier PHWRs had a large surface area ofMonel-400 (steam generator
tubes) in contact with the coolant 020. The corrQ,$iqn of this alloy at high
temperatures is adversely influenced by dissolved oxygen. In view of the high
Ni content 'If this alloy, Monel surfaces are one of the major sources of cobalt
in the system,. Thus it is essential to maintain a low level of dissolved oxygen
(10 ).1g/l), so as to minimise the corrosion of Monel and hence the input of
cobalt. Hydroxyl radicals can be scavenged by increasing the partial pressure of
dissolved hydrogen in the coolant. In PHWRs, hydrogen injection to a level of
10 to 15 em 3/kg of 020 at STP has been found to keep dissolved oxygen at
-10 ).1g/1. It is also to be noted that hydrogen addition to the coolant does not
influence the solubility of magnetite, since the solubility is dependent on the
cube root of hydrogen partial pressure(14). Following the development and good
performance ofIncoloy-800 as the steam generatcr tube material, Monel-400 is
being substituted with this alloy. Incoloy-SOO is not all that susceptible to
dissolved oxygen transients at h i ~ h temperatures and having a lower Ni content,
will have less cobalt inventory.
The third aspect of the coolant chemistry in CANOUlPHWRs relates to its
purification. A part of the coolant (1 % of coolant inventory) is withdrawn from
104 Water Chemistry
the circuit. cooled and then passed through a filter and mixed resin bed. In
order to keep the pH of the coolant constant, the Li form of the cation exchanger
is employed. while aD (02H)form of the anionic resin ensures no degradation
of isotopic purity. The use of organic ion exchangers is a cause for a chemical
transient. since the intrusion of any of the resin into the system will upset the
chemistry due to their thermal and radiation degradation. This is true for all
types of reactors.
Against the above background. the experience of coolant chemistry in
CANDUlPHWRs has been very satisfactory. Chemical transients are rare. The
radiation fields around the steam generator cabinets. measured 24 hours after a
shut down are fairly low and constant. On-line 'Y-monitoring of the outer surfaces
of primary piping (over the insulation) indicates that the major contributory
radionuclide to the radiation field is 6OCO and occassionally,fission products as
in other reactor types(4). The replacement of Monel-400 by Incaloy-800 is
expected to further reduce the radiation field build up on the out-of-core surfaces
that was observed earlier. Models for activity transport have been developed(8).
Typical specifications for the chemical control of the heavy water coolant
are given in Table 9.4.
Table 9.4 Chemical Control Specifications for PUT System in PUWRs(14)
Parameter/ Sampling
Constituent frequency
Isotopic 3/week
purity
Sp. Conductivity 3/week
IIday
Chloride 3/week
Fluoride IImonth
Range/
limit
95% min.
30 micro
Siemens/cm
Between
9.5 - 10.5
0.3 mgll
0.5 mgll
Remarks
From reactivity
considerations.
Specific conductivity
limited by the
concentration of
lithium hydroxide
(LiOH) maintained in
the coolant for keeping
iis pH within specified
limits.
Adjusted with lithium
hydroxide (LiOH).
This is the optimum pH
range for least corrosion
of the carbon steel in
the system
To minimise possible
stress corrosion.
Higher concentration of
fluoride can have a
corrosive effect on
zircaloy tubes and fuel
cladding.
Contd.
Water Chemistry and Material Compatibility
Table 9.4 (Contd.)
Parameter/
Constituent
Crud
Dissolved
Oxygen
Dissolved D2
Sampling
frequency
IIweek
3/week
lIweek
Range/
limit
0.1 m g / ~
for
steady
operation
10 f.Lg/1
during
steady
operation·
Between
3 - 20 mg/l
ofD2 at
STP
105
Remarks
Circulating crud gets
activated in the core and
will get deposited on the
fuel bundles and on the
PHT system surface.
Higher values of oxygen
damages the protective
magnetic layer and
increases the corrosion
of boiler tubes
specially of
Monel-400. Both will
lead to problems of
activity transport.
Maintained by injecting
hydrogen to the system
when pressurised.
• If the limit exceeds the value, it shall be brought back below the limit in 72 hours, failing
which the reactor shall be shutdown.
The heavy water moderator that fills the calandria is in a seperate low temperature
(-50°C) circuit. Boron Trioxide dissolved in Dp is added for reactivity control
and the required concentration is maintained by a by-pass ion exchange unit, that
also takes care of the purification. The radiolysis of heavy wl!ter releases D2 and 02
into the He cover gas of the moderator system. This gas is circulated through catalytic
recombiners, so that the concentration never exceeds four percent vN (Volume of
D2tTotal volume of cover gas). Other important chemical parameters are the isotopic
purity and chloride, the latter because the system components have stainless steel
surfaces.
In the secondary system of all CANDU/PHWRs, A VT is being employed
with morpho line as the alkalising agent. This poses problems, if condensate
polishing is also practised, as would be the case at a seawater cooled power
station, (such as MAPS at Kalpakkam, India). Since the condenser tubes are of
AI-brass and there is heavy biofouling, there are bound to be condenser tube
leaks. Two signigicant developments are worth noting in this context. An
in.l:ractive software code, "BOIL", stimulates the build up of chloride in different
parts of the secondary circuit due to seawater leaks in the condenser(25). It is
possible to establish the leak rate by measuring the chloride concentration twice
in succession over a period of time in the steam generator and feeding that data
to the code. The resulting determination of the leak rate helps the operators to
106 lfater Chemistry
initiate corrective action.
The other development relates to the performance of the condensate polishing
unit (CPU)(16). The impact of morpholine is both direct and indirect. The
concentration of morpholine is higher (2-3mgll) for a given pH, as against
ammonia (0.5 mg.l.). This results in lesser effluent volume from the polishing
bed prior to Its saturation with morpholine. As the selectivity coefficient of
morpholine (MOR) over sodium on the resin is rather poor, the retention of
sodium in the resin is highly dependent on the ratio of Na to M O R ~ The chloride
slip is indirectly controlled by morpholine absorption by the bed; it is minimal
untill morpholine saturation occurs. Hence, it is anticipated that the performance
of the condensate polishing unit would be poorer in the presence of morpholine
than that in the presence of ammonia under the same conditions of resin quality,
the ratio in the mixed bed and regeneration characteristics.
Water Chemistry and corrosion problems are experienced not only in power
reactors,but in research reactors as well. A couple of examples will illustrate
the point. In 1961, when the effects of water radiolysis '\fere not fully appreciated
in large systems, 300 mgtl of potassium chromate was added as a corrosion
inhibitor, as well as a biocide to primary coolant water (H
2
0) of the CIRUS
reactor in India. Radiolytically' produced H radicals, reduced the chromate to
trivalent chromium, which got precipitated as its hydrous oxide on the aluminium
clad of the metal fuel. This caused pressure drops and reduced the flow of the
coolant leading to fuel failures. A mixture of hydrogen peroxid\, and di sodium
salt of EDTA was used to clean up the coolant channels and fuel clad surfaces.'
Chromate was also removed from the system, thus solving the root cause of the
problem(17). In 1985, due to vibrational problems, the aluminium cladding of
the fuel bundles in the DHRUVA reactor in India was getting eroded and corroded
at a rapid rate. This led to the formation of alummium hydrous oxide turbidity
in the heavy water coolant. The turbidity was idel'\(ified as Bayerite aging to
Gibsite and t!te colloid was negatively charged. A m4tgnesium loaded weak acid
cation exchange resin was developed to clean the treavy water of its turbidity
and associated radioactivity. Magnesium was later hydrolysed in the resin pores.
When the contaminated heavy water was passed through such a special ion
exchange resin bed, the turbidity was removed and the clean heavy water returned
to the reactor(18). For a similar purpose Israel developed a carbon fibre filter
material.
In lccidental situations, where the primary coolant water (H
2
0ID
2
0) spills
out of the circuit, its chemical condition at that time determines the chemical
nature of the volatile radioactive fission products such as iodine and the release
behaviour into the containment atmosphere. If the coolant is alkaline as in
CANDU/PHWR, most of the iodine will be retained in the aqueous phase as
iodide. On the other hand, if it is a BWR neutral coolant. a considerable fraction
of iodine will De in the form of 12 and hence will volatalise. PWRNVER situation
depends on the pH at that time, which is determined by the ratio of lithum to
boric acid.
The severe nuclear reactor accidents in NR.X, TMI-2 and Chemobyl-4 have
Water Chemistry and Material Compatibility 107
brought the role of water and steam chemistry in aggravating the effects into
sharp focus(10). The temperature of the core materials will continue to rapidly
increase to levels much higher than in the normal operating mode. Consequently.
several interactions get initiated at fast rates. when water/steam comes into
contact with very hot surfaces. With increasing temperatures. these processes
are:
1. 2H
2
0 + C 2H2 + CO
2
2. H
2
0 + C H2 + CO
3. 3H
1
0 + 2Al 3H
1
+ AlP3
4. 2H
2
0 + Zr 2H2 + Zr0
2
5. 3H
2
0 + 2Cr 3H
2
+ Cr
2
0)
6. 4H
2
0 + 3Fe 4H2 + Fc
3
0
4
7.
8. H
2
0 + U0
2
More volatile U bearing species.
9. H
2
0 + Fission products More volatile species.
(Here H
2
0 signifies water and lor steam depending upon the situation).
Chemical reactions excluding 3 and 7 played important role in CN-4. while
reactions 4. 8 and 9 and possibly Sand 6 were of significance in TMI-2. On the
other hand.reactions. 3. 7 and 9 were reported to have influenced the course of
the accident in NRX. The net result in all cases except 8 and 9 is the production
of hydrogen. In the special case of 2. it would be a mixture of combustible
gases. The individual accident scenario will determine the extent to whict. the
above chemical processes involving high temperature water/steam proceed(29).
In the case of loss of coolant. the temperature of zirconium cladding of th(.
affected fuel elements can go up within a few minutes to about 1030 °c due to
decay heat. This is the temperature required for the initiation of the self sustaining
stage of the zirconium-steam reaction No.4. This exothermic process results in
the production of large amounts of hydrogen as wen as a further rise in
temperature. The consequent pressure build up coupled with a further rise in
temperature can lead to the deformation of the zirconium fuel and pressure
tubes (coolant tubes) in the reactor. The possibility of the rupture of pressure
tubes is always a real one. In such a situation. the steam-hydrogen mixture enters
the restricted volume in the reactor vault which houses important equipment. In
the absence of mixing and large containment volumes. there is a chance for a
hydroge., build-up and its possible deflagration(29). If the environment is inerted.
monitOring of hydrogen and oxygen in such restricted volumes on a continuous
basis as well as installation of catalytierecombiners a$ back up safety
featutes are expected to mitigate this risk. Hydrogen explosion was one of the
for the breach of the containment in Chernobyl-4.
Once the irradiated fuel is exposed to the hot steltm environment in an accident
situation. chemical speciation of fission products will depend upon their
interaction with steam. Thl,ls, directly or indirectly those chemical'reactions of
No.9 will strongly influence'the radioactive "Source Term".
Since chemical species in the vapour phase and their transport rates are
J08 Water Chemistry
expected to be influenced by the vapour phase composition, the presence of
hydrogen generated in an accident will have a significant impact on the chemical
speciation of fission products. Theoretical studies using estimated thermodynamic
data for the vapour species and the condensed phases enable predictions to be
made on the influence of variable vapour composition, (steam to hydrogen ratio)
on the nature of the chemical species and their relative amounts in the gas phase.
For example, it has been shown by calculations that in a hydrogen rich
environment, the major contributor to the ruthenium bearing'species is from
ruthenium gas. The total ruthenium content in vapour phase has been shown to
be maximum in a steam rich vapour. It decreases progressively with increasing
hydrogen content. Thermodynamic calculations indicate(30), the possibility of
molybdenum fractionating from the other constituents of the metallic inclusions
present in irradiated fuel. This is a function of the hydrogen to steam ratio in the
case of severe nuclear reactor accidents, such as the one at Chemobyl-4.
The above discussion clearly brings out the added importance of water and
steam chemistry vis-a-vis the special problems that are encountered in the safe
operation of nuclear power reactors.
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Power Stations. Proc. Symposium 3, CHEM TECH '80, International Congress.
Bombay, March, 1980.
2. Venkateswarlu K.S., (1981), Research and Development in Regard to Water
Chemistry and Associated Areas in Nuclear Power Stations, Proc. Topical Meeting
on Water Chemistry in Nuclear P'<Jwer Stations, pp.119-130. Committee on Steam
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1982, V-]-] to V-l-]4.
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the Influence of Water Chemistry on Fuel Fladding- Reliability, IWGFPT/ll, San
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5a. Joshi N.B., K. Nanjudeswaran and K.S. Venkateswarlu. (1984). An Overview of
Water Chemistry Experience and Crud Input Control at Tarapur Atomic Power
Station. lAEA Coordinated Research Programme Meeting on "Reactor Water
Chemistry Relevent to Coolant-Cladding Interactions, Budapest. June 1984.
6. IAEA (1987),Water chemistry specifications and their control. Reactor Water
Chemistry Relevant to Coolant-Cladding Interaction, IAEA-TECDOC-429.
PP. 15-41. International Atomic Energy Agency. Vienna.
7. Narasimhan S.V., P.C.Das. D.A.Lawrence. P.K.Mathur, and K.S.Venkateswarlu.
(1982). Indian Experience with Radionuclide Trasnport. Deposition and
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on Water Chemistry in Nuclear Power Plants, pp.193-203. IAEA, Vienna.
8. Lister D.R. (1988). Corrosion release-The Primary Process in Activity Transport.
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Water Chemistry and Material Compatibility 109
9. Garnsey R., (1988), Scientific Basis for the Choice of Primary/Secondary Water
Chemistry, Ibid., pp. 333-340.
10. Venkateswarlu K.S., (1986), Water and Steam Chemistry Under Accident Conditions
of Water Cooled Nuclear Reactors, Proc. CRP Meeting on Investigation of Fuel
Element Cladding Interaction with Water Coolant in Power Reactors, pp.70-73,
IAEA - BARC, Bombay, November 1986.
11. Venkateswaran G., (1986), Hydrogen Generation Through Zr-Steam Reaction and
Related Safety Problems Under Accident Conditions, Ibid., pp. 104-111.
12. Ramshesh V., (1986), Radiolytic Gas Generation During Normal and Accident
Situations, Ibid" pp.153- i 63.
13. Mathur P.K., (1986), Water Chemistry Control for MlDimising Activity Transport
and Radiation Field Build up Around Primary Coolant Circuits of Nuclear Power
Reactors. Ibid., pp.19-25.
14. Rodliffe R.S., M.V. Polley and E.W. Thornton, (1987), Modeling the Behaviour of
Corrosion Products in the Primary Heat Transfer Circuits of Pressurised Water
Reactors, Reactor Water Chemistry Relevant to Coolant - Cladding Interacton,
IAEA, TECDOC-429, pp.105 - 164. International Atomic energy Agency, Vienna.
15. Ishigure K., (1987). A Review of Models Describing the Behaviour of Corrosion
Products in Primary Heat Transfer Circuits of BWRs, Ibid., pp. 165-214.
16. Sundaram c.v. and H.S. Gadiyar, (1981), Material Behaviour in Nuclear Reactor
Water Systems", Proc. Topical Meeting on Water Chemistry in Nuclear Power
Stations, pp.19-67. Committee on Steam and Water Chemistry (COSWAC),
Department of Atomic Energy, India, April 1981.
17. Roy P.R., (1982), An Overview of Corrosion Problems Encountered in Reactor Core
Materials, Proc. Symposium on Corrosion and its Control in Power and Chemical
Industries, ppJ-l-1 to 1-1-21.
17a. Venkateswarlu K.S. and G.Venkateswaran, (1985), Evaluation of and Improvemf'nts
in the Performance of Zircaloy Cladding During and After its Residence in Water
Cooled Nuclear Power Reactors, IAEA Technical Committee Meeting on External
Cladding Corrosion in Water Power Reactors, CEN Cad an.' " J, France, October
1985.
18. Venkateswarlu K.S., Naik M.C., Narasimhan S.V., Paul A.R. and Venkateswaran
G., (1981), Pellet-Cladding Interactions, Res.Mechanica Le(ters I. 307-314.
19. Elek A. and K.S.Venkataswarlu, (1987), Analytical Techniques for Monitoring Water
Chemistry. Reactor Water Chemistry Relevant to Coolant-Cladding Interaction,
IAEA,TECDOC-429, pp.81-104, International Atomic Energy Agency, Vienna.
20. Lee Williams W., (1957), Chloride and Caustic Stress Corrosion of Avstenitic
Stainless Steel in Hot Water and Steam. Corrosion. 13, (August 1957), pp.67-73.
21. Cowan R.L., J.C. Eiliott, and O.H. Johanneson, (1977), BWR Coolant Oxygen
Control, NEDO-23631, June-I 977 .
22. Venkateswarlu K.S., S.V. Narasimhan, H.S. Mahal, and G. Venkateswaran, (1980),
Studies on Providing a Better Water Chemistry Environment to Minimise Stress
Corrosion Cracking in BWR Primary System Piping, IAEA Specialists Meeting on
Environmental Factors Causing Pipe Cracks and Degradition in Primary System
Components, International Atomic Energy Agency, Vienna, October 1980.
23. Cowan R.L., R.A. Head, M.E. Indig, C.P. Ruiz, and J.L. Simpson, ,(1988), US
Experience with Hydrogen Water Chemistry in BWRs, Proc. JAIF International
Conference on Water Chemistry in Nuclear Power Plants. Vol.I,pp.191-198, Japan
Atomic Industrial Forum, Tokyo, April 1988.
24. Venkateswarlu K.S., (1988), Coolant Chemistry in Press uri sed Heavy Water
Reactors: The Indian Experience, Proc. IAEA Coordinated Research Programme,
WACOLIN, Heidelberg, Germany, June 1988.
J 10 Water Chemistry
25. Narasimhan S.V. and K.S. Venkateswarlu, (1986), Modoling of Water Chemistry
Regime in the Secondary System of PHWRs, Proc. BNES Symposium on Water
Chemistry fQr Nuclear Energy Systems-4, pp.217.219, British Nuclear Enersy
Society, London.
26a. Kumbhar A., S. Rangarajan, S.V. Narasimhan, P.K. Mathur, and K.S. Venkateswarlu,
(1986), Evaluation of.Condensate Demineralisation Using Morpholine form of the
Cation Exchanger, Ibid .. pp. 363·367.
26b. Narasimhan S.V., K.S. Venkatesw!.rlu and K.S. Krishna Rao, (1988), Condensale
Polishing Under AVT (Morpholine) Situation: Performance Monitorins and
Diagnostic Techniques, Proc. JAiF International Conference on Water Chemistry
in Nuclear Power Plants, VoU, pp.1 OS· II O,Japan Atomic lndustri&l Forum, Tokyo,
April, 19GG.
27. Surya Rao V., V.V. Kothare, J. Shankar, and K.S. Venkatoswarlu, (1963), How CIR
Team Solved Corrosion Deposition Problems, Canadian Nlldear Technology.
(Winter,1963), pp.27·30.
28. Venkateswarlu K.S., R. Shankar, S. Velumurusan, O. Venkateswaran and
M. Ranganathnn Rllo (1988), Removal of AI Turbidity from Heavy Water Reactors
by Precipitation Ion Exchange Using Magnesium Hydroxido, Nuclear Technology,
82. pp.243·250.
29. Venkateswarlu K.S., V. Ramshesh, U.R.K. Rao and O. Vonkatoswaran, (1986), An
Assessment of Hydrogen Dependent Safety Issues in PHWRs". MEA Technical
Commillee Meeling or. Hydrogen Issues r,loled 10 StJj,I)' In Nue/,ar Power Plants.
Tokyo, November, 1986, International Atomic Bnergy Agency, Vienna.
30. Bhardwaj S.R. and K.S. Venkatelwarhl, (1088). Possiblo Molybderium Practionation
from Ru. Pd and Rh in Severe Reactor Accident •. Symposium on. Nuclear Reactor
Severe Accident Chemistry. North Arnerican Chemical Consros., Toronto, June
1988.
10
GEOTHERMAL POWER AND WATER CHEMISTRY
The utilisation of geothermal energy is extremely important in the quest for .
energy resources not based on fossil fuels. A wide gap, however,exists between
the availability of this energy source and the amount that is being turned into
process or space heat or electricity. The complex water chemistry of the hot
geothermal fluid, which interacts with the materials of construction of the steam
- water circuit, is a major cause for the under utililsation of this energy
The hostile working environment mars the reliability of the equipment. Since
the chemical composition of geothermal waters is site-specific, any treatment
programme cannot be generalised.
There are two broad categories of geothermal wlter-steam sources. They
are classified on the basis of thermal gradients in a volume of the earth over and
above the normal heat flow, and are given below:
(a) Hoi waler fields, in wide areas with moderately high temperature
gradients of 30 to 50°C per km depth having surface temperatures
below 100°C.
(b) fields in narrow zones, of temperature gradients of above
50°C per km depth, having surface temperatures above 100°C.
Some of the important geothermal locations in India{l) are given in
Table 10.1.
In some of the locations like Puga, although the surface tel1)perature is a
little above 80°C, in view of the height (the boiling point of water' at height.
being near about 85°C) the geothermal wells can gener'lte steam.
112
Water Chemistry
Table It.l Geothermal LocatioiDs iD IDdia(l)
Name and Highest Temp. Name and Highest Temp.
Location at surface °C Location at surface °C
Manikaran (HP) 100 Puga(J&K) 82·
Jumnotri (UP) 90 Agnigundala (AP) 80
Tapoban (UP) 89 Rajawa .. (J&K) 80
Surajkund (Bihar) 88 Chongo (J&K) 78
Sirguja (MP) 88 Duchin (J&K) 78
Khorkum (J&K) 85 Nulna (J&K) 78
10.1 GEOTHERMAL ENERGY UTILISATION
One can visualise two main types of utilisation of geothermal energy on the
above basis<2,3). One is essentially electrical energy generation using dry steam,
in a few instances, or more usually a steam water mixture. The other type is a
mixed system, wherein the hot water is used for space hot house
cultivation, supply of low process heat and recovery of chemicals like borax.
The growth of installed capacity (MWe) of geothermal power world wide
upto 1990 is given in Table 10.2.
Table 10.1 Growth orthe IDstalled Capacity (MWe) or Geothermal Power
Year MWe Year MWe
1910 0 1965 575
1916 8 1975 1290
1935 56
1980+ 3888 (1444)+
1940 250
1990+
5827 (2770)+
1955 380
1995+
8967 (3170)+
(projected)
+From "Geothermal Resources",Encyclopedia o(Physical Science &; Technology, 2nd Edition,
Vo!.7, pp 323·360, Academic press (1992). The figures (oJ: USA are given in brackets.
Italy, Japan, Mexico, New Zealand, Phillipines and USA are among the
countries that generate electricity from geothermal sources. The Geysers
geothermal field with several wells in California, is the only one in USA where
dry steam forms the dominent resource. Its combined output in 1990 was about
1770 MWe. While the projected increase in installed capacity (MWe) between
1990 to 1995 is modest in the case of Italy and Mexico, in the Phillipines it is
expected to rise sharply from about 890 MWe in 1990 tQ 2165 MWe in 1995.
10.2 CHEMICAL COMPOSITION OF GEOTHERMAL
WATERS
The dissolved solid content of geothermal waters ranges from that of ordinary
well water upto concentrated solutions as high as 40 percent by weight(4). The
principal constituent is sodium chloride. Usually potassium and calcium
chlorides are also present, though to a much lesser extent. Thus chloride is the
main anionic constituent, the next in importance being bicarbonate. Silica in
Geothermal Power and Water Chemistry
113
the form silicic acid is present in the range of 200 to 600 mgll. Some typical
compositions of geothermal fluids are given in Tables 10.3 and 10.4.
Table 10.3 Composition of Some Geothermal Fluids(8)
Location
Weitap, NZ
Otake, Japan
Broadlands, NZ
Ahuaehipan,
EI Salvador
Carro Prieto, Mexico
East Mesa, USA
Components (Appr. Wt. %)
NaCI KCI CaCI
2
H
2
Si0
3
Total
dissolved
solids (mg/I)
72
62
65
82
78
72
10
0.5
10
11
9
1.5
6
5
19
23
26
2
4
3,000
3,800
4,000
15,000
20,000
7 9 2 24,000
Raykjanes, Iceland 72 8 16 2 29,800
The total chloride and TDS vary considerably not only from region to region
but even within the region itself.
The concentration of fluoride in geothermal brines is limited by the solubility
of calcium fluoride(CaF
z
)' Fluoride is readily leached from rhyolite, but it is
leached slowly from silicified rocks. The concentrations of both fluoride and
bisulphate under saturation conditions in these fluids is inversely related to the
calcium concentration.
The pH of geothermal waters is determined by different equilibria in different
locations. Published values range from 4.9 to 9.1. The pH and the electrolytic
composition exercise a profound influence on the corrosion and material
compatibility of geothermal waters.
When geothermal water flashes to steam, a number of gases are released. A
major component is carbon dioxide, accounting for about 90 percent or more
by volume of the non-condensible gases. The other components are H
z
S,CH
4

Hz and NH
3
• In some fields, such as Lake Marvin in Iceland HzS is one of the
major components.
10.3 CORROSION AND MATERIAL COMPATIBILITY
The corrosion of equipment used in the production of power from geothermal
water or steam or for hot water distribution is generally due to the hot electrolyte
solution entained in the steam, HzS contamination and the possible presence of
oxygen(5). Usually geothermal waters are free from oxygen and as such chloride
induced stress corrosion is not problem.
However. if air gets in, as it does in many situations and if the waters are
acidic. high surface corrosion rates prevail. Stress corrosion cracking is also
possible, HzS in the steam or liquid phase causes micro cracks on the surface of
steels. Copper or cupronickels are not compatible with H
2
S. The general
corrosion characteristics of geothermal fluids are given in Table 10.5.
....
....
....
Table 10.4 Characteristics of Some Geothermal SteaDl and Water Phases(4)
Location Nature of the fluid Temp pH H
2
S CO
2
CI- HCO
l
- Sol- NH/NH
4
+
°C
(mg/l)
Ahuachapan Turbine inlet steam 156 103 2716 2.3 0.9
Separated water 156 7.0 9710 24 41
Cerro Prieto Turbine inlet steam 160 1500 14100 0.8 110
Separated water 160-180 7.7 16.0 45-74 6
Larderello Turbine inlet steam 183 630 42612 I.l 205
Separated water Steam dominated resources.
Matsukawa Turbine inlet steam 147 586 4153
Separated waier Steam dominated resources.
Condensate 25-47 4.0-5.9 57 49 2.2 4.6 3.7
Otake Turbine inlet steam 127 61 5347
Separated water 127 6.6-8.4 1385 46 148 006
Condensate 26-42 5.0-5.7 5
The Geysers Turbine inlet steam 171 222 3260 194
Separated water Steam dominated resources.
Wairakei Turbine inlet steam 101-175 36.5
1933 • 3.5 1.6
~
Separated water 101-175 8.2-8.6 2.0 21 217p 28 0.16 ~
--------- ....
n
::s-
~
~
<.:;.
~
Geothermal Power and Water Chemistry
115
Table 10.5 Corrosion Charade,ristics or Geothermal Fluids(5)
Corrosive Materials in
Type of
Phase
contact Corrosion
Liquids acidic steels Surface
Water-Steam oxygen steels
Surface
Water-Steam 02 and CI- steels
Stress
Water-Steam H
2
S steels
Stress
Steam H
2
S
Tempered steel fatigue
(turbine blades)
Condensate H
2
S and 02
steels surface
Corrosion experienced in geothermal power plants may be summarised as
follows(6): As the two phase fluid is quite erosive, (in addition to being corrosive),
carbon steel valves and elbows have a short in-service life, due to turbulence
induced erosion at these points. For steam lines, carbon steel has been found to
be satisfactory, provided air (oxygen) in-leakage is prevented. Sulphide induced
stress cracking of high strength casing in the pumps used to extract geothermal
fluids from underground have been frequent. Geothermal steam has been
observed to cause a sharp reduction in the fatigue endurance limit of turbine
blades, as compared with high pressure steam from conventional boilers. In
such cases, e..g. at The Geysers, where the steam is dry, cracking of 12 percent
Cr, steel turbine blades has been reporteq. Consequently, thicker and heavier
blades are found to be necessary. At locations where saturated steam is fed to
the turbine, blade cracking is not a problem. Use of special materials such as
carbon steel clad with SS 316 as turbine blades, showed a marked improvement.
10.4 CORROSION MONITORING
As earlier, The Geysers geothermal power plant is the largest in the
and from 1972 onwards a programme of corrosion monitoring and H
2
S
abatement was implemented. The corrosion monitoring system utilises several
techniques to determine corrosion rates and aMlyse data. The electro-chemical
method employs the linear polarization technique for r!lpid corrosion rate
determination. It measures the potential osciJIation on electrodes, with or without
crevices or pits, for the determination of passivity, pitting and crevice corrosion
suceptibility. Electro-resistence methods are also employed. Additionally pipe
and plate-tvpe "oupons are incorporated as corrosion monitors in in-plant
systems.
In The Geysers power plant(7), corrosion monitoring in the hot condensate
in three units, without measures for abatement of HlS indicated that,
<a) Stainless steels and Al alloys are only partly passive
(b) Pitting and crevice corrosion susceptibility of stainless steel is small
< c) At is susceptible to erosion-corrrosion in areas of high turbulent flow
(d) Corrosion rates are strongly dependent on condensate velocity.
Uneler the same conditions, the cold condensate imparted some susceptibility
to lItainJess steel for pitting and crevice corrosion.
10.5 THE H1S PROBLEM
For the abacement of H
2
S, at The Geysers(7), initially, direct contact condensers
116
Water Chemistry
were used where steam from the turbine exhaust was mixed directly with cooling
water, containing ferric sulphate as a catalyst, to oxidise H
2
S to elemental sulphur.
But later on the level of H
2
S in steam from new reservoirs being higher the
catalyst could not be regenerated quickly enough and the sludge caused severe
operating problems. To compound this situation, the corrosion monitoring
programme showed substantially increased corrosion rates on stainless steels
exposed to the hot condensate treated with the iron catalyst. On the other hand
aluminium alloys showed a better performance. This is indicated by data in
Table 10.6.
Table 10.6 Corrosion Studies with Reference to HzS Abatement by Iron
Catalyst(5)
Probe Condensate Corrosion rate.
in miles per year( m p y)
Without iron c a t a l ~ s t With iron catalyst
304 SS Hot 0.5 0.5 to 2.5
416 SS Hot 0.5 0.4 to 2.5
6061 Al Hot 2.8 0.1 to 0.6
3003 AI Hot 7.4 *
0.1 to 0.4
304 SS Cold 0.5 0.1
316 SS Cold 0.5 0.1
*Erosion.
To overcome the corrosion problems caused by H
2
S contamination. a new
method for its removal is now being practised at The Geysers. Unit 15 is equipped
with surface condensers using SS 304 and a Streinford system designed to acheive
more than 90 percent H
2
S remova!. In this process the non-condensible gases
are directed to a unit where H
2
S is oxidised by sodium vanadate at pH 9 to
elemental sulphur and water. The overall performance of the system has been
satisfactory.
The Electric Power Research Institute and the Department of Energy, USA
have evaluated two methods for H
2
S abatement in ali geothermal power plants.
Both depend upon an upstream removal of H
2
S. The following advantages are
expected.
(a) Turbine blade failure caused by fatigue corrosion due to H
2
S can be
controlled
(b) Turbine efficiency is increased by reducing boric acid deposits on
turbine blades.
One demonstration process uses CuS0
4
scrubbing. Efficient removal of H
2
S
dependes upon high pH. copper content, contact time and pressure. The other
process is based on condensation and re-evaporation of the steam in a single
heat exchanger. Here the non-condensible gases are seperated from the
condensate. The shell side of the heat exchanger is made of SS 304 and the
tubes are of titanium.
10.6 TURBINE STRUCTURALS
It was mentioned earlier that turbine blades exhibit fatigue corrosion in the
Geothermal Power and Water Chemistry 117
presence of H
2
S. Chrome iron (12 percent Cr) in the hardened or martensitic
state is susceptible to stress corrosion cracking in the presence of geothermal
steam. However, in its ferritic form, the alloy enjoys immunity provided that
chlorides are present in quantities less than 10 mg/l in residual water droplets of
the steam. Thus softened and tempered stainless steel is being increasingly used
for turbine blades. On the other hand, in this condition, the blades and other
surfaces are susceptible to erosion in the presence offNlt moving water droplets
in the steam. By a proper choice of the speed of the turbine blade tip, this risk is
minimised.
The internal parts of a turbine are normally resistant to attack from geothermal
steam. However, during a shut down air ingress might occur, which, in the
presence of non-condensable gases remaining in the turbine will lead to serious
corrosion. The erosion-corrosion rates at the turbine rotor and casing and nozzle
diapharm at Matsukawa. Japan ( which has acidic water and H
2
S) were computed
to be about 20 mil/y. Hence it is preferrable to purge the turbine internals with
a stream of hot nitrogen with suitable venting.
10.7 CONDENSERS
From a corrosion view point highly adverse conditions exist in the condenser
and gas extraction equipment of a geothermal turbine. Surface corrosion will be
exhibited by steels in contact with the condensate from the steam flashed i ~ the
unit, due to the presence ofH
2
S and oxygen. The inner surfaces of the condensers
are therefore' protected with a coating of epoxy resins or aluminium spray.
Austenitic steels arc recommended for use as gas extraction rotors, while 99.5
percent pure aluminium has been suggested for the inner cooler tubes. The latter
material is said to be r.liltant to geothermal steam except at high temperatures.
Surface corrosion rates reported for several candidate materials for the
condenser tubes are shown in Table 10.7.
Table 10.7 Sureace Corrosion rates (MIBlYear) of Materials in Contact with
Geotbermal Fluids(8)
Geothermal Tllnp. Cu& Ni& Carbon Ferretic Austenitic
fluid °C alloys Monel Steel Steel Steel
Condenste 70 0.2-5 0.4'-4 3-4 0.1 0.1
Aerated steam 100 10-40 8·10 18-20 0
Well head 125 0.3-10 1 0.3-0.5 0.1 0
flushed water
Well head 100 0.3-4 1·4
0.3-6 0.3 0
flushed steam to 200
It is evident that the condenser tubes cannot be of Cu or Ni alloys, as in
many fossil fuel fired power plants.
At this point. it IS appropriate to mention that in addition to the problems of
corrosion, th..: utilisation of geothermal waters will also lead to a lot of scaling
and deposition on surfaces. This is specially so when wet steam under a pressure
ofS kg/cm2 (100 psig) in the temperature range of 175 to 315
0
C is made use of.
The scale formation affects e v ~ r y aspect of the plant from the production
118 Waler Chemistry
reservoir to the reinjection system. The rate f)f scale build up and corrosion
inside the steam turbines used in flash cycles is not generally known. Extensive
field testing is require.d. In many cases, scaling is only due to calcium carbonate
and silica. It may become necessary to clean up the deposits on turbine blades
and valves. The Salton Sea (USA) geothermal waters have an average of2,50,000
mg/l of dissolved solids, making them very prone to scaling. A set of pressure-
volume - temperature - composition - energy data is required for predicting the
conditions of minimum scaling and optimum operating conditions,including
reinjection of the spent fluids. The data for NaCl - H
2
0 analysed by the
International Association for the Properities of Steam will serve as a model in
this context. As regards prevention of scaling, lowering of the pH to 3.0 reduces
the polymerisation of silica and supresses the precipitation of CaC0
3
and metal
sulphides. Use of organic polymers as antiscaling agents is being tried out.
Another approach is to 'sludge scaling', in which finely divided silica is added
to the geothermal fluid to promote silica precipitation. This would, however,
require the handling of high levels of suspended solids.
When the geothermal water temperature is not much above 100°C, it is
impractical to produce steam by flashing. In such cases, a binary cycle is proposed
wherein the geothermal water circulating through a heat of exchanger,transfers
energy to an organic liquid with a low boiling point like isobutane. The vapour
pressure of gaseous isobutane so generated will be enough to drive a turbine
and can later be condensed by surface water, with a cooling tower. Recent studies
report the use of a direct contact heat exchanger to overcome scaling problems
due to the high salt content of geothermal waters. This type of approach through
a binary cycle, completely eliminates the problem of corrosion in turbines.
10.S DIRECT USE OF GEOTHERMAL WATERS
At temperatures lower than 100°C at the well head, geothermal waters are not
suitable for electricity generation, but can be used for space and process heating.
In India, this will probably be the main application sinee, well head temperatures
are less than the boiling point of water.
The materials to be used in the heat transport system in such cases could be
the same as at Klamath Falls, USA. Here the Iburied supply pipe is of carbon
steel. Fan coil units are conventional copper tube units with aluminium fins.
Heat exchangers are of the shell and tube variety using carbon steel shell and
copper tubes. Operational experience shows t\1at copper fan coils and tubes
give good services in low chloride neutral pH waters free of oxygen. Nevertheless
problems arose because of CO
2
and H
2
S content. CO
2
apparently produced
dezincification of even low zinc brasses in high velocity regions. Experience at
Klal'1ath Falls indicated that when H
2
S is greater than 0.1 mg/l, the low
temperature geothermal water produces excessive scaling on copper tubes
leading to under deposit attack.
It is evident ffom the information presented in this chapter, that in the
utilisation of geothermal water/steam resources for the generation of electricity
or process heat, the problems due to water and saturated steam chemistry are
more severe than inlfossil fuel fired plants, because the working fluid is
contam,inated to a high degree with gases and dissolved solids<8l.
Geothermal Power and Water Chemistry
119
REFERENCES
1. NCST ( I 9 7 ~ ) . Geothermal Energy Utilisation, National Committee on Science &
Technology. New Delhi. India.
2; Wahl E.E. (1977). Geothermal Energy Utilisation. John Wiley. New York. 1977 .
3. ArrTlstead H.C.H .. (1978). Geothermal Energy. E & EN. Spon Ltd .• 1978.
4. Ellis II P.E and D.M. Anlikcr. (1982). Geothermal Power Plant Corrosion Experience
- A Global Survey. Materials Performance, February 1982. 9-16.
5. Pruce L.M., (1980). Corrosion Problems Come into Focus as Interest in Geothermal
Energy Grows. Power, July 1980.84-87.
6. Cartee J.P. and S. Cramer. (1980). Field Corrosion Tests in Brine Environments of
the Salton Sea Geothermal Resource Area. Materials Performance, September 1980.
7. Rank I.A. and G. Kekuksa. (1976). CQrrosion Monitoring in the Cooling System
of the Geysers Geothermal Plant. Materials Perforn.ance. July 1976.
8. Venkateswarlu K.S .• (1981). Corrosion and Material Comratibility Problems in the
Utilisation of Geothermal Energy. All India Conference on Corrosion Control.
Institute of Energy Management. Bombay. March 1981, H-I to H-9.
11
ANALYTICAL TECHNIQUES FOR WATER
CHEMISTRY MONITORING AND CONTROL
11.1 WATER AND STEAM CHEMISTRY MONITORING
An effective programme of water the steam chemistry monitoring as the basis
for exercising the necessary chemical control requires. reliable sampling. good·
laboratory facilities, a dedicated Chemistry Task Force and on-line analysers
with low maintenance problems(l).
United States surveys showed that while more data on the chemical quality
of steam and water are required at more frequent intervals. the power plants are
deficient to the extent that,
(a) One or more of the important on-line analysers do not exist in a
majority of stations.
(b) Effectiveness of most of the on-line analysers is compromised by crud
deposition in the sampling lines/nozzles and
(c) A significant fraction of the analysers are not in use.
For prevention or minimising the corrosion in the steam water circuits of a
power plant. the major chemical parameters which one monitors. preferably by
on-line instrumentation are conductivity. pH. dissolved oxygen. sodium, chloride
and silica. In order to evalute the steam chemistry. it is desirable that direct
sampling and continuous instrumental analysIs of the steam samples from
predetermined turbine extraction stages be adopted. Since steam is under high
pressure and at a high temperature. pressure reducers and sample coolers form
part of steam analysis instrumentation(l).
Chemical specifications are maintained by anatysing samples from various
points in the system, and by dosing appropriate amounts of various chemicals.
The manual method of taking samples. obtaining bL ratory an>tlyses and
Water Chemistry Monitoring and Control 121
adjusting chemical addition rates in order to correct deviations from the
specifications is probably satisfactory for steady state operation of earlier designs.
However, it is unlikely that any reasonable sampling frequency could keep
specifications to within limits during transient operation or during periods of
condenser leakage. For modern units, the most reliable means of achieving an
efficient control is by a completely automated chemical sampling, analysis and
addition scheme. This calls for a sophisticated design of the entire chemical
control system and more importantly reliable maintenance(3,4).
In this chapter, analytical methods in the laboratory based on chemical and
instrumental techniques as well as on-line monitoring for different chemical
parameters are described. Water chemistry monitoring in a power plant might
involve as many as 25 source points from which either the samples are drawn on
the spot or sampling lines routed to a central sampling station. Reliable and
reproducible sample collection is an essential condition. In case of long sample
lines leading to a sampling station, adequate flow ensures that the chance of a
blockage is minimised. Sample nozzles must be kept clean and they will have to
extend within the flow-line in an inward direction, so that the bulk fluid is sampled.
One should always bear in mind that external factors such as dust, humidity and
temperature might interfere with the caliberation exercise. A two phase system
like that of saturated steam poses difficulties in terms of sampling (as opposed
to sample) reproducibility. On the other hand, with single phase fluids such as
feed and boiler water (i.e. boiler blowdown) condensate and superheated
steam,this doubt on sampling integrity is absent. The problem of sampling
superheated steam at the turbine in-let is very exacting and the stearn purity so
monitored will be the reference point for any other chemical control. There is
scope for improvement in sampling of superhead steam.
A very reliable indicator of water purity is its conductivity. The lowest
theoriticallimit of specific conductivity for water is about 0.05 J.1s/cm at 25°C
Taking this as a reference, the quality of water in different sections of the power
plant can be judged. It is best to cool the sample to 25 ± 0.2°C. Very good on-
line instrumentation is available and it is becoming a standard practice to install
a number of conductivity probes specially in the hotwell section so that early
warning of condenser tube leakage is available in the control room. As mentioned
in Chapter 6 specific conductivity measurements are also made use of in
monitoring the performance of OM plants. The basic principle involves the
generation of a current when an AC voltage is impressed upon two electrodes
immersed in the cqueous test solutions. The current is measured by an AC bridge.
In the conductivity meters, the signal is amplified and measured on the scale in
terms of specific conductivity values. The cell constant of the electrode cell is
very important and depending upon the range of specific conductivity to be
measured,. cells with an appropriate cell constant are used. The measurement
also has to be compensated for the temperature of the sample, electronically
and all conductivity measurements are reported at 25°C. Modern instrumentation
measures conductivity automatically with temperature compensation. The
cleanliness of the conductivity cell, specially the electrode surfaces is very
important. In addition to measuring the specific conductivity, one also measures
"Cation Conductivity" wherein all the cations in the sample are removed by
122
Water Chemistry
passing it through a H+ form of the cation exchanger. If the sample is degassed
(free from COz) after it is put through the cation exchanger, it is called "Degassed
Cation Conductivity".
Another important instrumental measurement is the alkalinity of the boiler
water, for which pH monitoring is essential. It is a less reliable parameter for
high purity feed water as compared to specific conductivity. On-line
instrumentation gives the pH indication in the control room. In several power
stations it has been noticed that pH, as measured in the laboratory is different
from on-line measurements. This is possibly due to poor response of the on-line
electrodes, and COz ingress in laboratory measurements. The cleanliness of the
on-line as well as the laboratory electrode surface is an important parameter in
this context. Of the various reference electrodes and junctions available for
continuous monitoring, calomel (HgzClz)or silver-silver chloride (Ag-AgCI)
electrodes with fritjunction and lID saturated KCI reference solutions give good
results. Ion selective electrodes, sensitive to H+ can also be made use of for pH
measurements. As with specific conductivity measurement, temperature
compensation is a must; special precautions recommended include low sample
flow, electrode arrangement in parallel pairs and special electrode construction
to minimise streaming potentials.
It is desirable to know the sodium level in feed water. Sodium limits in steam
have been revised to values as low as 3 J1g/l. In fact, the Central Electricity
Generating Board, UK envisages the determination of the Na balance in the
entire water steam cycle. On-line sodium analysers are available in the market.
At sea water cooled power stations such on-line probes, installed in the condenser
hot well will suppliment the conductivity instrumentation in detecting the
condenser tube leak at a very early stage. On-line sodium analysers are in service
in the Madras Atomic Power Station. The sodium ion specific electrode is capable
of detecting 0.05 J1g/l of Na. Commercial instruments having working range
from 0.1 to 1000 J1gn are available.
Equally important is the chloride content of feed water, especially in boning
water nuclear power reactors. Hence a BWR power station laboratory has to
analyse a comparatively larger number of samples for chloride than in other
stations. Recourse has been taken to make measurements with chloride ion
specific electrodes. Not only liquid junction but also solid state ion specific
electrodes are in use for the determination of chloride. On-line instrumentation
is also employed, though it is some what less reliable than conductivity
measurement.
Chloride can also be determined in the laboratory, using Hgl+ - Fe)+ - eNS'
procedure. MIS Bharat Heavy Electricals Ltd ( R&D Unit), India has developed
a PVC coated wire electrode containing red HgS - HglCl
z
as the sensor with
Hg - HgS04 as the reference electrode. With this system, it is possible to measure
chloride at level of as low as 5 J1g/l, 1 in a flowing sample. Lower concentration
level measurements are possible in combination with an ion chromatograph.
One of the alkaline conditioning agents used in boilers is ammonium
hydroxide. Once-through boiler operators only make use of this reagent. In
view of the volatility of ammonium chloride, one opinion is that the presenCt' of
Wilter Chemistry Monitoring and Control 123
chloride in steam, in such a situation, is due to the added ammonia. Hence,
thero is a speicific need to monitor this additive in different sections of the
water and steam cycle. On-line ammonia analysers are becoming usefuI.One
such analyser is based on a probe which responds to the partial pressure of
ammonia across a gas permeable membran,. The resultant pH change in the
probe develops a potential which can be measured and used for judging the
partial pressure of ammonia.
aased on electrochemical techniques, on-line instrumentation has been
developed for the measurement of dissolved oxygen. Several such instruments'
are available in the market. These are based on the development of a potential
or I current directly proportional to oxygen concentration in water. Silver or
platinum serves as the cathode material, while lead is used as the anode. The
electrodes are seperated by an oxygen permeable membrane. The oxygen
dllS()lved in the sample diffuses through the membrane, 'thus creating a potential
c>r C\llTent in proportion to its concentration. This i ~ amplified and measured.
The electrode reactions are:
At the cathode :
At the anode
Oa + 2H
2
0 + 4e- -+ 40H-
Pb + 40H- -+ PbO
a
?" 2H
2
0 + 4e-
(11.1)
(J 1.2)
The minimum detectable limit is 0.001 mg/l. The Coulometric method can
allo be adopted as an on-line technique. However the limit of detection ill
0.00$ msll. Another method of determining dissolved oxygen is by its fast
"aotion with metallic thallium (TI). ,This results in the formation of soluble
nOH. The specific conductivity of this solution is directly related to dissolved
oxy,on in high purity water. In the laboratory, the well established Winkler's
test procedure, using colorimetry with 5 cm absorpotion cells will lead to a
detectable limit of 0.005 mg/I. An oxygen analyser should find a place in the
main condenser area at the discharge of the condensate pump.
Another important constituent which must bel monito:ed is silica. As seen
oarlier, the distribution of silica between water and steam phase depends upon
the temperatures and pressures of the two phases. Since 'Silica from steam has a
tendency to deposit on turbine blades, very strict limits are imposed on silica
levels in high pressure steam. In addition, the silica level of the DM water from
the mixed bed is an important guide in assessing the performance of the anion
exchange resins. On-line analysers for silica are now commercially available. It
mllY be mentioned that MIS BHEL (R & D Unit) have developed and introduced
lnto eIle market a combined on-line analyser for chloride, silica and copper.
In the laboratory, colloidal or 'non-reactive" silica is monitored by the use
of a turbidimeter based on the principle of light scattering. To measure reactive
silica a number of we't chemical methods are available. The colorimetric
procedure recommended by AS ME that depends upon the formation of the blue
heteropoly silicomolybdate can be used to measure silica upto 20 J,lg/l, if 10 cm
cells aro uscd. Since most of the power station laboratories have 1 cm cells, it is
Ildvised to concentrate the blue colour by extracting it into a small quantity of
an organic mixture (cyclohexanol and amyl alcohol in the volume ratio of 1 :9)
containing 0.2 M Aliquat 336. Through this additional step, concentrations
124 Water Chemistry
of silica lower than 10 J.lg/l can be measured even with 1 em cells.
In both steam and feed water. copper has been specified to be kept at very
low levels (2 and 10 J.lglJ). The extractive photometric determination using
Neocupron reagent can detect a level of 20 J.lgn with 1 cm cells. Use of 10 cm
cells or alternatively a copper ion selective electrode gives a level of
1 J.lg/l under ideal conditions.
Other instruments useful in a power station laboratory are the flame
photometer and atomic absorption spectrophotometer. Ion chromatograph is
proving to be a very useful addition to the range of equipment.
11.2 AUTOMATED CHEMISTRY MONITORING AND
CONTROL
On-lint: chemical instrumentation can be integrated into an automated system
for chemical monitoring and control. For steam generators making use of nuclear
heat. the main requirements of such a system are
(a) An ability to control the chemistry in the All Volatile Treatment (AVT)
mode for long periods.
(b) Reliable detection of condenser leaks and if the leak is large enough.
initiation of automatic control of the boiler water chemistry by using
phosphate treatment in case of recirculating drum type units and
(c) An ability to log data and provide the chemist with a summary of
post incident steam generator conditions at regular intervals or to
diagnose the system chemistry behaviour.
For meeting the above needs. modern power station designs incorporate a
dedicated mini computer as the basic component(5). Chemical analysis
information is fed to it by commercial on-line analysers located at strategic
points in the steam/water circuit. Acting on information from these analysers.
the computer actuates valves which control the additiol1 of appropriate chemicals
at the correct dosing points. For example. operation of the phosphate system is
such that the automatic addition of phosphate to the boiler will begin when a
condenser cooling sea water leak is confirmed by a signal from the sodium
analysers. The computer controls the phosphate addition by feed back
information supplied by on-line analysers measuring the phosphate concentration
and pH of the composite boiler blowdown. In addition to initiating stipulated
chemical dosing. the computer has to log and display data from all on-line
analysers. interpret.give alarms and execute preventive action to correct off-
normal trends in water chemistry.
For the instrumental and automated chemical control system. using a
computer to operate satisfactorily. a number of on-line analysers and probes
are needed. These are in addition to the ones described earlier. viz.,hydrazine
analyser amd a phosphate analyser(S).
The computer should be dedicated and possess the following functional
abilities:
Waler Chemistry Monitoring and Control
125
(a) Acquisition of data from all the chemical analysers on the secondary
side
(b) Automatic calibration of the analysers for ensuring accurate
measurements and to detect instrument malfunction,
(c) Monitoring for all the system's alarm devices for diagnostic purposes
these include temperature and flow indicators on analyser feed lines,
flow switches on chemical dosing tanks and other pertinent indicators
associated with the steam generator
(d) Detection of a condenser leak via the sodium ion analysers
( e) The starting and maintenance of phosphate treatment upon the
detection of a significant condenser leak
(f) Storage and organization of a twenty four hour history of the analyser
date and the sections ofthe.controller for display on the CRT screen
in a numeric or plotted form; a printed copy unit for selecte1 permanent
paper recor?s is also desirable and
(g) Direct digital control of the hydrazine and pH Control loops, if desired.
Two sodium ion analysers are required to be installed for the purpose of
rapidly detecting condenser cooling water leakage. One signal per minute from
both instruments could be sent to the computer where the following logic
sequence is enacted:
(a) Temperature and flow rate of the sample to each instrument is checked
(b) If the temperature and flow rate of the sample to the analyser are within
specification limits,the data from the analyser are examined to determine,
if an abnormally high level of sodium exists in the condensate,
(c) An affirmative answer by one or both analysers initiates automatic
instrument calibration and
(d) If water calibration, both analysers reconfirm the high sodium level
and temperature and flow rate of the sample to each are acceptable, a
leak is declared detected and phosphate addition begins
The process of the above logic sequence for positive detection of condenser
leak takes about 10 minutes.
11.3 SAMPLE CONDITIONING PHILOSOPHY
Analysers based on electrochemical principles, such as those for measuring pH,
conductivity, dissolved oxygen and hydrazine can provide adequate accuracy
only if the sample is maintained at a constant temperature. For this purpose it is
recommended that each sample is cooled to a constant temperature (20
0
C or
2S°C).
For an efficient chemical control,it is essential that the sample flow to the
analysers is always maintained. To make the computer aware of any discrepancy in
this respect, Chromel-Alumel thermocouples and flow indicator tramsmitters are
needed to be installed ahead of each analyser. Abnormal signals from them will
alert the computer to the doubtful integrity of the signal from the associated analyser.
126
Water Chemistry
In conclusion, it can be said that on-line monitoring of chemical parameters
and their automatic contjol through a computer. will go a long way in providing
reliable operation of the high temperature and high pressure steam generating
system. whether in the fossil fuel fired or nuclear heated sesments of the electric
power industry.
,UlfEReNCeS
1. Venkatcsswarlu K.S., (198\), Water lind Steam Quality, for Mllintenance of
Oeneration Efficiency, Proc. All India Canference on Water Chemistry for Industrial
and Thermal Power Slatio"s Boile,s, 0.\/1 to 0-1111. Indian Institute oi Plant
Engineers. New Delhi.
2. Venkateswarlu K.S .• (1982). Feed Water Quality Control for Fossil Fuel Fired and
Nuclear Boilers. Proc. Seminar of Instrumenl Society of America (Bombay Chapter). "
JNTEQ. 6-13. Nov.1911l.
3. Strauss S.D .• (1988). Water Treatment Control and Instrumentation. Power (Special
$e13tion) May 198B. W.1610 W.30.
4. Jonas 0 .• (1989), Developing Steam Purity Limits for Industrial Turbines. Power.
May 1989.78-83. .
5. Venkateswarlu K.S .• (1988). Chemical Instrumentation Needs of Modern Steam
Oener/lting System. Chemical Busi",ss. 24-26. June 1988.
12
DESALINATION, EFFLUENT TREATMENT AND
WATER CONSERVATION
The availability of clean drinking water is still a major problem not only in
the semi-arid and desert regions of the world, but also in both rural and urban
areas of the developing countries. However, the science of water purification,
to make it fit for drinking, has made great strides during the last 30 years. Among
these new technologies, Reverse Osmosis (RO) stands out as the one that gained
wide acceptance and appIication(l). S.Sourirajan, who along with his colleagues
has pioneered this technique, has this to say about Reverse Osmosis ... In the
context of water scarcity in many parts of world and public concern on the
quality of our environment, the effective utilisation of RO for the water treatment
problem alone would make the social relevance of RO. second to none". In
addition , RO finds wide ranging application in waste water treatment and
consequential abatement of pollution and water reuse(l,l). The Technology
Missison on Drinking Water launched by the Government of India has RO as one of
the metbods for providing clean and safe drinking water in rural India. Removing
the dissolved salts from brackish or seawater to make the water acceptable for
drinking is popularly known as Desalination. The standards for drinking water u!>
set by the World Health Organisation are detailed in Chapter 2.
Examples of Osmosis, are the passage of water through cell walls, uptake of
soil moisture by the roots of a plant etc. Osmosis is the process whereby, when
two having different concentrations of an electrolyte (such as NaCl)
are seperated by a semi-permeable membrane. pure water from the solution
having lower concentration of the electrolyte flows across the membrane
into the one at higher concentration. This continues untill the concentration of
the dissolved solute on both sides becomes equal. This flow or diffusion of
water basically due to the difference in the [otal solvation energy on either
side of the membrane and the flow will result in the equalisation of energy on
128 Water Chemistry
both sides. Since there is a flow in one direction, it would be appropriate to
relate it in terms of a pressure and this is called the osmotic pressure. This
phenomenon can be easily demonstrated in the laboratory. It is also dependent
upon temperature, since basically energy terms are involved.
As the name implies Reverse Osmosis (RO), is the opposite of this process. By
exerting hydrostatic pressure on the side of the solution :laving a high
of electrolytes, the flow due to osmosis is at first stopped and then reversed at a
higher pressure. Thus it is possible to transfer pure water from a salt solution, like
seawater, across a membrane by application of the required pressure. The translation
of this principle to large scale application is what makes RO so attractive to
desalination and effiuent treatment. The required technology has been well developed
during the last 25 years(4). .
As an approximation, it is noted that the osmotic pressure of a solution having
1000 mg/l of dissolved salts (NaCI etc.) is about 0.7 kg/cm
2
(1 Opsi). Since seawater
has a TDS of about 35,000 mg/l, one can say its osmotic pressure is of the order of
25 kg/cm
2
(350 psi). for the desalination of sea water, a pressure in
excess of25 kg/cm
2
has to be applied in order to over come its osmotic pressure
and start giving a reverse flow of desalinated water across the membrane. This flow
will increase with an increasing positive difference between the applied pressure on
the sea water side and 25 kg/cm2.
The expression governing the flux of water (W
F
) across the membrane is given
by,
W
F
= KA (1lP- Lill)
t
In the above equation,
W
F
Water flux through the membrane,
IlP Differential of the applied pressure, (kg/cm
2
)
Lill Differential of the osmotic pressure, (kg/cm
2
)
A Membrane area {in sq. cm),
t Membrane thickness (in microns),
K Membrane constant.
(12.1)
If one wants to increase W
F
, A andlor (1lP - an) have to be increased, while t
has to be decreased. These factors have to be optimised to suit the electrolyte
concentrations in the water resource, as well as the quantum of drinking water
needed per day. The effect of temperature is not noted in the above expression.
RO membranes are sensitive to temperature, while the viscosity of water
decreases with increase in temperature. These two are opposing effects. Thus
at higher temperatures, the membrane performance deterioates while the water
flux across membrane increases. Again onO; has to optimise.
In an ideal situation, only pure water gets transferred across the membrane.
But in reality, a small part of the electrolytes also get transported. To quantify,
one uses a term, 'Rejection Level', which indicates the amount of electrolyte
left behind in terms of a percentage. Thus, the Rejection Levels of monovalent
cations and anions (e.g., sodium, potassium, chloride, fluoride) are about 90-92
percent while those of divalent ions (Ca, Mg, Sulphate) are about 93-95
Desalination. Effluent Treatment and Water Conservation
129
percent. Most of the membrane have pore sizes around 5 Angstrom units and
thickness of about 100 microns.
The earlier type of membranes had a tight but thin surface layer backed up
by a thick porous substrate. These are known as asymmetric membranes. The
rejection of electrolytes occurs at the thin surface layer and the porous layer
acts only as a support. Subsequently thin film composite membranes have been
developed and these have helped in reducing the operating pressure. The
membranes have been made use of in several geometrical configurations,
prominent among them being tubular, spiral wound and hollow fibres. Of these,
the later two configurations have found wide application in the water industry.
The output of the tubular configuration, which is also bulky, is on the lower
side as compared to the other two geometries.
One can conceive the spiral wound geometry as a rolled sandwich. A sheet
material that acts as a water carrier is sandwiched between two membrane layers.
The three layers are then wound cylindrically over a plastic tube through which
the purified water flows out. The plastic tube has perforations on it to allow
this to happen. The sandwich layers are seperated by a plastic netting. The
membrane configuration is placed in a suitable pressure vessel (cylindrical)
made of stainless steel or fibre reinforced plastic. The feed water flows from
one end of the pressure vessel to the other and the product (purified water)
comes out of the plastic tube along the central axis of the membrane
configuration. A good surface to volume ratio is available and is not affected
by suspended solids or turbulance.
Another popular configuration is known as the 'HoJ]ow fibre'. As the name
implies, extremely thin strands of a hollow membrane, are packed in a U shape
in a cylindrical pressure vessel. This configuration bears a close resemblence
to nuclear steam generators with a U shape bundle of tubes fixed in a cylindrical
vessel. (It may be recalled that the hot primary coolant flows through the U
tubes and steam is generated on the shell side). In the hollow fibre RO Unit, the
feed water flows around them, while the product water comes out of the fibres.
Here again, an excellent ratio of surface to volume is acheived, but the
configuration is susceptible to fouling by suspended solids.
While RO is a physical process, water chemistry comes in because of the
feed water (raw water). As we saw in the beginning, raw water contains all
sorts of impurities and some of these affect the efficiency of RO. It is self-
evident that with RO pore sizes in the range of 5 - 10 Angstrom units, suspended
material is a serious threat. Suspended solids have to be removed from raw
water to the maximum possible extent. In addition to normal clarifying and
filtration procedures, the use of a fine 5 micron catridge filter, just before the
water enters the RO unit is being advocated. On the chemistry side, calcium
salts (bicarbonate and sulphate) pose a serious scaling threat. It was noted earlier
that for both calcium and sulphate, the rejection level is very high, being 95
percent, so that they concentrate quickly in the feed side of RO unit. Once the
saturation solubility is exceeded, calcium sulphate precipitates out. The counter
treatment procedures are essentially the same as discussed under cooling water
treatment. To prevent the precipitation of calcium sulphate, the water is dosed
130 Water Chemllt1'Jl
with sodium hexa metaphosphate, while the scaling of calcium bicarbonate il
prevented by keeping the Langlier Index in the negative range (acid dosing).
Iron and manganese present in raw water have a tendency to get partially oxidised
at neutral pH values and the oxidised forms, Fe (III) and Mn (III) might hydrolyse
and precipitate. The acid dosing referred to above will bl;; able to overcome this
problem.
It is pertinent to point out that the type of chemical treatment noted above is for
industrial water (either directiy used or fed to a OM plant for further purification).
For domestic consumption, the residual chemicals must conform to the tolerances
prescribed by WHO for drinking water. Product 4nalysis, before public distribution
is therefore an important requirement when RO is used for rural water supply. This
would call for the establislunent oflocal chemical testing facilities, based on simple
procedures.
The membranes are also subject to biofouling. Once again chlorination ofraw
water is the only remedy. However, the residual chlorine needs to be removed before
the raw water enters the RO unit, as otherwise the membrane will get damaged by
chlorine interaction. In this respect cellulose acetate membranes are somewhat better
than the polyamide type. On the other hand cellulose acetate membranes are
suscetidble to hydrolysis, but this is prevented by acid dosing that is done for other
reasons mentioned above.
As noted earlier the membrane performance is affected by temperature. While
the water flux across, the membrane increases with temperature, the membranes
deteriorate much quicker. RO operates best at 2S
o
C. One can eui,ly see
the limitation it imposes in arid zon:s, where the daily as well as seasonal
fluctuations in temperature are wide.
Economies dictate the utility of a RO unit. when it is coupled to a
demineralisation plant for producing high purity water. It is obvious that the
capital cost will increase when RO is added. it has been shown that
operating costs, particularly in terms of the savings effected on regenerant
chemicals is such that a break even point can be realised. From a chemical point
,of view, this break even point is reached when the TOS in the raw water is
as CaC0
3
.With marked improvements in membrane performance
and technology, this break even point has been reduced to 1100 mg/l expressed
as CaC0
3
. One should bear in mind, not only the cost of regene18nt chemicals
used in the OM, but also In conclusion it can be inferred that RO
offers an attractive route for rural water supply and it is also an attractive
precourser to a full scale OM plant.
12.1 EFFLUENT TREATMENT AND \VATER
CONSERVATION
In view of the very large volumes of water employed by industry, it is but natural
that attention is paid to two aspects at the back end of any process using such
water. Since water is a precio.us resource, the priority is to conserve it. Another
aspect is the treatment to be applied to a shearn of industrial effluent or waste
Desalinarion, Effluent Treatment and Water Conservation 131
water, with due regard to pollution control, before it is discharged into the
environment. Apart from legal requirements on the effluent discharges, it is
unethical to discharge such waste water which an unsuspecting public might
come into contact with and some times even make use of it, leading to hazardous
consequences. Thus industrial effluent or waste water discharge into the
environment is as much of a moral issue as one of law and chemistry. The best
way is to reclaim as much water as possible even though it may not be of the same
quality as the input, for reuse.
Unlike the similarities in the quality of water needed by industry, specially
the core industries like power, fertilisers and steel, the effluents generated by an
industry are specific to it . As such universally applicable effluent treatment
procedures are not avaiable. General techniques such as precipitation, filtration,
ion exchange, reverse osmosis and even distillation are made use of to meet the
treatment requirements, before the waste water is either discharged into the
environment or reused. The tolerance limits of some of the parameters set by the
Indian Standards (IS :2490,Part 1,1981), for the discharges to the environment
are given in Table 12.1 (5).
Table 12.1 Tolerence Limits for Discharge as per Indian Standards
(IS: 2490, parI I, 1981)
Constituent! Effluent to
earameters Surface Public sewer
Suspended solids mg/l 100 600 200
Dissolved solids mg/l 2100
2100 2100
pH
5.5 - 9.0 6.5 - 9.C. 5.5
Chloride mg/l
1000 1000 600
Sulphate mg/l
1000 1000 1000
Zinc mg/l 5 IS
Lead mg/l 0.1 1
Mercury mg/l 0.01 0.01
Ammonical nitrogen 50 50
BOD 30 350
]00
Oil & grease mg/l 10 20
]0
Temeerature °c 40 45
As mentioned in the begining, large volumes of water are used by industry.
The water requirements of some of these, without recycling or are given in
Table 12.2(5,6). In the power generation sector, a 210 MW unit consisting of a
drum (normal level) with water wall boiler tubes, econcmiser, superheater and
reheater have a water holding capacity of about 320 cubic meters. The full steam
water circuit will, of course have a much greater holding capacity.
It has been estimated that in the production of industrial alcohol, viscose
rayon, pulp and paper and steel, as much as 50-60 percent of the water can be
recovered and recycled.
In this section, Ii few illustrative examples of effluent treatment in some
132
Water Chemistry
industries are reviewed.
Table 12.2 Water Requirements for Industrial Operations(5,6)
Industry
Fertilisers (Ammonia)
a) Gas based
b) Naphtha based
c) Fuel 011 based
d) Coal based
Fertilisers (Urea)
Petrochemicals (Gasoline)
Cement by wet process
Chrome leather
industrial alcohol
Cubic meters of water used
per ton of the product
10
17
24
69
6
25
12
32
65
Viscose rayon 160
Pulp and paper 275
Integrated steel plants 150 - 300
It is important to realise, that in power stations, either thermal or nuclear,
water is recirculated to a very extent. If cooling towers are employed for
condenser cooling, there will be some loss of water due to evaporation. On the
other hand, when river, lake or sea water is used for this p':rpose, it is directly
discharged in·to a large water body after passing through the condenser. The
waste water in power stations could be the boiler blowdown and the cooling
tower basin (if it exists) blowdown waters. Simple treatment will make these
volumes of water environmentally safe and reusable. For example,the blowdown
from boiling water reactors, is purified of its radioactive constituents present at
a low level. by ion exchange and effluent is or discharged into the
aqueous environment. The effluents that really need a treatment in a power
station are the acidic arid alkaline regenerative waste streams coming out of the
demineralisation plants. Use of sulphuric acid in place of hydrochloric acid,
generally reduces the effluent load. Neutralisation and dilution ponds are available
adjacent to the DM plant and usually a treated and neutral effluent water is
discharged into the environment. Water conservation is best seen in nuclear
power reactors using heavy water as the moderator and coolant. Special
instrumentation is available to detect heavy water spill!> and recovery systems
from the ambient atmosphere are installed to recover as much of it as possible.
Afler upgrading, the heavy water is reused. In all nuclear power stations,effulent
trealment is one of the important activities, in view of the need for discharging
"as Iowa radioactivity" as possible (ALARA criterion). Reverse Osmosis is
fInding increasing application in such situations.
In modern fertiliser plants, an integrated approach is adopted for effluent
treatment, water conservation and its reuse. The utilisation of chalk which is a
b) product of the ammonium sulphate production process by Gujarat State
Fertiliser ':orporation
4
India is a good example(7). A slurry of chalk fills a pond
Desalination. Effluent Treatment and Water Conservation 133
known as the chalk pond. The water from this pond is utilised in the phosphoric
acid plant for fume scrubbing (which makes it acidic), cooling condensers anc
other odd jobs. The acidulated effluent is returned to the chalk pond. On the
other hand, ammoniacal effluents from ammonia and urea plants are also fed to
the chalk pond. Thus the chalk pond serves simulataneously as a neutralisation
facility for both acidic and alkaline effluents by using a by product, and functions
as a mediunl for water cycling. Even in making the chalk slurry, contaminated
process condensate from an ammonium sulphate plant is used. Of course, this
would mean that chalk pond water might con tam 1.5 to 2 percent of ammonium
sulphate. By making use ofthis m a phosphoric acid plant, the mineral value could
be recovered in the form of diammonium phosphate.
In some plants ammonia and urea bearing effulents are mixed and subjected
to thermal hydrolysis at 200°C under pressure with steam. The ammonia and
carbon dioxide generated are stripped and recycled, while the treated effluent
could be used as make up to the cooling tower. In the steam reformers, where
naphtha is cracked, the water coming out of the units contains fine carbon particles.
These are collected,by using a drum filter and the water is reused.
One of the largest consumers of water per ton of the product is the steel
industry, wherein it is used for coke making, scrubbing of blast furnace gases,
steel making, rolling etc., in addition to power generation in its captive plant(8).
To save on fresh water, saline water is also used (in part) at shore based steel
plants. The average percentage distribution of water usage at a shore based plant
is given in Table 12.3.
Table 12.3 Water Consumption in a
Shore Based Steel Plant(8)
Process % of the total Distribution as percent
Fresh water Sea water
Power generation 47.8 10.3 37.5
Blast furnace 14.9 7.1 7.8
Rolling mills 11.6 9.7 1.9
Strel making 8.2 4.3' 3.9
Coke maki.lg 5.7 3.0 2.7
Sintering 1.1 0.4 0.7
Miscellaneous 10.7 5.7 5.0
Total 100.0 40.5 59.5
Thus, as much as 60 percent of the total water requirement at a shore based
steel plant is met by sea water. Consequently material compatibility problems
arise that are similar to other situations, where sea water is used. These include
corrosion and marine biofouling. The advantage lies in the effluents getting
dIscharged into the sea, where the dilution factor is very high.
In the steel industry, effluents and suspended solids constitute the bulk of
pollutants. Chemical and organic contamination is also a common factor in the
waste water from tlhe coke oven batteries. The volume and composition of
effluents arising out of a coking plant are dependent upon the nature of the
coal, the temperature and the process of carbonisation and the recovery of
ammonia. A representative range of contaminants from a coke oven plant is
given in Table 12.4.
134 Wa.e. Chemistry
Table 12.4 Chemical Contaminants in the Waste Water from a Coke Oven
Plant(')
Chemical Constituent
Free Ammonia as NH)
Ammonium compounds as NH)
Chloride as HCI
Thiocyanate as CNS
Thiosulphate as S
Chemical oxygen demand
Range in mg/I
20-500
100-3000
500-9000
100-600
100-1000
3000
Ammonia is removed from the coke oven gas by contacting it countercurrently
with a solution of phosphoric acid in a two stage spray type absorber. The lean
solution so produced is recycled into the process. Water washing of the residual gas
gives an effluent that is almost free from ammonia. A number of techniques such as
ion exchange, electrolysis, adsorption on high surface area, synthetic polymers etc.
have been developed to remove the other pollutants, before the water is reused.
Waste waters from organic chemical industries such as refineries, petrochemicals,
pesticides, plastics, dye-stuffs etc. require treatment procedures that will effectively
destroy the organic contaminants before such waters are reused or discharged into
the environment. Among different processes, Wet Air Oxidation (WAO) of the
organics has gained favour<8). The process is based on the observation that dissolved
or fmely dispersed organic compounds in waste water can be hydrolysed and oxidised
by bubbling compressed air or high pressure oxygen at elevated temperatures(upto
320°C) and pressures (210 kglcm
2
). There is an induction period, followed by fast
oxidation, which slows down with time. The behaviour is typical of a free radical
initiated process. W AO is self sustaining at Chemical Oxygen Demand (COD) levels
greater than 15 gil. After oxidation in a reactor (30 to. 60 mm) the waste water
stream is cooled and depressurised. The efficiency of the process is judged by the
percentage reduction acheived in the COD and Total Organic Carbon (TOC) levels
of the waste water. A few examples are given in Table 12.5(10).
Table 11.5 Examples of the Efficacy of Wet' Air Oxidation(IO)
Contaminants in Waste Waters
Acrylonitrile
Amines
t-Butyl alcohol
€arbon tetrachloride
Dye stuffs (composite)
Epoxy resins
Formaldehyde
Herbicides (composite)
Monoethanol amine
Pesticides (composite)
Phenols
Polythylene
Polyglycerine
Sulphides
Efficiency (as percentage) for
COD TOC
,
65
86
91
99
·94
94
86
97
79
88
97
97
90
89 83
98
Desalination, Effluent Treatment and Water Conservation
135
An added benefit of WAO is its ability for recovering some inorganic chemicals
like sodium carbonate (from black liquor in paper and pulp industry) ammonium
sulphate (from coke oven scrub liquids) and chromium (from sludges of glue
manufacture ).
As noted in Table 12.2, the paper and pulp industry is one of the very large
consumers of water per ton of the product. During pulping and bleaching
processes, lignin and its degradation products are released which are resistant
to biodegradation. A number of chemical processes have been developed to
overcome this problem. The chief among them are massive lime treatment (doses
ranging from 3000 to 10,000 mg/l of lime) and coagulation with alum and ferric
alum. Because of the cost of chemicals specially in the coagulation process,
there is a neec! to explore alternate techniques. A recent process developed in
India(ll) makes use of the plant's waste cellulosic material as the medium for
lignin adsorption under acidic conditions. The acidity which is around a pH of 2
is determined by the zeta potential of the cellulosic fibres. The cellulosic material
is suspended in water, which is then 'acidified (less than pH 2). The Iingin
containing waste water is then allowed to mix with this. Under these conditions,
lignin precipitates out and is adsorbed on the cellulosic matrix, thus freeing the
waste of its contaminants. At an initial COD to fibre ratio of I, nearly 70
percent reduction has been observed for both COD and colour. Thus the process
offers a good alternative to other chemical processes. Wet Air Oxidation can
also be adopted to these wastes.
Because of the decreasing availability and increasing cost of Water for
industrial activities, it is very essential to recycle as much waste Water as possible
by a proper choice of effluent treatment, which will in
reduce the discharge of pollutants into the environment. • .. :".
REFERENCES
I. Mayor L., (1985), Reverse Osmosis for Water and Waste Water Treatment, Corrosion
and Maintenance, 8, 211.
2. DesaI R.P., (1992), Modern Processes for Treatment of Input and Waste Water-
Reverse Osmosis and Membrane Technologies, Proc. All India Convention on
Industrial Water Treatment and Conservation, E.I - E.12, National Centre for
Technical Development, Bombay, November,1992.
3. Misra B.M., (1992), Role of Membrane Processes in Treatment of Industrial
Effluents, Ibid., Q.l - Q.8, November, 1992.
4. Doshi A.D., (1992), Reverse Osmosis has Come to Stay on its Own Merit for Problem
Waters,Ibid., GC.l GC.6, November, 1992.
5. Gandhi M. and S.M.' Khopkar, (1992), Experience With the Sophisl1cated
Instruments for Monitoring of Effluents, Ibid., BB.I - BB.6, November, 1992.
6. Sukumaran Nair M.P. and P.N.N. PiIlai, (1992), Zero Effluent Approach for Fertiliser
Plants, Ibid., K.l - K.lO, November, 1992.
7. Pati! R.D., (1992), Water Management Practices in Fertilizer Industry, Ibid., G.I -
G.20, November, 1992.
8. Smhamahapatra P.K. and T.A. Subramanian, (1981), Water and Effluent
Management Technologies in Integrated Steel Plants, Corrosion and Maintenance,
4 , 221 -232.
136 Water Chemistry'
9. Randall T.L. and P.J. Canney, (1985), Wet Air OXIdation of Hazardous Organics in
Waste Water, Environmental Progress, 4, 171.
, ,
10. Ravindranath K. and S. Paul, (1992), Wet Air Oxidation of Toxic Industrial Waste
Water, Proc. All India Convention on Industrial Water Treatment and Conservation.
M.I - M.IS, National Centre for Technical Development, Bombay, November, 1992.
I I. Islam S., A. De, S.S.G. Sekar, S. Misra, R. Pant, and A. Panda. (1992), Removal of
Colour and COD of Pulp and Paper Pulp Effluents by Lignin Removal Process,
Ibid., Y.I - Y.9, November,1992.
INDEX
Algae, 43, 45
Alkalinity, ll, 35, 61, 73, 74, 79, 121
All Volat45, ile Treatment, 79, 82, 101, 102,
105
Amines, 80, 134
Filming, 80
Ammonia, 24, 36, 66, 79, 122, 123, 134
Anion Exchange, 58, 65
Anion Exchangers, 578, 61, 65
Strong Base, 57, 59, 60,61, 62
Weak Base, 59, 60, 61, 62
Barnacles, 43
Biofouling, 40, 43, 44
Biological Monitoring, 12
Biological Oxygen Demand, 12
Boiler, 69, 70
Drum, 70, 75, 87
High Pressure, 70, 75
Low Pressure, 72, 75
Once-Through, 72, 75,8$,84, 122
Recirculating, 72
Boiler Water, 69, 75, 80, 83, 90
Conditioning, 72
Quality, 73
Brass, 29, 45, 46, 69
Bromine Biocides, 42, 44
Calciam Salts, 50, 51, 130
Carbon Steel, 70, 101, 102
Carry Over Coefficients, 33, 34, 88
Cation Exchange, 58, 65
Cation Exchangers, 57
Strong Acid, 57, 59, 60, 62, 74
Weak Acid, 59, 60, -4, 106
Chemical Oxygen Demand, ll. 134, 135
Chloramines, 41, 42, 44
Chloride, 12, 78, 89, 99, 105, 122
Chlorination, 40, 41, 42, 43, 48
Chlorine Demand, 42
Chromate, 53, 106
Coagulants, 48, 49
Condensate Polishing, 66, 70, 79, 100
Condenser, 3, 43, 45
Conductivity Cation, 81,86,89, 121
Conductivity Specific, 2, 10, 11, 23, 61, 66,
67,121
Cooling Tower, 3, 48, 52, 53
Cooling Water, 47, 48
Monitoring, 48, 54
Quality, 49
Corrosion, 26, 27, 38, 70, 97, 113, 115, 117
Acidic, 115
Caustic, 29, 76
Crevice, 50, 76, /15
Inter Granular, 2q
Pitting, 29, 71, 115
Stress Corrosion Cracking, 96, 98, 99
Corrosion Products, 28, 32, 95, 97
Cupronickel, 45, 47, 69
Cyclohexyl Amine, 36, 66
Deaerator, 70, 80
Degausser, 61, 74
Demineralisation, 3, 56, 60
Density of Water, 20, 23
Deoxygenation, 37
Deposition/DepositFormation, 31,50,97,117
Desalination, 4, 127
Deuterium, 96, 105
Dielectric Constant of Water, 21, 24, 33
Dissociation Constant of Water, 20
Dissolved Oxygen, 28, 71, 75, 78, 80, 90, 99,
101, 102, 103, 123
Dissolved Solids, 2, 1 12
Total,6, 74, 113, 121:1
Drinking Water Guidelines, i, 8, 130
Economiser, 70, 80,
Effluents, 127, 128,130, 131
Fertiliser, 132
Paper, 132, 135
Steel, 132, 133
Feed Water Quality, 66, 80, 83
Ferrous Sulphate, 46, 47
Fission Products, 93, 95, 98, 107
Fluoride, 7, 104
Geothermal Water Quality, 113, Jl4
Graphite, 2, 93, 94
Ground Water Qualit), 15
Hardness, /1, 76
Calcium, 1 I, 49: 50, 51
MagneSium, 11, 49
Hardness of Water, I I
Heat Exchangers, 3, 52
Heaters, 70
[{P,70
LP,70
Heavy Water, 96, 102, 103, 105, 106, 132
Hot Conditioning, 102
Hydrazine, 36,37,38, 75, 79,80, 102, 125
Hydrogen, 71, 95
Dissolved, 100, 105
Explosion, 2, 107
Injection, 99, 100, 103
Hydrogen Sulphide, JJ3, U5-Jl8
Incaloy-800, 69, 100-104
Inconel-600, 97, 100, 101
Ion Exchange, 3, 57, 58
Ion Exchange Beds, 61
138
Anion, 61, 104
Cation, 61, 66, 104
Mixed. 61, 62, 65, 67, 100
RegeneratIOn, 62, 63
Co Current, 62, 63
Counter Current, 62, 63, 66
Stratified. 64, 65
Three Resin Bed, 64
Ion Exchangers, 59
Capacity, 59
Cross Linking, 59
Gel,60
Macroporous, 60-62
Osmotic Shock, 59
Type-I, 60, 61, 63
Type-ll, 60, 61, 63, 65
Ionic Product, 20, 23, 24
Langlier Index, 51, 52
Lithium Hydroxide, 24, 102, 103
Magnetite, 28, 70. 96. 102, 103
Formation, 28.29. 102
Sob1bility, 29. 30. 103
Make up Water Quality, 48
Man-Rem Problem, 31. 95
Material Compatibility, 4, 26. 38, 93
Mixed Ferrites, 96
Moderator, 1. 93. 94, 102. 105, 132
Molybdate, 54
Molybdinum,108
Monel-400, 69. 102-104
Morpholine, 36. 66. 79, 106
Mussels, 43
Nuclear Acc.idents, 106
Nuclear Reactors, 93
Power, 93
BWR, 94. 98-100. 122
Face, 95
FOSSIL, 1
PHWR, 94, 102-104
PWR, 94, JOO. 101
RBMK,94
VVER, 94, JOO. 101
Research. 106
On-Line Analysers, 120, 125
Chloride, 122. 123
Copper, 123
pH, 121
Silica, 123
Sp. ConductIvity. 121
Organics In Water, 9, 10, 17. 61
pH, 10, 20. 21. 36, 80. 81. 100
Change With Temperature, 24
Phosphate, 52. 53, 79, 82. 102
Addition, 76
EqUIlibria, 77
Hide Out, 78
Water Chemistry
Phosphate Treatment, 76. 125. 130
Congruent, 78
Coordinated, 76. 77. 101
Phosphenates, 53, 54
AMP, 53. 54
HEDP, 53
Point of Zero Charge, 32, 44
Polyelectrolytes, 49. 50
Polyphosphate, 52-54
Pukarius Stability Index, 51
Radiolysis of Water, 96
Reactor Water Quality, 99 101
Reverse Osmosis, 3,4,56. 127. 128. 132
River Water Quality, 13. 14. 16
Ruthenium, 108
Ryzoar Stability Index, 51. 52
Scale, 49-52. 117, 130
Sea Water Cooling, 9. 43, 82
Silica, 33. 35, 62. 65. 81. 90. 123
Sodium Absorption Ratio, 9
Stainless Steel, 45. 69. 93. 98. 115
Steam, 86. 115. 120
Explosion. 2
Generator, 69. 125
Quality Specific'ations. 3. 87. 89. 91
Reheat. 90
Saturated. 87. 121
Super heated, 87. 121
Steam-Hydrogen Ratio, J08
Super Heater, 70
Surface Active Agents, 50. 51
Surface Tension of Water, 20
Thermal Power Stations, 70. 83. 91. 93
Water Chemistry. 70
Turbine, 70. 72. 86. 87. 116
Uranium, 1. 2, 106
Uranium Dioxide, 2. 94. 106
Viscosity of Water, 20
Water, 5. 7. 13. 25. 39
Thermophysical Properties. 19-22
Water Chemistry, 4.26.38. 93. 120
Automated, 124, 125
Computer Control/ed, 124, 125
Quality, 6, 7,8. 10. n 13, 15
Water Conservation, 4, 127, 130, 132
Wet AIr Oridation 134. 135
Zero Solids Treatment, 83
Zeta Potential, 31. 32, 47
Zinc,53,54
Zircoloy, 94. 95, 102
Zirconium, 2. 106

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Water Treatment

Industrial and Power Station

.

K.S. VENKATESWARlU
Former Head Water Chemistry Division Bhabha Atomic Research Centre Bombay

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PREFACE

After my long association with the Bhabha Atomic Research Centre, Trombay, several colleagues suggested that I should write a book on Water Chemistry, considering my deep involvement with the development of this subject. Since I felt that writing a book would be no easy task, I deferred it. Three years later during my recovery from surgery, which restricted my outdoor movements my wife persuaded me to start this task. In deference to her wishes and that of other friends, I made a beginning and soon found that MIs Wiley Eastern Ltd. would be willing to publish it. From then onwards, there wns no going back and the result is this monograph, "Water Chemistry and Industrial Water Treatment." Around 1970, it was realised in the Department of Atomic Energy, BARC and Power Projects, that water chemistry research and development is essential for the smooth and safe operation oflndia's nuclear power reactors, as they all make use of light or heavy water as the heat transfer medium at high temperatures and pressures. To co-ordinate the effort, a Working Group on Power Re-actor Water Chemistry (PREWAC) was set up, which was later transformed into a Committee on Steam and Water Chemistry (COSWAC). I was associated with this effort from the beginning as the Convenor, PREWAC, Member-Secretary COSWAC and subsequently as its Chairman until the end of 1989. The International Atomic Energy Agency, refle,cting the world wide emphasis on this subject in the nuclear industry, conducted several co-ordinated Research Programmes on' Water Chemistry in Nuclear Power Stations during the 80s. I was privileged to be associated with this effort on behalf of the Department of Atomic Energy. In terms of infrastructure, BARC has set up a dedicated Water and Steam Chemistry Laboratory at Kalpakkam (Near Madras). In addition to chemical programmes, studies on marine biofouling were also initiated. These experiences have given me a close feel for this interdisciplinary subject. The Central Board of Irrigation ane Power, New Delhi has also indentified

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No. Germany for Fig. United Kingdom for Fig. Nos. Berkeley Technology Centre.8. and 4. with thanks. USA for Fig.1 and National Association of Corrosion Engineers. 4. No. 3. 4. USA for Fig. Nos. MIs.3.7. 5. Power (an international journal).1 and 4. MIs. 9. the permission readily and gracioasly given by: The Central Board ofIrrigation and Power. Nuclear Electric.4.ACKNOWLEDGEMENTS The author acknowledges. USA for Fig.2. New Delhi.6. No. India for making use of technical information and data inclusive of some figures from their reports cited at the appropriate places. American Power Conference. Vulkan-Verlag GMBH. 4. .

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Introduction Physico-chemical Charcterstics of Natural Waters Properties of Water at High Temperatures and Pressures Water Chemistry. xi xiii 1. 2. Material Compatibility and Corrosion Treatment of Natural Waters for Industrial Cooling Demineralisation by Ion Exchange Water Chemistry in Fossil Fuel Fired Steam Generating Units Steam Quality Requirements for High Pressure T'lJ'bines Special Problems of Water Chemistry and Material Compatability in Nuclear Power Stations Geothermal Power and Water Chemistry Analytical Techniques for Water Chemistry Montoring and Control Desalinati~n. Effluent Treatment and Water Conservation Index 5 19 26 39 56 69 86 93 111 120 127 137 . 3.TABLE OF CONTENTS Preface Acknowledgements List of Figures List of Tables v v. 10. 12. 7. 6. S.. 11. 9. 8. 4.

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ts in boiler water Caustic solubility data shown on P. No.3 7. T coordinates Caustic solubility data shown on a Mo!.3 4.2 Plot of pKw of water vs temperature Mechanism of the first step in iron corrosion Possible species of iron under aqueous environment Solubility of magnetite in the pH range of 3 to 13 Solubility of magnetitie at 300°C vs pH300 Conceptual representation of electrical double layer Ray diagram of carry over coefficients of salts and metal oxide contaminar.LIST OF FIGURES Fig.6 4.7 4.:"r diagram Dissociation of HOCI and hOBr as a fUHction of pH Important problem areas in cooling water system Sodium contamination in mixed bed J.1 5.steam circuit in a power plant Corrosion and deposition processes in water cooled nuclear power reactors Stress corrosion cracking of stainless steel .2 6. 24 27 28 30 30 31 33 34 3S 41 48 63 64 64 70 97 99 4.1 4. 3.2 6.8 5.2 4.resin mixed bed Stratified bed Simplified water .1 9.1 6.egeneration 3 .4 4.5 Title Page No..1 9.1 4.

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Thermophysical parameters of water as a function of temperature and pressure 21 Variation in the properties of water with temperature and pressure 22 Density of water: variations with temperature and pressure 23 .1 6.10 2.2 2.6 3. Haryana IS River water analysis with seasonal variations as used 16 by electricity generating industry. India Thermophysicai properties of water 20 Changes in surface tension and viscosity of 20 water with temperature . Specific conductivity of water at different temperatures 23 Changes in pH of water.8 2.4 2.6 2.3 2.7 2.2 4.3 3.2 3.1 Pale No.4 S.11 2.4 3.3 4. India Typical analytical data of impounded raw water 17 from a reservoir. 2.1 3.LIST OF TABLES Table No. ammonium and lithium 24 hydroxide solutions as a function of temperature 32 PZC values of some corrosion product species Distribution of silica between steam and water phases 3S Relationship between pH values at 2SoC and 36 concentration of alkali sing agents 37 Thermal decomposition ofhydrazine SO Solubility trends among scale forming calcium salts 60 Characteristics of standard ion exchange resins .1 2.12 3.1 4.S 3.7 4.9 2.S 2. TItle Water quality vs total dissolved solids 6 Chemical constituents of significance in natural waters 6 Constituents of drinking water having significance 8 to health WlIO guide lines (1984) for aesthetic quality of 8 drinking water 11 Specific conductivity vs water quality 11 Hardness vs water quality 13 Classification of natural waters Example of river water monitoring in Andhra 14 Pradesh Saline water intrusion into coastal wells in Kamataka IS Chemical composition of some brine waters.

8 Tide List o/Tables Page No.5 7.5 9.1 9. UK (CEGB) specifications for high pressure-high heat flux boilers cooled by sea water CEGB primary targets for once-through boilers High pressure steam quality specifications Turbine part failures-US industry eXperience Maximum permissible concentration of silica in boiler water Guidelines for reheat steam Steam purity limits in industrial turbines Feed and reactor water specifications for boiling water reactors PWR reactor water quality specifications VVER-400 reactor water quality specifications Chemical control specifications for PHT system in PHWRs Geothermal locations in India Growth of installed capacity of geothermal power Composition of some geothermal steam and water phases Characteristics of some geothermal steam and water phases Corrosion characteristics of geothermal fluids Corrosion studies.2 7.3 8.7 12. 6.3 10.xiv Table No.4 10.1 8.3 7.4 7.4 12.6 7.2 9.1 7.5 10.4 8.1 12.7 7. USA (EPRI) guidelines for make up water and condensate Central Electricity Generating Board.2 7.6 10.3 9.3 12.2 10.5 Comparison of mixed bed performance Water quality specifications for low pressure boilers Water quality limits (max.4 10.1 10.with reference to H 2S abatement by iron catalyst Surface corrosion rates of materials in contact with geothermal fluids Tolerance limits for discharge as per Indian standards Water requirements for industrial operations Water consumption in a shore based steel plant Chemical contaminants in the waste water from a coke oven plant Examples of the efficacy of wet air oxidation 82 84 87 89 90 90 91 99 101 101 104 112 112 113 114 115 116 117 131 132 133 134 134 .2 8.9 8. 67 73 74 76 77 78 78 81 7.2 12.) of medium pressure boilers Reference data for conventional co-ordinated phosphate treatment pH vs percentage of different species of phosphate Reference data for low level co-ordinated phosphate treatment for high pressure boilers Solubility of trisodium phosphate as a function of temperature Electric Power Research Institute.

This was at a time when there was no fire as there was no vegetation. Mrs. When this happened over an area now known as Oklo in Gabon. which was any way not a supporter of combustion due to its low oxygen content. Subsequent "rains" would restore the chain reaction. water vapour in the atmosphere started to condense and there were "rains". This pulsating system. if not to two billion years. It was a time when the isotopic composition of uranium (U) was such that the more easily fissionable U-'23S was about 3 per cent and not the present value of 0. . the chain reaction stopped. Neither were there combustible gases such as hydrogen or methane in the atmosphere.. When the surrounding water evaporated due to the heat generated by the fission process." The association of water with he. born of the power of heat. that one which arose at Jast. Indira Gandhi quotes a translation of Rig Veda's "Hymn of Creation" thus: "Then even nothingness was not. known as the Fossil Nuclear Reactor.7 per cent. releasing considerable quantities of energy.at. nor existence. It was a time when the atmosphere was not very dissimilar to the composition of the gases emanating from volcanic eruptions and contained much water vapour. generated about 1011 KWH of thermal energy. since water which acted as a neutron moderator was lost. Rain water began to accumulate and flow over the surface of the earth.1 INTRODUCTION In her engrossing pictorial volume titled "Eternal India". W.energy dates back to hundreds of miJJion of years. As the temperature of the earth's surface cooled down to below l00oC. What covered it 1 In whose keeping 1 Was there cosmic water in depths unfathomed ? '" All of tliem was unillumined water. Africa. There was a time in the very distant past when the earth and its environment were so different from what we experience now. A time when the north east comer of present day South America fitted snugly into West African coast. the water streams surrounded the "Jow enriched" uranium mineral deposits and a nuclear fission chain reaction ensuec1.

Even in the case of rain water. are present. zirconium reacted violently with the high temperature steam. horticulture.4 in Ukraine. If it is in a boiling condition.. graphite. as compared to ground waters such as bore wells. The information that is needed to appreciate this added aggressiveness needs to be discussed. high temperature water (say at 27S°C) jmplicitly means that it is also under high pressure. Their safe co-existence in modern industrial systems having multi metal surfaces. At this limit. one hears of "acid rain". viz. it will be a two phase system.2 Water Chemistry Skipping over the chasm of two billion years. With heavy industrialisation. the only "impurities" would be the hydrogen and hydroxyl ions formed as a result of such a dissbciation. In general one might say that water becomes an aggressive fluid at high temperatures.t to such an ideal. the limit being dictated by the dissociation constant of water at that temperature-. The basic physico-chemical properties of water are dependent upon the temperature. Unlike at Oklo. and the metal zirconium were available in plenty. in the Chernobyl plant in addition to low enriched uranium. specially sodium chloride. Geothermal waters have a high salt content as well as dissolved gases. etc. agriculture. so that if at one place calcium (Ca) is more than magnesium (Mg) at another location. to April 1986. water can be kept in the liquid phase even above 100°C by the application of pressure. The level of dissolved salts in natural waters is important since it determines the use to which the water is put. depending upon the location and the prevailing environmental conditions in the atmosphere. the water becomes loaded with dissolved impurities leached from the surface and the subsurface as the rain water percolates into the soil. In nature. the purity of water varies all the way from relatively pure rain water to sea water with high salt content. Thus. Once rain falls on the earth's surface. While graphite caught fire. At 200C the theoretical conductivity of water is 0. There are many examples of rivers picking up impurities as they flow over different terrains. Sea water contains the maximum content of dissolved electrolytes. Being under pressure also means that water or a steam-water mixture at high temperatures will always be a closed system. Theoretically. There was al. health spas. producin~ hydrogen that combined with oxyt. a combustible material. As is well known. The consequential problems of material compatibility and corrosion in high temperature water and steam are of extreme . Thus. drinking. it might just be the reverse. Surface waters such as rivers and lakes have relatively less dissolved solids. which led to the world's worst nuclear accident. it was tho short supply of cooling water relative to the accidental production of excess heat energy in the Chernobyl nuclear reactor No. pure water is characterised by as Iowa conductivity as pOllible. Thus. some impurities such as dissolved gases.o speculation that contact of high temperature water with the molten co(e of uranium oxide led to a steam explosion in parallel with the hydrogen burn. high or ultra pure water is only a laboratory curiosity and in nature a rain drop in a clean atmospheric environment is the neareJ. the power of heat and the power of water are always competitive as well as complementary.05 micro siemens per em (j1S/cm). Different facets of the physical and chemical characteristics of natural waters are reviewed in this book. (oxides of nitrogen and sulphur).en leading to a devastating explosion. is the subject matter of this monograph.

there is some difference in the feed and boiler water treatment for low and medium pressure industrial boilers as against the high pressure boilers employed by the electricity generating !lector. In saline waters. In other "high tech" industries such as fertilisers and oil refineries.on depends upon the changin"g thermal and chemical environment. high purity water can be produced on a large scale through ion exchange. A combination of these two techniques is also being advocated for use in the industry. release of corrosion products and their subsequent redepositi. A number of techniques have been developed over the last five decades. although the use of cooling towers. both sels of units mean the same. as well as environmental considerations. this book deals only with ion exchange and reverse osmosis techniques. while in thermal power stations.0. power plants employ water for cooling the condensers. The largest volume of water used in the industry is for cooling in chemical processes. Process-water heat exchangers and cooling towers are employed for 1his task. The role of dissolved electrolytes. Special techniques have been developed to prepare ultra-pure water for use in the semi-conductor industry. the level of sodium and chloride have been specified to be less than 5 ppb each*. either added intentionally or picked up from surfa~s or through unexpected contamination IS equally relevant. as well as in processes such as naptha cracking. These are generally once\through systems. Surface oxidation. Depending upon the source of water and the seasonal variations in its composition. treatment is essential for combating biofouling and corrosion. In subsequent chapters the units used lire mgtl and Ilg/l which are more or less equal to ppm and ppb respectively. The qualit}" of steam is of paramount importance in all these activities. Co-generation is an attractive concept. while a lower order of purity can be achieved by reverse osmosis. However. In addition to distillation. Since the physico-chemical properties of water are a func~ion of temperature and pressure.Introduction 3 importance in the smooth functioning of the steam generating industry. inspite of common features. . the output is high pressure steam that drives the turbine. These are of special importance in nuclear power stations. On the other hand. milJigrarn/ litre (mgll) is II more appropriate unit. both hot water and process steam are supplied by the former class. As an example:for modern high pressure turbines. . in which both the power and the process h~at requirements of industries such as fertilisers and petrochemicals * Impurities are expressed as 'parts per million'. (ppb). a cooling water treatment prbgramme is adopted. In fact marine biofouling is so diverse and so persistent that studies to evolve counter measures would take years at each of tbe coastal sites.to dissipate heat are coming \ipto vogue at inland locations due to the limited supply of water. high pressure steam is also used f~r motive power. (ppm) or at a still lower levellls 'parts per billion'. When the specific gravity of water under consideration is nearly 1. Natural waters need to be demineraIised wholly to make them fit for use in a high temperature heat transfer circuit. which is compatible with the materials employed in the circuit. Depending upon the requirements of the chemical process industry. Even w'ith sea water cooled condensers.

while the high pressure steam drives the turbine for power production. as well as sea water. Hydrogen sulphide (H 2S) contamination of geothermal waters is a serious problem. This will be a means of water conservation. As the stearn generating system operates round the clock for prolonged periods.effluents. a part of the exhaust steam. sea water poses special problems. Nuclear powered steam generators and their primary heat transport systems have their own additional and specific problems in terms of the radioactivity of the fissiop and corrosion products. in desalination through multiflash evaporation or membrane technology. An appreciation of the chemical problems in this area has been provided in this volume. it is necessary'to detail the chemical and instrumental techniques needed by a water chemist. Limiting radiation exposure (0 operating personnel is the primary objective of water chemistry control in a nuclear power s~ation. Desalination of brackish waters. high pressure water/steam is vital. In modern power stations.4 Water Chemistry can be met by a single plant with considerable fuel savings. the hot water effluent can still be made use of for district heating. especially as a precurser to ion exchange in water demineralisation. In India. has gained considerable itnportance in water starved areas like the desert states around the Arabian Gulf. No discussion on water chemistry is complete without reference to the chemical and instrumental techniques that are needed for monitoring the properties of water and the measurement of the levels of dissolved impurities. . Such systems make use of what are know. particularly the aquatic environment through the discharge of liquid . A water chemist would have to make a variety of measurements to enable him to render useful advice to the management. In this practice. Even if a geothermal well is not steaming. as water is a precious resource. With its high salt content. the designers of equipment look for materials that are suitable in the working environment of geothermal fluids. while the treated water is recycled. and providing safe drinking water in villages under a Technology Mission. in addition to being a source of valuable inorganic chemicals. Since. This natural resource is confined to a few places around the world and is a useful supplement. it has become absobtely necessary to devise effluent treatment processes that trap the harmful pollutants. The ("ffects of the changes in the steam chemistry within the system due to the changes in pressure can be overcome by adhering strictly to the steam purity limits needed at the high pressure end. The issue is taken up from the design stage itself and is finally reflected in the selection of material and water chemistry control. material compatibility with high temperature. on-line instrumentation for chemical monitoring and computer controlled chemical addition are becoming more popular. In view of the increasing concern about polluting our environment. Thus.n as extraction condensing turbines. An attractive as well as an additional source of energy is available from geothermal wells. chemical control cannot be easily effected. In addition the life of the plant is extended by providlftg protection against equipment corrosion. which is at a low pressure is used to provide the process heat. reverse osmosis is steadily gaining ground.

Thus. most of the fresh water (84. 14. only a very small fraction of fresh water. This is not the case with agriculture or domestic use. viz. taste.. . viz. Natural waters can be classified into two categories. the need for the conservation of available fresh water is obvious.16 per cent constitutes ground water. On the other hand. the temperature ranges only from above OOC for surface waters to a little over 100°C for geothermal waters.55 per cent. This is more significant from a chemical point of view than from a physical perspective. 0. while that in lakes and reservoirs~mounts to 0. odour. suspended solids etc.33 per cent is in form of soil moisture and atmospheric water vapour. According to United States Geological Survey(l). The important characteristics that signify water quality are described below. Nearly 90 per cent of the water employed in industry is for cooling purposes and the balance for steam generation.2 PHYSICO-CHEMICAL CHARACTERISTICS OF NATURAL WATERS A multiplic!ty of water characteristics is encountered in nattire. Industry employs water from all types of water resources. At ambient temperature they find maximum use in industry and agriculture. Of the balar)ce. The water quality requirements are somewhat different for different uses. either electrolytes or gases. Ground waters are expected to be free from organic odour and have a relatively less variable composition at the same source. The volume of sea water is fifteen times greater than that of fresh water.. Another 0. From relatively clean and pure rain water with little dissolved impurities. Hence. Surface waters might possess colour.004 per cent flows through rivers and streams. sea water (inclusive of estuarian water) and fresh water.9 per cent) is locked up as ice in glaciers. the chemical contamination stretches upto sea water with a very high dissolved salt content.

120 (Health) Less than 3 Less than 0. specially the presence of pathogens.2 Chemical Constituents of Significance in Natural Waters (1) Chemical Constituent Bicarbonate Carbonate Calcium Magnesium Sodium Iron Manganese Chloride Fluoride Sulphate mg/l 150 .000 10. The bacterial content. it can certainly be upgraded by properly designed and executed treatment procedures. The seasonal variations in the quality of some surface waters could be large enough to make the use of such waters more problematic. For this reason the concentrations of inorganic and organic substances dissolved i. hardness. The United States Geological Survey(l) has classified different waters on the basis of their Total Dissolved Solids (TDS) content as given in Table 2.1. Above these levels. such chemicals can cause undesirable effects.1. deposit formation and corrosive nature of water. This exercise should cover not only the major dissolved constituents. detergents. . with respect to several chemicals that might be present in natural waters.2 300 .000 (Laxative action) Note: The above1are however nOllo be taken as drinking water standards.200 25 . Total Dissolved Solids(l) Water Quality Fresh Slightly saline Moderately saline Very saline Briny TOS (mg/l) Less than 1000 1.7 .n a body of water and their spatial and temporal variations need to be monitored.05 250 0. It is not advisable to condemn a particular body of water as unsuitable. Under this category comes silt and suspended solids.400 (Taste) 600 .000 to 3. in addition to dissolved salts.1 Water Quality vs.50 60 (Irrigation) 20 .6 Water Chemistry 2. the self purification capacity and the water intake structure also have a bearing on quality.000 Greater than 35.000 to 10.000 to 35.000 3. the ratio of sodium (Na) to that of calcium (Ca) and magnesium (Mg) etc.000 The underlying chemical relationships between pH.1 WATER QUALITY Experience has shown that many diverse factors will have to be taken into account before making comments on water quality. which may be the only available source at that location. but also the minor ones such as heavy metals. Whatever might be the quality of water available to a user. determines. alkalinity. pesticides etc. Table 2. Table 2. the buffering capacity. The United States Geological Survey(l) has given the significant concentration.1.

8 mg/l. the limits are the same as for human consumption. In India. the total dissolved solids. In addition WHO has also issued guidelines for the "aesthetic quality" of drinking water (1984). provided the increase is not due to the admixture of industrial effluents containing trace toxic constituents such as chromate.4. Under the US law. Less than 500 mgll of TDS is usually satisfactory. in case no alternative supply is available(3). These are as fol!ows : The lower control limit of 0. It should have no unpleasant odour (dissolved gases) or taste (absence of certain dissolved solids).3. Thus the flexibility in the range of fluoride control limits in India (as well as in other tropical -:ountries) is much less than say in England or Canada.3 WATER FOR IRRIGATION The chemical parameters that are important for water used in irrigation are. the relative proportion of sodium (Na) and potassium (K) to divalent cations such as Ca and Mg and the concentration of boron and other toxic elements. There is also a certain amount of avoidable confusion. is the presence of fluoride. The upper control limit for fluoride in the same temperature range is reduced from 1.3). the Technology Mission on Drinking Water laid special emphasis on fluoride. One of the well documented problems concerning drinking water. cleaning and laundry jobs. its suitability decreases with respect to cooking. What is not well publicised is the temperature effect on the fluoride limits in drinking waterS).50 C. A case in point is the smell of chlorine that is once in a way detected in domestic water supply.Chemical Characteristics 7 2. both inorganic and organic as well as of microbiological nature to health(6). which are a little difficult to quantify. although the upper limit may go up to 5000 mg/l. A result of this is the fonnulation of National Interim Primary Drinking Water Standards (NIPDWS) in 1985(7). The World Health Organisation has stipulated that drinking water should have a TDS content of less than 500 mgll. For domestic animals.7 to 0. while above 1500 mg/l is not suitable for irrigation except under severe constraints(3). which are slightly different from those issued by WHO in 1984 (Table 2. carbonate. the Environmental Protection A~ency is charged with the task of conducting a regular review of the guidelines for drinking water as applicable in the USA. .9 mgll at an ambient annual average air temperature of 10°C is reduced to 0. refer to constituents of significance. The presence of toxic elements usually arises due to contamination by effluents discharged from nearby industries. as a result of excessive chlorination.6 mgtl at a temperature of 32. although this can be relaxed to 1500 mgll. Drinking water should also be free from colour and turbidity.Physioo . between 500 to 1500 mg/l needs special management. Mg. sulphate). since the beneficial effects of a little fluoride in dental care are also known. This is due to the dependence on temperature of the rate of the biological uptake of fluoride by body fluids. 2. These are summarised in Table 2. as well as iron contamination in rural water supplies(4). With an increase in the hardness of water (Ca.2 DRINKING WATER SUPPLIES The quality of water for domestic use is judged from its total dissolved solids content. The WHO guidelines for the quality of drinking water (1984) as given in Table 2.

3 0.8 Water Chemistry 'table 1.S 10. Constituents of Drlnkinl Water Havlnl SIIDlficane.OS O.0 SOO (u CaCOJ Odour not to be detected at all 0.OS O.0 1. is obtained by dividing mgll (or ppm) by the equivalent weight of the ion under consideration.1 0.0 10.3 0. .01 O.OpS 0.4· 10.0 3. mgll S S Sodium and Potassium ion concentrations in natural' waters are relevant to irrigation as these cations reduce the permeability of soils. • Equivalents per million (epm).03 0.gil !Jg/I !Jg/I !Jg/I pcill pcill mremly Limit of WHO Guideline (1984) 0.OS O.002 0.0 • Level variation with climatic conditions.0 (uN) 0.OS O.0 3. WHO Guidelines (1984) for Esthetic Quality of Drinklnl Water (7) Constituent Aluminium Chloride Copper Hardness Hydrogen Sulphide Iron Manganese pH Sodium Sulphate Turbidity Zinc Unit mgll mgll mgll mgll Guideline Value 0.S to 8..O S.O 4.0 0.3.4 to 2.001 Limit ofNIPDWS Guideline (198S) Mercury Cadmium Selenium Arsenic Chromium Silver Cyanide Lead Barium Fluoride Nitrate Hexachlorobenzene Aldrin Heptachlor Chlorodane I-I-dichloroethane DDT Carbon tetrachloride Lindane Benzene Gross ex Ra226 + Ra228 J3 + photon emitters O.01 O.e to Healtb(f.S I.1 6.0 ]S. Table 1. 0.S 200 400 mgll mgll mgll mgll NTtJ.01 0.2 2S0 1." Cl)nstituent Unit mgll mgll mgll mg/I mgll mg/I mgll mg/I mgll mgll mgll IAglI lAg/I IAglI !Jg/l !JgII ".01 0.OS . On the other hand.3 1.4.OS 1.1 O.

the water is not suitable for irrigation. Sea water with a salinity of 35 gIl has an average der. for producing drinking water. This is defined as. In addition. when the power station is on the coast. the biofouling characteristics of sea water at that particular lOCation are of much greater relevance than the chemical parameters. 2. being divalent. thus reducing Na and K uptake and helping to restore soil permeability.ot suited for domestic and irrigation purposes. main areas of concern are as follows: It can lead to blocking of functional groups of the ion exchange resins of water treatment plants because of irreversible absorption. desalination of brackish as well as sea water (an industry by itselt) has come into vogue in arid and desert locations.:===. If RSC is greater than 2. salination of super heaters and turbines. A factor known as the Sodium Absorption Ratio (SAR). but also its tendency to foam. which is the same as milli equivalents per Iitre('>.--.+ HCO. ' Na+ SA R . A variation in salinity of 1 gil causes the density to change by 0.sity of 1.:0= 2 Ca • + Mg2+ 2 (2. corrosion in the condensation zone can also result because of volatile decomposition products. the optimum RSC spread being from 1.0281 kg/l at O°e.2) The concentrations are again expressed in epm. also called Sodium Hazard. most of these methods (a) . is coastal saline groundwater.Physico . 2. In recent decades.4 SALINE WATERS Sea water is r. This can le~ld to steam entrainment of boiler water. another criterion that has been used is known as RSC (range of soil carbonates). is defined as. Rsc-(coi. leading to reduction in the ion exchange capacity as well as damage to the resins. Sea water is used for cooling power rlant condensers.0008 kg/I. (b) When carried into the tlOiler with the deionised water.25 to 2. This is used for horticulture rather than for agricultural purposes.)-(ca 2++ Mg2+) (2. ~Iso made use of. partial precipitation). Since Ca and Mg concentrations are also governed by presence of bicarbonate and carbonate ions (i.5 epm.e.5 epm.1) The concentrations are expressed in equivalents per million (epm)*. However.Chemical Characteristics 9 Ca and Mg ions. This poses several problems with respect to power station water chemistry.==.S ORGANIC WAD Natural waters contain organic matter in addition to inorganic substances. In this context. Several techniques have been developed to isolate organic substances from water and to estimate them quantitatively(I). The two . it may get decomposed into acidic products which can affect not only the boiler water pH. are pleferentially taken up by the exchange sites in soil.

Such examples of acidic or alkaline water. as given in Tabie 2. In certain instances. Some surface waters passing over areas that are rich in sodium and potassium exhibit an alkaline pH. There are instances when.rmiqf!tionA)fTotal Organic C. The electrical conductivity (EC) of water is related to its total dissolved solids content.6 CHEMICAL PARAMETERS GOVERNING WATER QUALITY The quality of surface water from rivers and lakes is important to industry. Therefore. rain water woule have a pH in the aciaic region. rather than 'depending on potassium permat}ganate value of the raw water. For drinking water a pH of 6. The Association of Boiler MaJlllf~cturers. Biofouling due to surface water is also a problem that has to be tackled. power plant laboratories usually determiIie only the potassium permanganate value. Thus. however. The hydrogen ion concentration is represented by the pH value. Since. more care needs tq:biexerclsed. Oxidising agents such as chlorine or ozone i:an also be tried.S(9).. 6. leading to the phenomenon of "acid rain". not common. (VGB) found that ultra violet (UV) spectrophotometry cao:ieaout in the range of 200 to 340 nm may furnish very useful information about these organic substances (hUJJlic acid.2.0 to 9. In view of variations expressed due to blending of water from different borewell farms. parameter. 2.5 is recommended. It is essential to appr. These are flocculation. there are instances where the industry experien~ chan~es in water quality on a day to day basis.0 to 8. The water quality is usually judged on the basis of its value.anien exchangers as absorbers. water quality monitoring is an essential activity for any industry thatmakes-use of a water source.Qf. subsurface or groundwater (from a borewell farm) is also used. . The breakdown of organics in steam generating systems is leaaing to problem situations in several power stations.S to 8. as it determines the chemical or de mineralisation treatment needed.eciate: -the Significance of limits set on chemical parameters defming wat~ quality. it is a very useful indicator and is expressed as microsiemens/cm at 25 0 C. In principle it is adlf~to seParate organic substances from the raw water through an appropriate. Sophisticated analysers are marketed fot this task. Germany. flocculation-decarbonizathmand use. it is possible to carry out the ion exchange as well as organic substance removal within the plant. while for irrigation the range can be slightly wider viz.) without the need of isolating. lignin suiphonic acid etc.10 Water Chemistry are expensive in terms of time involved as well as equipment.we-treatment. Clean sea water usually has a pH of 8. Under certain conditions. are however. By IlhcHarge the pH of natural waters lies in the neutral range. Since it is easy to measure this. For this.mon (TOC). addition of preliminary purification stages ahe~ad ofDM plant is recommended. Consequently more ahd mot' ~Iectrical utilities are switching over to the dete.0. to make it compatible with the construction materials of cooling and heat transfer circuits. water qualit)"'Varies with location and seasons. identifying and quantifying the individual constituents. due to contamination of dissolved gases such as SUlphur dioxide· or oxides of nitrogen.

represents the total consumption of potassium dichromate during hot oxidation of water sample~"'~ covers a majority of organic compounds and oxidisable inorganic specf~/ Alkalinity is usually defined'in terms of bicarbonate. Hardaess VI. Description of Water Soft water Moderately soft Neither hard nor soft Moderately hard Hard water Very hard 50 • 50 • 100 JOO • 1. .Chemical Characteristics Table 2. due to presence of Ca and Mg in combination with anions such as carbonate and sulphate. Mg hardness and the sum of these two viz. extra hardness will mean the consumption of more soap in washing and also scale formation in cooling water circuits and boilers. Itt concentrations abOve 3000 mgll.Physico . Spec:ifie Conduetlvity vs.5. On the other hand. 3000 Oreater than 3000 Water Quality Excellent Good Permissible Needs treatment Unsuitable for most purposes 11 A commonly indicated water quality parameter is its hardness. tn the presence of large ~ntrations orMg. the total hardness. The presence of these two divalent cations is essential for ensuring soil permeability as well as for the growth of crops. soluble silica would cause the precipitation of magnesium ~roxy silicate. but only half of carbonate content. Bicarbonate alkalinity is also called methyl orange alkhlinity or M-alkalinity.Hnity causes the precipitation of Ca and Mg leading to the problelll of scaling on heat transfer . one measures what is known as Ca hardness. In tenns of hardness. I Mg is toxic. ' Table 2. 61·120 as moderately hard.Sp 150 • 200 200 • 300 Greater than 300 . the United States Geological Survey Classification of Waters(2) base'" on hardness [expressed as calcium carbOnate (CaCOJ> mill} gives. Water Quality(') Specific Conductivity (~S/cm) Less than 250 250 • 750 7S0 .droxide ion concentrations.6. surfaces. 121-180 ¥ hard and above 180 as very hard. As against the above. It should be remembered that very soft water induces corrosion in iron pipe line.6(9). the water quality is designated as shown in Table 2.While hardness per ~ 1S not harmful to health. Thus. it is better to avoid hard water for drinking. while P-alkalinity (Phenophalien alkalinity) signifies thepresence of carbonates and hydroxide ions. As defined P-alkalil}ity includes all the hydroxides.0-60 as soft. Water Quality(') Hardness expressed as mgll of CaCO) 0. The measurement of Ca and Mg is through simple volumetric procedures. Highqi alk.. Chemical Oxygen Demand (COD). carbonate and hy.2000 2000..

as otherwise it is harmful to plant growth.12 Water Chemistry Coming to the presence of other anions in natural waters. is indicated. the best results are obtained in less dynamic laboratory applications and in monitoring the quality of cooling tower water in industry. (c) Calcium chloride. The presence of . This leads to five types. through the biological oxidation of organic matter present in water samples.7 CLASSIFICATION OF WATER QUALITY Using the specific conductivity and the SAR value of natural water. presence of toxic chemical etc. although its practical determination is open to a number of reservations. If the water quality deteriorates (low dissolved oxygen. a salinity hazard diagram has been constructed to classify waters meant for irrigation. the fish will be affected and this will be reflected in the record of their emitted electrical impulses. viz. The BOD ofa water body. The fish swimming against the stream of. (d) Sodium chloride and (e) Mixed type. There are five groupings in terms of conductivity and four in tc:rms of SAR. Consequently. BOD is the quantity of oxygen consumed at 20°C and in darkness during a fixed period of time. A discussion on water quality is not complete unless mention is made of the biological monitoring of surface waters(ll). While nitrates are needed for increa"ing agriculture productivity. BOD or BOD.). The geochemical system of water quality classification rests on the basis of the predominant cations and anions that are present in equivalents per million. (b) Sodium bicarbonate. the normal activity of the fishes can be recorded.C2S4 (Bad) etc. In this technique a number of fish are maintained in a channel through which l\ part of water stream is diverted and their physiological responses are recorded for symptoms of stress. boron concentration should not exceed 1 mgll. Another classification makes use of the specific conductivity and Biological Oxygen Demand (BOD) as the defining parameters(3). is the most satisfactory parameter for characterising the concentration of organic matter. If BOD is greater than this value. The problem of fluoride has already been dealt with.water in the test channel emit signals of the order of 10 to 15 IlA. By convention. In waters meant for irrigation. chloride takes precedence over others. more than 50 mgll is not to be allowed in water for domestic use. If chloride is present at over 250 mgll. By suitable amplication and integration. 2. a part of the organic matter carrying bacteria and pathogens is likely to escape removal and pass into the water distribution system. especially for domestic use. While such systems have been used in many countries for monitoring the quality of flowing river water.(IO). it is not suitable in food processing and if it is over 1000 mgll. Their muscle potentials are of the order of 60 to 80 mV wl1ich are attenuated by the dielectric constant of water. (a) Calcium bicarbonate. which is the quantity of oxygen consumed during 5 days of incubation. the water is not suitable for industrial cooling because of the corrosive effects of the chloride ion on several metallic surfaces. water quality is often referred to as CIS I (Excellent) --. WHO has imposed a limit of 4 mgll on the BOD of raw water to be used for pubic supply.

8 EXAMPLES OF SURFACE WATER QUALITY IN INDIA To illustrate some of the points discussed above. Class 5: Unsuitable for all purposes.Physico ~ Chemical Characteristics 13 toxic substances inhibits bacterial life and gives a low BOD which is not necessarily a sign of clean water fit for consumption. PWD.S. 2.1 RiverWaters In a study of the Cauvery river by the Soil Mechanics and Research Division. natural waters have been divided into five classes as shown in Table 2. Government of Tamil Nadu(9). Considering specific conductivity and BOD together. A study was also conducted of the water quality in 14 reservoirs and an attempt was made to correlate the electrical conductivity with either bicarbonate. it has been shown that all along its course. Class 4: Suitable for irrigation. Class 1: Suitable for public consumption as well as other uses. Obviously water drawn from these locations.7 Classification of Natural Waters(3) Specific Conductivity BOD LOW 9S% of the time less than 4 ppm Class I Class 2 Class 3 Class S@ HIGH More than S% of the time above 4 ppm Class 4 Low (9S% ofthe time less than 7S0 IlS/cm) Intermediate High (95% of the time more th'ln 22S0 IlS/cm) @ All toxic Constituents come under this class. These are only typical examples and a voluminous data is available on water quality of surface and ground waters in India. the water is of the calcium bicarbonate type. but treatment required for drinking and for industry. In most . watering cattle. The water quality as a function of the beginning and end of flow season in the river all along its course indicated . will be less suitable for irrigation. Class 2: Suitable after some treatment. that TDS is less at the end of the flow season. turns it into sodium bicarbonate type. except at certain locations in Salem and Tiruchirapally districts where the discharge of industrial effluents into the river. water quality data assembled by different organisations in India. chloride and sulphate.7 : Table 2. Class 3: Not suitable without proper treatment for any purpose. are presented below. 2. except for . but not fit for irrigation if a better source is available.

NO.9 F' Silt SAR 1.9 1380 31 7.8. the chloride went up from 9 to 13 percent(1J). the data on Godavari and Tungabhadra river waters at relatively unpolluted locations. however. .14 Water Chemistry cases. the rainfall lowered the specific conductivity.8 1. While the bicarbonate value diPPed from 44 percent to 17 per cent of the total anions.6 920 68 24 180 464 120 137 0. Several variations of water quality can be seen from. Conductivity Ca Mg mgll Godavari River June '82 AErn'I2 39 7.4 - 8.' River SeEt.8 298 127 "7 S. Data or River Water Monitoring In Andhra Pradesh(U) Parameters Temperature 0c pH Sp. The Maharashtra Engineering Research Institute has carried out water quality studies of Krishna. The reservoir waters are mostly of the CIS I or C2S 1 type.3 1. Interestingly the C.. At Tungabhadra's sample location. the parameters do not vary much between the beginning and the end of the rainy season indicating scanty rainfall. clearly shows the effect of rainfall on the water quality of the Godavari at'the sampling location~ as shown in Table 2. while an increase is seen in bicarbonate and silt.8 2. the river water is not suitable for irrigation because of salinity. SI type were mildly acidic in nature. In addition. Krishna.6 Tl:lnga~Juidra Jul~-'n. These studies were extended to locations down stream of paper mill discharges into both the rivera..1 0. while some showed a good correlation with chloride. mgtl mgtl mgll mgll mgll mgll HC03' mgtl SO 47 2.l.S SSO 20 18 64 201 39 104 5.9 In Godavari's sample locations. Bhima and Tapi rivers as well as of several reservoirs(12).8..4 117 3.3 186 4..S 62 189 mgll mgll Na K CI' SO. heavy pollution was noticed down stream at Nasik.4 2. It was seen that the change in water quality after mixing with the effiuents was more marked for Tungabhadra than' with Godavari. the correlation was good with bicarbonate. Godavari. Bhima and Tapi river water was mostly of CIS I or C 2S l type with only a few locations showing C 3S I' On the other hand the water quality in the Godavari ranged all the way to CSS I indicating that in some locations.4 0. Table 1. There was one reservoir which showed sulphate correlation with EC. '82 29 28 7. This study by the Andhra Pradesh Engineering Research Laboratories(13). whil~ C2S1 type were alkaline. calcium and chloride.0 "00 13418 182 14 34.

Muharikpur 29.ion Into Coastal Well.530 930' 1.400 11.10. there are ~umerous examples of wells where the groundwater is highly saline. in the Gurgaon District of Haryana.312 16. Similar studies on sea water intrusion have been reported from Thane District in Maharashtra(15).5 (113) 6. The chemical composition of some of these well waters is given in Table 2.9)(14).8.540 2.S • 6.0· 7.210 2.8.S • 7. large quantities of natural waters are employed by the electricity generating units for cooling condensers(17).970 .11 are required.11 gives six examples of raw water quality from different parts of India(18).110 5.480 8asirpur 24.320 11. From the same source of raw water.Chemical Characteristics 2. so that they may be termed as "brine wells".0 (101) 200· SOO (7S) 30·70 (60) 7.0 (II) EC ( IlS/em) 200 (142) 800· 1200 (38) ISO· 300 '(IS) > 1200 (30) > 300 (37) Chloride (mgll) 30 (17S) 70· ISO (47) Note: The number within parentheses indicates the number of well in the range of the parameter measured. Table 2. A study of 334 wells along the coast line ofDakshina Kannada district.9. a number of such brine wells exist and are being used as a base for thriving salt industry.760 7. A few comments on the data in Table 2.555 12.400 1.8. 2.0 (48) > 8. Table 2. A although it is from a canal drawn from a big river. As such it would be instructive to have data of the type of water quality available to such utilities. they make use of a smaller amount for the production of demineralised water. The quality of otherwise good groundwater in wells is brought down by such intrusion due to excessi~e withdrawal. Saline Water Intru. is also a partial dumping ground for the sewage of a metropolis.182 16.Physico . Karnataka is illustrative of this phenomenon (Table 2.4 Cooling Water Quality in Electrical Utilities in India As mentioned earlier. as well as the highest permanganate value am~mgst the set indicating a high organic 10ad.S (61) SOO· 800 (49) 7. Chemical Composition 01 Some Brine Waters.3 Highly Saline Ground Waters In the arid and semi-arid regions ofIndia.The latter poses problems for the demineralisation plant. This is clearly reflected in higher value of specific conductivity. . Sourc.500 2.300 2.e.670 3. In Karnataka(14) pH 5. Table 2.S • 8.10(16). naryana(16) Constituent in mg/I TOS Chloride Sulphate Calcium Magnesium Sodium Sultanpur 28.2 Coastal Wells Intrusion of highly saline water into the wells along the coast is a fairly well known phenomenon. About 50 km southwest of Delhi.350 5.

5 '2. Sept.8 0.3 268 257 245 0.1 177 7.0 146 156 34 2.8 D: E: F: River water by the side of an urban metropolis in North India.8 1.9 49 59 5. Sept. (River) Raw Water Analysis with Seasonal Variations as used by Electricity Generation Industry.6 877 7.6 92 126 48 400 8.9 10. Table 2.5 32 43 5. C Jan.6 101 121 49 10. Ground water (Borewell farm) in South India by the side of an urban metropolis and sea.4 19.6 112 134 278 8. ~ ""t ~ g :! ~ ~ a . Sept. 438 8. River water in Central India with other industries nearby. River water in Western India. Sept.6 771 76 222 247 146 0.0 51 65 5.4 60 85 7. E F Jan.5 76 63 84 7.2 277 8. A Apr.5 479 8.7 470 8.5 15. Jan. B Apr.6 98 120 50 306 8.3 158 7.5 113 123 348 8. India(l8) Chemical Parameters Specific Conductivity IlStcm pH Total Hardness mgll as CaC03 Total Alkalinity mgll as CaC03 Chloride mgtl Permanganate Value meq/I A: B. Apr.6 309 8.2 0.2 83 72 136 7.0 3.2 85 127 45 970 7.8 1.0 119 112 35 7.6 126 8.0 102 146 34 4.9 0.'"'0.11. Apr.0 11. C: Jan.8 17. Sept. Jan. River water in East India. Sept. Apr. Apr. River water in South India. D Jan.3 523 233 50 0.6 0.

C. during the demineralisation process. 5. USGS Water Supply Paper. 943. India (19) Specific conductivity uSI<. 2. although river water. belongs to the class of weak anions. in all other cases.Physico . probably due to the locations of industries nearby.C.5 \0 mg/I as CaC0 3 110 16 2 10 138 This type of analytical information is needed for designers of demineralisation plants. (1971). Organic load is seen in Source C. National Environmental Engineering Research Institute Staff (1987). Source F is moderately "clean".'1.12. as well as the nature of these ions. Table 2. A nuclear power station located near an artificial reservoir created by a dam on a river in India uses raw water whose typical analysis is shown in Table 2. 3. 2220. R. bicarbonate decomposes after the passage of w~ter through a strong acid cation exchanger giving rise to carbon dioxide which needs to be vented off. This imposes a considerable load on the demineralisation plant of the utility. 2200. Source D. While all the cations belong to what is known as the class of strong cations. while at location E. (1982). Source E is from a groundwater farm (typical borewell waters) and one can readily see the high salt content. Basic Groundwater Hydrology. As seen later. Kemp.\.H.Chemical Characteristics 17 Sources Band C are fairly clean.B. In general. Basic Groundwater Hydrology. Typical Analytical Data of Impounded Raw Water from a Reservoir. the condensers are cooled by sea water. Apart from E. the major anion. USGS Water Supply Paper. where the balance between cations and anions is clearly established.m pH M Alkalinity P Alkalinity Total dissolved solids mg/I Total suspended solids mgll Silica in mgll as Si0 2 Turbidity in mgll in silica units Total hardness mgll as CaC0 3 Ions Ca Mg K Na Total Cations mg/I as the ion 22 9 2 21 mgll as CaC0 3 54 36 3 45 138 Ions Bicarbonate Chloride Nitrate Sulphate Total 275 8. R. REFERENCES I. the bicarbonate.12(17). Water Research. Heath. (1982). Nagpur. the values of specific conductivity are lower in September. has a greater content of dissolved impurities as seen by high values for specific conductivity and chloride. P. seasonal variation is seen. India. Report on Technology Mission on Drinking Water in Villages and Related Water Management. 4. Heath. WTM/CSIRINEERII004 . The power plant condensers are cooled by the same raw water in case of A.2 110 Nil 145 5 \0 5 90 Anions mg/I as the ion 134 11 2.C. Chemistry of Natural Waters .D and F. indicating the general dilution effect of the monsoon.

V. Water Pollution & Management Reviews.5 I.B. Gajendragad and C. Central Board of Irrigation and Power.• 17. Central Board of Irrigation and Power.127. Water Chemistry Purdom. pp. 2nd ed .D. J. Nliganna (1985). 7. pp. 18. P. World Health Organisation. of Power and River Valley Development. Sheela and A Shyamala (1985). III . p. Academic Press. Venkateswarlu (1985). pp. 124 . M. V. A. 19. US Salinity Laboratory Staff (1954). Soundarapandian V. Biological Monitoring of Surface Waters. pp. 25. Proc. Seasonal Variation of Water Quality Along the Coastal Tract of Karnataka . (Ed. (1971). pp. 14. Narisimha Rao (1985). Geneva. Reiff.t 16.Gogate. Indian Geographers. V. Rameshwar Rao C. 103 . Chandrakantha. Biswas. New Delhi.S. and T... Production and Quality Control.V. US Dept.W. G. K. lind A. Proc. 9: 10.R. TrailS.525. Central Board of Irrigation Powe'r. 60. 187 . Strauss. 1988). 113 . (1985). 13 19. 91-102. Ibid . National Interim Primary Drinking Water Standards as given by Laws E. Nair (1983). Maharashtra. Studies on Pollution of River Waters (Godavari and Tungabhadra) by Effluents From Paper Mills. Proc. Power. athi. New Delhi. of Agriculture Hand Book. Workshop on Water Chemistry in Thermal Power Stations. Central Board of Irrigallon & Power.A Case Study. New Delhi. and K. New Delhi. New Delhi. (19!l4). S. Study of Water Quality of Ri vers and Reservoirs in Maharashlra State. .18 5. K.192. In Water Pollution & Toxicology.• I. Ranganna. 41 . Saha. Demlneralisation of Water: Principles. 19 . Diagnosis and Improvement of Saline and Alkaline Soils. Inst. M. 16. Seminar on Water Quality and its Management. Encyclopedia of Physical Science and Technology. From Raw Water to Pure Steam: Problems in Thermal Power Stations. Corrosion and Maintenance. 8. Monitoring Organics· An Overview.M . Sila (1987). pp. V. S. 17. USA. pp. Central Board of Irrigation and Power. 2nd ed . Water and its Impurities. Seminar on. Ground Water Resources of India With Special Reference to Their Salinity and Pollution Hazards. B.. 13.• WHO. II.K.110.S.K. Water Pol/ution and Management Reviews. Salinity Ingress Coastal Parts of Thane District.23.P. (1982). (Sept. Importance of Water·Quality in the Use of Large Volumes of Water for Condenser Cooling in Power Station. pp. Ind. 91 . 12. B. pp.46. Venkateswarlu (1975).). Re . (1988). 154 • 155. 8. Kokani. 95. Quality of River and Reservoir Waters of Tamil Nadu. (1981). ( 1985). 6. 15. Gurappa. G. Water Quality and Its Management.S. 9(2).G. Ramshesh and K. Padhye . Environmental Protection Agency. Nayak. Guidelines for Drinking Water Quality.A.127. Ibid.

The two hydrogen atoms are bonded to the oxygen at an angle of 104. through the use of cooling ponds.3 PROPERTIES OF WATER AT HIGH TEMPERATURES AND PRESSURES The physico-chemical properties of water arise as a result of the structure of the water molecule and its ability to fonn hydrogen bonds in condensed phases. These properties are unique to water.1 (I). around the first hydration shell.1 THERMOPHYSICAL AND THERMOCHEMICAL PROPERTIES OF WATER The trermophysical properties of water are listed in Table 3.ility of the lone pair of electrons on the oxygen. When water is employed in industry for cooling. An important example of anion solvation 'is the formation of a hydrated electron (commonly referred to as the solvated electron) wherein the positive ends of the water dipoles surround the electron. cooling towers etc. 3.5°. which in turn are hydrated (specially the cations) due to the co-ordinating ab. close to that expected in a tetrahedral arrangement. The O-H bond length is 0. The hydrogen bonding often leads to he formation of a secondary shell of hydration.957 AU. the temperature of water ranges from the ambient to about 60°C. in combination with process water heat exchangers. The only other substances that have such proclivity to a limited extent are liquid ammonia and liquid hydrogen fluoride. The two lone pairs of electrons on the oxygen are positioned to give a psuedotetrahedral arrangement. These two properties make water an excellent solvent in which elctrolytes such as NaCI dissociate into ions. The bent shape of the water molecule bestows it with a high dipole moment and bigh dielectric constant. In view of .

28 The combined effect of such decreases in density.9584 at 100°C. as shown in Table 3. this would mean an increase in the mobility of H+ and OH" ions that are present due to water dissociation. Thus a simultaneous and equal increase in the values of [H+] and [OH"] due to the \increased dissociation of wate. 007 374.2 Changes in Surface Tension and Viscosity of Water with Temperature(l) Surface tension (Dynes/cm) Viscosity (Centipoise) OOC 75.cal/mole Sp. upto 100°C and the other beyond 100°C where pressure i5 to be applied to keep water in the liquid phase. it is appropriate to consider the dependence of the physical and chemical properties of water in two temperature ranges. properties of water at higher temperatures (well beyond 100°C) under pressure are of no consequence in this segment of water use. . while at OoC it is 0.20 Water Chemistry this. the ionic product (Kw) of water is very small (pKw or -log IOKw = 14). either fully or in equilibrium with the steam phase.69 0. The behaviour of water and steam beyond the critical point of 374°C is also of interest.998 Vapour -57. when water is used to make steam. °c Critical pressure. Thus when one considers steam generation either for production of electrical or motive power.2: Table 3.8 -54. 3.9 0.r with temperature.15 212. On the other hand. the properties of water and steam at high temperatures and pressures become relevant for understanding the chemistry involved. would mean that the pH scale.32 -56. This is due to the collapse of some of the l.9971 at 25°C and 0.1 Thermophysical Properties or Water (I) ____ Property Heat ot formation at 25 0 C K. The pH is defined as log IOH+ and Kw is the product of [H+) and [OIl") concentrations. 79 100°C 58.000) at 4°C. surface tension and viscosity of water (25 to 100°C) is to increase the mobility of the cations end anions present.28 In view of the temperature difference between cooling water systems and the steam generating systems. the density of water is maximum (1.2 PROPERTIES OF WATER BELOW lOOoe In the temperature range of 0 to 100°C.2 0. At ordinary temperatures..32 3.callmole Energy of formation at 25 0 C K. the temperature in the boilers and the associated steam turbines is in the range of 250-320oC.64 1. The decrease in density results in a decrease in the surface tension and viscosity. g/cml Critical volume cml/g Liquid -68.drogen bonds and the release of water molecules trapped in the cavities.9999. Table 3. as wei: as pH as defined wIll be effected by an. Beyond 4°C the density decreases to 0. In the case of high purity water.6 I. Kg/cm2 Critical density. viz. Heat cal/gfOC Critical temperature.

07 0. so that a higher temperature can be reached. the pH of pure neutral water defined to be 7.5 7. due to its dielectric constant.25 at 100°C. This important property of water also undergoes a change with temperature.0 1.169 1.8 15. it has some relevance. For example.0 1. the neutral point shows only an apparent decrease.5 1.5(2.4 14.1 47.the value of the dielectric constant of water is 88.984 1.3 PROPERTIES OF WATER ABOVE 100°C In steam generating systems operating at temperatures well above 100°C.36 2. The very fact that the hydrogen ion concentration increases with temperature in pure water.3). the distribution of solutes is a fucntion of temperature and pressure. increases to 52 x 10.0 22.5 at 25°C and to 55.33 -4.3 Thermophysical Parameters oCWater as a Function oCTemperature and Pressur-e(l) Parameter Pressure K.5 Enthalpy KJMo)-t 1.) This means that water loses its ability to effect the dissociation of electrolytes and a fraction of the dissolved substances remains as an undissociated or neutral chemical species. Examples are Fe(OH)3' Zn(OH)2 and Ni(OH)2.14 . It should be made clear at this juncture that pure water at 100°C will continue to remain neutral and because of the compression of the pH scale at 100°C. Consequently. 3.14 at 25°C begins to contract with increase in temperature.5 15.0 1.7 33. The known range of the pH scale of 0 . Pressure in itself has only marginal effect on the water chemistry (except with respect to the elevation of its boiling point).213 0. The thermophysical parameters and other properties of water as a function of temperature and pressure are given in. 3.060 1. electrolytes such as sodium chloride dissociate into their component ions on dissolution in water.18 -1. The overall effect is that pure water at 50 to 60°C is a more aggresively corrosive fluid than at room temperatures and steps will have to be taken to keep the corrosion rates in the cooling water systems within acceptable limits. makes it much more aggressive to metallic surfaces at higher temperatures than at room temperature. which decreases to 78.1 32. This will be dealt with in greater detail in a later chapter. but has a profound effect on what has come to be known as steam chemistry. At OOC. While in the temperature range under consideration this effect might not be of that much importance for strong electrolytes such as NaCl. In the two phase system of water and steam.4 and 3.14 at 100°C.3 46. a Table 3.03 7.4 .0 at 25°C decreases to 6.Tables 3. whose value at 25°C is 1 x 10.72 14.000 1. rather than temperature alone.29 -5. the need for thermal efficiency requires the application of pressure.3.0114 1. bar Temperature OOC 100 200 300 Specific Volume Gibbs Free Energy KJMoJ-t cm3/~ 1.Properties of Water at High Temperatures and Pressures 21 increase in the temperature of water. the ionic product.0. for weaker electrolytes such as the hydroxides of corrosion products.0 1.9 22.3 at 100°C (and 760 mm Hg. As is well known.5 1.28 Entropy JMoJ-toK·t 1.

3 30.8 37.2 19.1 21. Table 3.7 0.0 31.5 296 194 148 121 lOl 1.5 14.4 Variation in the Properties or Water with Temperature and Pressure(2) Property Pressure K.0 308 205 162 132 113 100 150 200 250 300 350 • To convert values into centipoise mUltiply by 10-3 @ Phase transition ~ ~ .4 38.4 29.2 17.5 0.. ~ s· :! ~ .3 1.25 694 706 690 650 582 0.. .1 689 697 677 629 554 0.0 36.7 34.3 20.1 0...Bar Temp.75 57..75 712 733 736 718 674 0.8 0.8 27_1 20.2 35.4 28..6 703 719 713 684 628 0..oC Thermal conductivity mJ m-I sec-10K-I Static dielectric constant Farad Steradiam per meter Viscosity· J1N Sec mm2 0.1 287 185 137 110 @ 0.5 57..0 58...4 24.1 55.4 25.25 56.5 25.

Table 3.6 gmlcc at 250°C to 0.o. Of the different ions.10 200 1. 3. both measured at a constant pressure of 100 kg/cm2 (1450 psi). 250 to 300°C.S/cm 4..5(\ 10 3 4 10 1. like NaCI in water. the conductivity ofan elctrolyte.5 Density or Water : Variation with Temperature and Pressure(3) Density of Water at 4 K bar TempoC Density gm/cc 100 1. It so happens that the maximum conductivity of different electrolytes in water.6 x 10-4 ~S/cm.87 500 0.6 x 10-4 The limiting equivalent conductances of several ions in water have been determined as a function of temperature at saturation vapour pressure.5 x 10-8 ~S/cm at 25°C.6. the effect ofincreased ionic mobility due to the reductions in density and viscosity gets nullified at a certain temperature. This in turn makes water very aggressive to the metallic surfaces with which it comes into contact and thus promotes corrosion. Conductivity J.5 X 10-8 2.6 Specific Conductivity orWater at Different Temperatures Temp OOC 20 31 49 86 156 274 Sp.1 x 10-6 7.01 10 102 0. Since the number of ions of a given electrolyte are proportional to the dielectric constant (due to increase in temperature).5 sm/cc at 300°C.00 lOs 2.3 x 10-s 7.2 x 10-6 5.l. lies in the temperature range of interest (235 to 325°C) to steam generating systems of power stations. goes through a maximum when measured as a function of temperature.1 x 10-7 1.95 400 0.00 In the temperature range of interest to the steam generating sytems. the density of water decreases from 0.82 23 Density of Water at 500°C Pressure Density Bar gm/cc 0. In other words. The decrease in density and viscosity coupled with the increase in the dissociation constant of water with increase in temperature results in increased conductivity of pure water as given in Table 3. the conductivity of pure water at 275°C increases to 7.Properties o/Water at High Temperatures and Pressures Table 3.10 0. Compared to a value of 4.4 EFFEcrs OF TEMPERATURE ON THE IONPRODUcr OFWATER The effects of high temperature are nowhere more striking than on the pH value or the pH scale of water and alkali sing weak electrolytes such as ammonium and lithium hydroxides dissolved in water.1 shows the temperature . hydronium (H30+) and hydroxyl (OH-) ions show a large increase in A. viz. Figure 3.05 300 0.

5 at 25°C is lowered to 7.4 at 220°C. water would be most aggressive in the range of 230 to 250°C.. The minimum ofpKw (or maximum of Kw) lies in the temperature range of230 to 250°C. Although there is some difference in the pKw values as determined by different workers. Tem~eratures(8) dependence of the exponential of the ion product of water (pKw) in the range of 170 to 340°C. Mesmer.77 6. viz.5 a.1.28 LiOH 10.12 7. An ammonical solution of water that exhibits a pH of 9. On the other hand. the pKw of water decreases (or Kw increases) upto a certain temperature and then increases (or Kw decreases) as the temperature is increased further. Table 3. 3.76 at 220°C (Table 3. the neutr~l pH value of high purity water at say 240°C is 5. As seen earlier. Marshall and Frank(6) b Co a 11. Similarly water spiked with LiOH that shows a pH of 10.41 6. though both H+ and OHconcentrations will be at their maximum in equal measure.76 8.16 5. The consequences of such changes are discussed later.80 8.24 Water Chemistry 12.0 ~ ~ 11.1 being a little over 11. since the pH scale and the point of neutrality of pure water are defined in terms of pKw and the minimum of pKw value as seen in Figure 3. Cobble(4) c.50 8.89 NH40H 9.96 6.7 Changes in pH of Water. Thus.1 Plot of pKw of Water Vs.00 6.7). It is once again emphasised that pure water will continue to remain neutral under such conditions. Helgeson(7} d.67 5.5 at 25°C is reduced to 6.12 The dielectric constant will continue to decrease with increase in temperature in the range of 100 to 300°C. the trend is the same.50 7. the dielectric constant of steam will increase wfth an increase in presssure required to maintain such a .0 473 573 T E M PER AT U R E (OK) Fig. Baes and Sweeton(5) b.55.83 5. Ammonium and Lithium Hydroxide Solutions as a Function of Temperature TempoC 25 100 156 218 306 Pure Water 7. Thereafter the neutral point shifts to higher values.

U. J. REFERENCES l. Chem. 71. whether they are fired by fossil fuels or nuclear energy. The Thermodynamic Properties of Aqueous Solutions . Vol. and J. Plenum Press. we come across the behav~our of high temperature . In other words. . Acidity Meassurements at Elevated Temperatures. W. (1986). A certain amount of individuality characterises each system that arises from the interaction of specific materials of construction of the steam-water circuit. Franck (1985). E . F. Chem. 5. Phys. However. Reference Data. Analytical Scientists. and E. (1972). L. H. Soc. where specific volume. Thermodynamics of Complex Dissociation in Aqueous Solution At Elevated Temperatures. so as to achieve maximum efficiency and economy in energy generation . TPRDIBI08781R 86. M. (1991). (1957). J.• C.2°C).K.. 6. under such a condition. R. In natural systems such phenomena are encountered in geothermal waters/steam. Soc. Water in the Environment. a given solute will be distributed equally between the two phases. MSP (85)3. It is obvious from the above discusssion that the properties of water undergo significant changes as a function of temperature a'ld presssure. the density of water at 20°C as function . At the critical temperature (374. the greater is the solute content of the steam phase. and R. H. Phys. F. V. J. 3121. Walsch. Chem. Water A Comprehensive Treatise.W. and M. 815-823 (from the experimental Hugoniot Curve for water in this paper. Chem.1 the classical steam engines used for locomotion. Ind. C. 74. Am. 86.of pressure can be computed). Marshall W. However.295. A Review of!>H Calculation and Corrosion Product Solubilities Under PWR Primary Coolant Chemistry Conditions. 4. Mesmer. Baes and F. Dynamic Compression of Liquids From Measurements on Strong Shock Waves. 3. 463 ed. J. Sweeton (1970). 2.high pressure water fm . this is a limiting condition. Report No. 1937. 26. Helgeson H. (1964). pp.Properties of Water at High Temperatures and Pressures 25 temperature. Rice M. Chem. 5394. the ratio of the two dielectric constants (DC of steam / DC of Water) is unity. I. J.VI. In modern industrial practice. The vapour transport of solutes like silica are attributed to this dependence and the higher the ratio. which deposits the solute at a different part of the steam water circuIt where temperature and presssure are lower. Cobble J. Central Electricity Generating Board. 10. U. Phys. volcanic activity etc. K lyer. there are enough common points to broadly discuss and understand the application of the basic concepts of physical chemistry of water and its dilute electrolyte and non-electrolyte solutions to industrial practice. Sudarsanan M. 7. (1957). 8. cm 3/g is plotted against shock pressure in Kilobars. to highly complex steam-water circuits of power plants.ll-19. Phys. Todheide K. Franks. Polley. Thornton E. in which the ratio is a function of temperature and pressure. Bull. What is of greater interest is the range of 235-320oC.. Water at High temperaturess and Pressures.

that signifies different things to different professional chemists.1 CORROSION IN AQl}EOUS SYSTEMS Corrosion in an aqueou!> SY3tem occurs due to the interaction between the surface of the mr. On the other hand. between a metaJlic or a fine oxide surface (solid) and water (liquid) and steam (gas)(1). The focus of the present monograph is on water chemistry in such a high technolo~ based industry. water chemistry would mean the analytical determination of impurities especially the trace toxic inorganic and organic contaminants in water and the detoxification proC'esses thereof. On the other hand to a chemist in a power plant or other industries such as fertilisers. 4.4 WATER CHEMISTRY. The latter. corrosion signifies essentially the same to all professional metallurgists and chemists. water chemistry would immediately signify the chemical regime that is reqUired to be maintained in the steam-water circuits so as to minimise corrosion and material transport. To an environmental chemist. For a chemist involved in a chemical process industry. Material compatibility is the interface between the two specialities of watei: chemistry and corrosion s·ince what one is concerned with is basically an interfacial phenomenon. MATERIAL COMPATIBILITY AND CORROSION Water chemistry is a relatively new sub-branch of physical and inorganic chemistry. while effluent treatment and environmental chemistry of natural waters is touched upon only for the sake of completeness. water chemistry is equivalent to effluent chemistry and effluen~t treatment. Here it would lead to the generation of radioactive nuctides and their transport to unshielded locations where maintenance and repair are needed(l). although on a very small -scale is of serious concern to the chemists associated with the nuclear power industry.terials which come IOtO contact with the aqueous environment. many .

akened D1I. The stress could be chemical in the sense that the aqueous environment may be acidic or alkaline. t "'F ~.2) The primary corrosion product is [Fe (H 20)s OH]+. These two chemical species appear later. . To avoid or minimise corrosion.O It(OAAr~ON SHl:ATH _ ~TlOll WlTH F. The stress could be metallurgical in the sense that the material surface has defects.I) Fe (Bulk) + Fe 2+ + 2eo (4.DlSSOLIJTION.w. Fe (OH)2' Fig 4. The problems posed by faulty water chemistry or material incompatibility are the same in thermal and nuclear power stations as well as in chemical process industries such as fertilisers{3}. StopS I 1. . 4.AIUSATION Of IIt.VATION . Dipolo. great care has to be taken in selecting the construction materials as well as in controlling the chemistry of the aqueous environment.dbutod 1'" _ I'Ol. Fig. to. which gives the second hydrolysis product.1) (4.4.< :® 1 . The chemical stress can be viewed or understood in terms of thermodynamic and electrochemical concepts. ClOClDATION ME1l'L ""''ItII 2. where no other electrolyte is present to any significant extent.1 Mechanism of the First Step in Iron Corrosion . ran60111ly III o-H aond in H O . It might be thermal stress as in a steam generating system. Matenal Compatibility and Corrosion 27 times under conditions of stress. which show the combined effect of solubilisation and hydrolysi3(l). Basically. n Fe (Bulk) -+ (n .Water Chemistry. either inherent or as a result of the manufacturing process.1. ~e (!)H. which is the first step in the corrosion process.O DIPCU II ::. The polarisability of the water molecules on contact with the iron surface leads to the weakening of the O-H bond and gives rise to reactions below.nolec. corrosion would be the consequence of a combination of all the above stress factors. in many forms due to secondary reactions as shown in Fig. In reality.(U: IN PRESEN:£ OF SPEClflCALL Y IIBSOlIBtD ANION. it is the solubilising action of water on a metal surface like iron.. sa.2. In high purity water. corrosion is a process where the metal atoms leave their location on the surface and stabilise in the form of ions in solution.

In high temperature. if the water is deoxygenated. Fe 20 3 etc.28 Water Chemistry The secondary products are FeO.4. the percentage of iron present in each of the ab0ve forms also shows a pH dependence.2). (4. 2e' + 2Hp (4. which get converted to magnetite in a short time. FeO.5) ° ~ 20R' + H2 (4.4) 2e' + 1/2 2 + H 20 ~ 20R' Reaction (4. These secondary reactions being pH dependent. the principal corrosion product formed on an iron surface (carbon steel. corrosion is less. Fe 30 4 (Fig. Corresponding cathodic reactions may be written as. stainless steel) is magnetite. there is a possibility for Fe (OH)2 to exist as neutral molecules in solution. the smaller will be the cathodic reaction (4. Under the ccnditions specified.3) points to the pl)ssibility of hydrogen formation in a corrosion process.3) A • AGEING Ht· HEATING P • PRECIPITATION H • HYDROLYSIS • OXIDATION R • REDUCTION D • DEHYDRATION Fig.4). The lower the dissolved oxygen content of water.OH. In general. Fe30 4 .2 Possible Species of Iron under Aqueous Environment \ . while reaction (4.1) in terms of the fundamental galvanic dissociation of metal atoms (in this case Fe) from a surface in contact with water is anodic. slightly alkaline and deoxygenated aqueous environment. 4. Reaction (4.4) gives a clue as to the role of dissolved oxygen present in water.

galvanic ac~ion will cause one of the surfaces to corrode rapidly. Examples are.g. The former is a localised phenomenon occurring along the grain boundaries such as the corrosion of stainless steel in heat affected zones of a weld. a process of material transport.7). is set up in the closed.. From a metallurgical view point. There is evidence to indicate that magnetite is also formed directly on iron surfaces as follows: 3 Fe + 4 OH~ Fe30 4 + 2 H2 + ne - (4. Fe304 unC:ergoes a series of substitution reactions with the alloying elements (Cr and Ni) and complex ferrites such as CrFe 20 4 and NiFe 20 4 have been identified in the corrosion products. Thus changes in solubility of magnetite would mean that in a closed.an iron surface leads to a sudden volume expansion.3). Since pH scale as defined undergoes a change with temperature. the determination of the hydrogen content of steam (in view of the very limited solubility ofH2 in water) serves to monitor the overall corrosion process in the steam water cycle. although on a small scale.7) Compared to the bulk density of Fe (-8g/cc) that of:nagnetite is lower (-S.~ H2 + nOH. but circulating heat transport system. which as noted earlier could have its origin in chemical. caustic cracking of boiler.:f two dissimilar metals I alloys are in contact through an aqueous environment. A GO of -9. as a result of which porosity is developed. Material Compatibility and Corrosion 29 This reaction is known as Schikkor reaction(4). as experienced at inlets of condenser tubes of a sea water cooled power station. tubes. electrochemical and metallurgical parameters.corrosion. A purely mechanical form of attack is the erosion . Thus.9 kcal at 298°K (2S°C). There are other specialised forms of corrosion(5).6) H20 (Bulk) + ne. one must be very clear about what is specified by pH.S) is in addition to that from (4. measured at 2SoC or say at 300 oC.reaction (4. In actual practice. wi~h a thermodynamically favoured standard free energy change.. On stainless steel surface. it would be advantageous to complete the discussion on corrosion.3 and 4. magnetite gets transported (solubilised and redeposited) from relatively hot to cold sections of the system. Concentration of impurities in crevices and under deposits leads to an attack termed as crevice corrosio. Hence the direct formation ofFe 30 4 on . e.2 g/cc). The de-zincification of brass is an example of selective leaching from an alloy. cracking of stainless steel in a chloride environment etc. What was discussed so far is a general at&tk occurring uniformly over metallic surfaces on contact with water. 4. Before dealing with the behavior of magnetite and other oxides in high temperature aqueous environment. intergranular corrosion and selective leaching need (0 be mentioned. The use of sacrificial electrodes is a direct application resulting from this form of corrosion. Another form is known as stress corrosion caused by a synergistic effect of tensile stress and conosive environment. 4.Water !hemistry. as illustrated in Figs.2 SOLUBILITY OF MAGNETITE (FE 30 4) In the temperature range of interest to power station water chemistry the solubility of magnetite and other corrosion product oxides is proportional to the temperature and pH(6. extremely localised attack resulting in pits and even pin holes such as in chloride induced pitting of stainless steel under stagnation.(Bulk) (4.4 Different sections of the steam water circuit are at different temperatures. circulating . The hydrogen generated in. Pitting is one such.

4.373 K 6.4 Solubility of Maanetite at 300 ·C VI.01 - '! I I '$ !l 3 4 ~ 0 ~ 0 8 8 8 0 ~ 8 9 0 ~ l- I- 5 6 7 10 11 pHaoo Fia.3 Solubility of MaaDetite in tbe pH RaDae 3 to 13 <') 1 I I I I I 'i ~ 0 8 0 at 100 - 1 • 8 10 I- 0 .573K 2..lI! ···s 6 3 4 5 6 la 1 1 6 9 10 11 12 14 13 pt4298K Fia.413K 4.JO C(Fe)lI/mo1 dIi.1 2 ..1 - 0 0.423K 5../ .. t: U- ~ 8 l- c1 - • ~ 0. 10' .f lei 1O' 1~ 1..' Water Chemistry lfl ld 1. pHJOO <') .32:1K lrJ. :::1 1- 0 8 0 0 0 LL.523K 3. 4.

. However. As the size of the particle decreases.... Material Compatibility and Corrosion 3/ high temperature and high pressure water (and steam) circuit. The second one is a diffuse outer layer of counter ions mobile with respect to the surface as shown Fig. ROLE OF ZETA POTENTIAL The deposit forming species are oxides.5 Conceptual Reprentation 01 Electrical Double LayerS) . hydroxides and frequently hydrous oxides. except that unde: deposit attack is promoted by the formation of deposits allover the place. When any solid is in contact with an electrolyte solution. In fossil fuelled power stations.. the surface forces prevail over the mass forces. This is popularly known as the 'man-rem' problem and is a direct consequence of water chemistry at high temperatureS<2). but arranged in two layers which is known as the electrical double layer.~E___l~JE""-. electrochemical and metallurgical faclors operating at the interface of a metal and high temperature waterS). viz.. 4. while the surface forces is proportional to the surface area of the particles (i.. square of the diameter of the'! particles). this phenomenon is of no serious consequence..3 DEPOSIT FORMATION VS. it acquires a surface charge which is balanced by in equal and opposite charge in the liquid layer near the surface.e.BULK OF THISOLUTION FIRST LAYER l' 1----- DII'I'UIE LAYlR Fig. 4. Two major forces are responsible for the deposition of such particles.t . to the cube of the diameter of the particles). in a nuclear power station. The mass force is directly proportional to the mass of the particles (i. ZlTA POTENTIAL i E . The first one is the adherent monoionic layer of counter ions held by chemical forces and immovable with respect to the solid. 4.e. The latter are as a result o( normal chemical. the mass forcos and the surface forces. this would mean the transport of corrosion protlucts through the reactor core and their activation »Y neutrons. These are transported to ollt-of-core surfaces and get deposited on them. leading to radioactive nuclides.Water Chemistry.SHEAR PLANI k-.. thereby contributing to a radiation field which prevents accessibility to the system for maintenance.'..

8) Where K is the proportionality/constant and pH is that of the aqueous phase in contact with the oxide surface.as the only potential determining ion(8).4 8.44 7. ~ and hence the surface charge becomes zero and this pH is known as the Point of Zero Charge(PZC) of the oXide. Table 4.85 5.32 Water Chemistry The difference of potential existing between the shear plane and the bulk of the solution is called the Zeta potential (~.7 ± 0. since PZC is expressed in units of pH.4 9. .3 ± 0.7 6. with H+ or OH. have MOR groups at the surface.0 4.Fe 20 3 Fe 304 CoO Co (OH)2 NIO Nl (OH)2 Cu(OH)2 CuO Cu 20 PZC at 30°C PZC at 90°C (in pH units) 7.ions.4 10. At PZC.36 Cr Mn Fe Co Ni Cu The apparent decrease in pH of water and dilute aqueous solutions is also seen in the values of PZC as a function of temperature. At a particualr pH.2 ±0.4 10.5 6.2 6. the surface has an equal tendency to reiease H+ or OH.3 12.5 ± 0.0 7. The acidic property of these MOH g.pH) (4.8) it can be seen that the oxide surface is positively charged when pH is less than PZC and negatively charged when pH is greater than PZc.5 11. ~ at a constant temperature can be represented as ~ =K (PZC . 4. Pri~ary corrosion products.5 5. Hence.) The magnitude of ~ is a measure of surface charge on the solid surface and its sign is the resultant of the charge on the surface and the charge on the first layer.Fe20J y . Table 4.4 ± 0. From equation (4. NaOH and Si02 at minimum values in the water phase of a steam water circuit.4 11 to 12 9.1 PZC Values of some Corrosion Product Species(8 ) Metal Species hydrous Cr 20 3 Mn(OH)2 Mn0 2 FeOOH Fe(OH)2 a.0 ± 0.4 to 7. as seen earlier.0 to 4.4 DISTRIBUTION OF IMPURITIES BETWEEN WATER AND STEAM While efforts are made to keep impurities such as NaCl.1 lists the PZC values of several corrosion product oxide and hydroxide species.8 11.:::lUPS becomes pronounced as the pH decreases.4 8. they can never be .

Na2 SO.r::: -"- ===::::::..9) For neutral compounds such as oxides. K increases with temperature which would automatically involv~ the pressure of the steam phase.: Ii! • 1 ~~I~ .--I-:::::::::::: ~'a -.. Thus in general. for electrolytes such as NaCl. ii:!~ ~~ CuO N10 ii:l!I.. CaCI 2 NaCI NaOH 160 120 80 60 40 30 DRUM PRESSURE. This is so since the pressure and temperature decrease in the various stages of the turbine leading to the deposition of substances like NaCl and Si0 2 on the turbine blades. 4....2 K .. On the other hand.-. _~::::~ ~ ~~~r--.Water Chemistry. a!. a steam generating system promotes concentrations of such impurities in the water phase..formance of the turbine. an equilibrium between the neutral form and the respective ions also comes into play. Material Compatibility and Corrosion 33 brought down to zero level.~ ~-l·~l7i1ii!Fi§"'iil -- 10-3 10-4 10-5 10"' 10-7 I . CaSO. Hence the basic information on solubilities of salts and metallic oxides in steam and their distrIbution coefficIents. K = ppm(steam) ppm(water) or K = mole / Kg. Martinova(9) has described what are known as the carryover coefficients into steam from water as a function of pressure. ~~ :"""- '. such deposition will lead to the failure of the turbine blades..steam mole / Kg.II.. needs to be discussed for a proper understanding... ATM LICI MgO 10' Fig. This is generally known as a 'ray diagram' and is shown in Fig.6.. 4.. "il!! ~~ aa BaC I i r I I. the distribution coefficient depends only upon the solubility..6 Ray Diagram of Carryover Coefficients of Salts and Metal Oxide Contaminants in Boiler Water(9) ...:::::::: -.. The distribution coefficient K IS defined as the weight ratio of the concentration in the steam phase to that in the water phase. in-·~~~ -.. B2 0 3 [a.:: =. If allowed to go unchecked.a - I I I -[ J ..It1\! I Fa 3 0. Al 20 3 1 JI 220 200 --- I " L + 4 I... " -".. NaOH etc. Dependil'g upon their solubility in the steam phase under the conditions of pressure and temperature of the steam. - .. water (4. By implication. As seen earlier decrease in the dielectric constant of water with temperature will effect this equilibrium in favour of the neutral species. the distribution of such impurities between the two phases is of special rele\ ance to the per. 100 10-1 10.. I ~a [i 20 a. I~ I- .---I..

6 it may be noted that in general. 4. 4. it may be seen that at 2900 C (550Of) and a concentration of 50 percent in the water phase. Si02. .7. The International Association for the Properties of Steam has compiled extensive data on the distribution coefficients and other relev. OF 800 1000 Fig./ 1 ppb . LIQUID CONCENTRATION 1000 SATURATED WATER tOO VAPOR CONCENTRATION 1000ppb 87% ! I Ii 100 I 80% 100ppb I 400 I I I I 20CI / . Thus from Fig. The same data and extrapolations are shown in Fig. The overall conclusions are the same through either method of data representation. on a Mollier diagram. concentrated caustic solutions are possible at virtually every stage of pressure decrease (turbine expansion) that crosses the saturation lines.34 Water Chemistry From Fig.8. As an example Fig. the oxides exist as neutral molecules. 4.7 Caultic Solubility Data Shown on P. the carry over coefficients of Fe304 arid other Fe oxides. temperature (T) coordinates. Calculated data on the vapour pressures of concentrated caustic solutions are also shown in Fig. 4. 4. NaCI and NaOH in steam-water cycles of power plants(10.1J).8. the carry over of metallic oxides to the steam phase is much greater than of salts.7 shows the solubility data of NaOH on pressure(P). considerable quantities of the substances can be camed over into steam. This is to be expected since in the water phase also./ I I I 10ppb . 4.ant information pertaining to Fe30 4. T Coordinatel(lO) The caustic solubility constant composition lines approach the saturation curve asymptotically. If one considers only those area!! with a very small amount of superheat. upto 1000 ppb of NaOH can be expected to be present in the steam. If one proceeds from the assumption that the concentration in the liquid phase can attain very high values locally./ 400 100 TEMPARATURE. Si02• NaCI and NavH are of special importance. The data are basic in nature and valuable in understanding the vapour carry over of oxides and salts. In ~le context of a power plant.

020 0.7 1.030 0.7 +- Pressure . 4.Water Chemistry.8 ENTROPY..012 0. 'of Si02 in water 0. Suffice to say here tha[ increasing concern for low pressure turbine blade and rotor damage by stress corrosion and corrosion fatigue has caused new limits on allowable steam contamination by NaCI. 87% .. IF 1.1 DistributloD of Silica betweeD Steam aDd Water Phases (Kgleml) 86.... NaOH and Si02 to be recommended..2 206.0075 0.050 0. of Si02 in Steam Cone...080 0..5 ROLE OF ALKALINITY IN STEAM-WATER CIRCUITS It has been known for some time that mild steel or carbon steel (one of the main . Table 4.4 U 1... . 1200 1. 4.2 shows the data on this distribution coefficient as a function of pressure..2 172.0045 0. ..0 121.8 148.3 190.8 Caustic Solubility Data shoWD OD a Mollier Dlalram(lO) Silica is one of the impurity deposits that causes considerable damage to turbine blades.0 103.. BTU/LB. (psig) 1273 1529 1793 2039 2193 2550 2815 3059 Cone. The steam carry over ofSi02 is essentially due to the distribution of this compound between high temperature water and steam phases..8 FII. Table 4..1 137. Material Compatibility and Corrosion 35 1300 III ! ~ 1250 .160 Since the solubility ratio decreases noticeably with decrease in pressure (a condition in the steam turbines from the inlet of steam to its e~aust) deposits of silica on the turbine blades are to be expected. Such limits have an impact on the required purity of steam generator feed water.

Because of their differing dissociation constants.00 0. but higher than ammonia is required to attain the same pH value in the condensate. the ratio (concentration in steam / concentration in water).00 80. A study of the distribution coefficients of these three volatile compounds between water and steam showed that for ammonia.60 5.00 Bearing in mind the role .075 0.10) of hydrazine and the associated rate constant are given in Table 4. The volatile compounds. as compared to the non-volatile alkalies such as NaOH have the advantage of being easily carrieo over into the steam phase... the value of this ratio for morpholine increases with temperature.4.3.(ll) in the cycle.. Somehow.10) The typical values for the halftimes of the de('omposition reaction (4.. its role in increasing the pH of the water .05 0.steam circuit has not been well recognised. Thus it has been a practice to make use of volatile alkalising agents such as ammonia..50 50. the concentration of morpho line required is more than that for ammonia.20 1..02 0. different quantities of each of these reagents ate required to attain the sam!" pH..08 0. hydrazine is often added as an oxygen scavenger.00 ]0. Despite this obvious advantage.5 9.S 8. ~ydrazine is rarely considered as a.n alkalising agent in the steam generating industry...0 8. Table ~ 3 Relationship between pH values at 25°C and Concentrations of Alkalising Agents(ll) Concentrations in mg/l Ammonia MorEholine H~drazine pH Value attained 7. The main decomposition reaction is.11) (4..36 Water Chemistry components of the steam-water circuit) exhibits a minimum rate of corrosion at 25°C in the pH range of 8 . Hydrazine. Its distribution ratio increases with temperature. They thus give corrosion protection to that part of the cycle where steam comes into contact with the surface of the construction materials. Thu~ while pH is upgraded during the condensation process. On the other hand. morpho line end hydrazine. while a concentration lower than morpho line.30 1. the magnitude of the ratio is smaller than that for ammonia. .03 0. 13). 3 N2 H4 . decreases sharpl) in the region of 25°C to 100°C after which it decreases asymptotically with temperature.0 0. N2 + 2H2 (4.S 0.10. However.0 9. as given in Table 4. because of its tendency to decompose under the cond:tions of temperature prevalent in the boiler side(ll.)f dissolved oxygen in promoting corrosion. 4NH3 + N2 A small part also decomposes as N2 H 4 . on the other hand is a good compromise candidate. This means that sufficient alkalisation in the condensing phase is not achieved with ammonia.

N2 + 2H20 + 4 Fe 30 4 (4. The deoxygenation is most effective in the pH range of9 . The deoxygenation reaction is given as.Wate. While the reaction is hardly perceptible at 20°C. Ch.5 DEOXYGENATION As mentioned earlier. if employed as an alkalisina agent.0 6. In general. As the purity of water increases.e. the time is reduced to less than 10 hours with 200 percent excess. it is complete in a few seconds at 170°C. A heterogeneous surface absorption (on metal or metallic oxides) reaction has been postulated. At present hydrazine and several forms of catalysed hydrazine ~e employed for this purpose(l2..13) ...1066 0. hydrazine decompo..5 1..02] . metal ions are found to catalyse the reaction..mlstry.7 41. 4.0169 0. deoxygenation is an established practice. [N2H4.0025 0. N2H4 + 6 Fe20 3.. N2H4 + Two additional mechanisms appear to operate during the process of deoxygenation in addition to the one given in equation 4. as well as on its initiation. N2 + 2H 20 Surface Another heterogeneous process is where heamatite (Fe 20J) in the steamwater circuit is reduced to Fe30 4.4620 Thus in the temperature range of interest (:!50oC .4 Thermal DecompositloD of Hydrazine(l1) 37 Temperature °C 160 t 112 (Sec) 200 250 300 307. Material Compatibility and Corrosion Table 4. pH. N2H4 . the rate falls showing that impurities present in water catalyse the reaction. these include temperature.. Coming to the parameters that govern the deoxygenation the effect of temperature is appreciable. dissolved oxygen is the main culprit in causing corrosion of iron and ferrous alloys on contact with water.14) Experience indicates the involvement of all three mechanisms...10. The reaction has a period of induction and proceeds very slowly at room temperature. This is especially true of Cu2+ and other 3d transition (4. To minimise this problem.5 k(sec· I ) 0. presence and concentration of catalysts etc. Thus. faster and the need for replacement will be high..12) 2 . (4.13) ° .. while 10 percent excess hydrazine requires 40 hours for scavencing dissolved oxygen (at a particular temperature).. reagent concentration.tJOO°C). especially at high temperatures. tnere are several parameters which have a marked effect both on its rate. The effect ofhydrazine concentration is very pronounced.12. N2 + 2H20 Although the above equation denotes a simple bimolecular homogenous reaction.. which further reacts with oxygen.

dso catalyse the process. 2. Proc.. (1973). V. Technical Report No. 8. 8th International COllferellce Oil the Properties of Steam. Gould G.S. Venkateswarlu. The discussion in this chapter clearly indicates that water chemistry and corrosion are closely interlinked. (1982). . Martinova O. Proc. DAE Symposium on Corrosion alld its Control in Power and Chemicallndustries. S. Chemical Business. 7. Schikkor G. Venkateswarlu K.. polley. (1986). TPRDIBI08781R 86. lAPS. T.. and References therein. (1980) Corrosion and Compatibility of Materials in Nuclear Power Stations. S. S. provide. Amercian Power Conference. 1089.25 and (1993). 5. Activities of the International Association for the Propertics of Steam. 53. (1988). Pro('. Kalpakkam.. Materials Behaviour in Nuclear Reactor Water Systems. 13. Corrosion & Maintenance. Symposium High Temperature/High Pressure Ell'ctr(. (1929). (1979). Proc. G. Proc. 4. MS P (85) 3. 10. Venkateswarlu K. and M. C. (1978). February (1988).38 Water Chemistry element cations. and K. Role of Water Chemistry in Corrosion Control. AUgem. Vulkan Verlag. A Status Report. A large amount of basic physico-chemical information has been generated and collateci.. Physico-chemical Interactions at the Mctal-Water Interface alld Their Significance to Deposition Problems in Nuclear Power Stations. Potter and F. International Congress. A Review of pH Calculation and Corrosion Product Solubilities Under PWR Primary Coli ant Chemistry Conditions.. (1978).l'try ill Aque'Jus SolutiollS. CHEM TECH '80. Gactiyar. and K. Corrosion in Power Industry.. pp. New Delhi. Electrochem. . Ramshesh V. Sundaram C. DAE Symposium. 176-186.chemi. pp. Solubility of Inorganic Compounds in Sub-Critical and Supercrillcal Water. Z. pp. Chicago. S. W. Venkatcswarlu K.. S. The proceedings of several conferences organised by the International Association for the Properties of Steam. and H. Fundamental Research in the Field of Water Chemistry in Power Plants During the Last Years and its Demands: Proc. (1976). of Symposium 3. Venkateswarlu K. c.19-67. 533-546. Bombay. Topical Meeting on Water Chemislry in Nuclear Power Stations.33. January (1973). 9. II. Venkatc~warlu. valuable data in this regard. 212. Chem.. 3. S. R. pp. Baroda. W. Pocock. 143-48 Thornton E. 24-26. UK. Essen. Use of Hydratine for Deoxygenation: . Deoxygenation: An Essential Ingredient in Steam Generating Industry. 6. REFERENCES I. (1987) The Solubility of Magnetite in Water and in Aqueous Solutions of Acid alld Alkali. Allorg. Heitmann H.. 35. J. Catalysed hydrazine is available in the market. Bohnsack. 12. Central I::lectricity Gelleratillg Board Report.. Central Board of Irrigation & Power. ( 1986). (1981). It has been observed that certain organic additives (derivatives of quinion~). April.hemistry and Physics of the Surface of Metals and their Oxides.. G. Venkateswaran G. Z. leading to a favourable material compatibility (or the lack of it) in high temperature and high pressure water-steam circuits. V. 4.

lakes and even underground borewells. Stringent control of water chemistry. as well as on tbe capital and operational costs and environmental requirement of the industrial location. It has been roughly estimated that 90 percent of all the water used by industry is for heat transfer and cooling while about 8 per cent is used for process requirements and about 2 percent for steam generation. The type of treatment to be adopted depends upon the quality of the available source of natural water. On the other hand. is employed for all the three purposes mentioned above. In this chapter.5 TREATMENT OF NATURAL WATERS FOR INDUSTRIAL COOLING Water finds extensive use as a heat trasfer and cooling medium in chemical process industries and power generation through the deployment of heat exchangers. Water from rivers. Tile water quality criteria and hence the treatment procedures are different for these three end uses. In addition. it is also made use for generating high pressure steam in thermal and nuclear power stations. will have to be removed by suitable pretreatment procedures. attention will be focussed on the chemical treatment and quality of water needed for industrial cooling. after proper chemical treatment(1). sea water is used only for cooling the condensers and process . essential for steam generation. efficient and cost effective.. some site-specific variations of the general water treatment procedures are ullavoidable. while this is not so for the other two uses. Although water from a particular source may be acceptable for drinking or for agriculture. condensers and cool~ng towers. Efforts are constantly being made to envolve improved water conditioning programmes that are environmentally friendly. io. Thus. certain suspended and dissolved impurities present in it. after special purification procedures. so that it is acceptable for industrial cooling with or without further chemical conditioning.

though of a different nature and magnitude. power stations located at Dhuvaran. dams and lakes for condenser cooling. On the other hand. The effect is a function of the size of the organisms. Sunlight penetrates the low depth turbid water systems like lakes and river banks and supports the photosynthetic activity of the phytoplankton consisting of different types of algae such as the blue greens.s).system when the blowdown water is drained into the environment. 5. biofouling prob'lems are severe with sea water applications and antifouling practices are all pervasive(l). phosphates.40 Water Chemistry water heat exchangers (once-through) of power plants and oth.. the discharge limits are set much lower at 0..1) The oxidising property and the disinfecting action of chlorine is due to HOel.1 BIOFOULING IN NATURAL WATERS Power stations at inland locations make use of surface waters from rivers. heat exchangers etc.g. When chlorine gas is added to water. greens and the diatoms.6. pH) temperature and the nature of the chlorine species. Because of the larg~ volume of running sea water in once-through systems. Surface and groundwaters also experience biofouling. Hence there is a need to regulate the release of chlorine content in the effluents(6. Such raw waters contain their natural flora and fauna. In India. the water quality. The flora mainly comprises phytoplankton in association with bacteria and fungi fed' '. heavy chemiea) industries such as petrochemicals located along the coast. Since large volumes are involved in once through systems. the period of exposure.2 mg/1 of chlorine at the condenser outfall. silica and carbonic acid present in these waters. Such discharges are permitted for not more than 2 to 3 hrs in a day. At the same time this imposes the need for handling bulk quantities of hazardous chlorine. hypochlorous (HOCI) and hydrochloric (HCl) acids are formed. (e. no other method appears to be economically viable. a chemical treatment of sea water is practised. It has been observed that residual chlorine present in the combined form and as chlorinated organics is detrimental to fish.). invertebrates and algae in natural water. Residual chlorine present in water from a cQoling tower basin could be detrimental to fresh water ec<. there is no question of a chemical treatment. el 2 + H20 -+ Hel + HOCI (5.3 mg/l or even 0. iron.Jy nutrients like nitrates. Environmental concerns have led to the lowering of the allowable discharge limits to less than 0. Kalpakkam and Tuticorin on the east coast make use of sea water for cooling the power plant condensers and process water heat exchangers(3).. Tarapur and Trombay on the west coast and Ennore.05 mg/I. mostly in the form of pressurised gas cylinders round the clock. We shall first deal with the problem of biofouling encountered in the use of natural waters for coolin. Only at a few locations. depending upon the material of condenser tubes. with or without the aid of cooling towers. For continuous chlorination. Hypochlorous acid dissociates to give hydrogen and hypochlorite (Oel) ions . condensers. The conventional and the widely practised method for controlling biofouling is through the chlorination of the coolant water(4.

Chlorine present as HOCI and OCI. while in slightly alkaline waters (8 pH). which possess a disinfecting property.2. it is necessary to know the chlorine demand of the water. an effective antifoulant measure in fresh water systems. Herein comes the role of dissolved bromide in sea water. is still effective in controlling marine biofouling. 100 80 ~ 0 20 40 ~ > ci 80 40 20 0 4 5 6 7 ~ S! Z III 60 t .: ~ 80! 100 8 pH 9 & 10 11 Fig. Chlorine also reacts with ammonia present in water producing chloramines. In order to get the free residual chlorine.is termed free residual chlorine and that existing in the f:-rm of chloramines etc. The effectiveness of HOC I as compared to other forms of chlorine species could be due to its small molecular size and electrical neutrality which allows it to penetrate the cell wall..could be due to its negative charge. these are of importance in water chlorination due to their persistence in water for a longer period of time as compared to HOCI.th~ amount of chlorine consumed by the organics and inorganics. Dissosiation of HOCI and HOBr as a function of pH(15) It has been suggested that death of bacterial cells results from a chemical reaction of HOCI or a chlorine compound with an enzyme system essential for metabolic activity. it is obvious that chlorination is quit. Chloramines have comparatively slow diffusion through tne cell wall. (e. which has a pH of 8. The difference between various disinfectants is attributed to their ability to penetrate the cell. The presence of 68 mgll of bromide in seawater.. it is less effective. results in a complex chemistry of chlorinated seawater(6).1. however. 300 times less than that of HOCI.5 (Fig 5. which may impede its penetration into the cell. The lesser bactericidal effect of OCI. The OCI. Chlorine reacts with nitrogenous compounds like proteins. ~e2+) present in water before free residual chlorine is detectable in water.. two to three times a day.Treatment of Natural Waters for Industrial Cooling 41 depending on temperature and pH of the water.g.. the dissociation is considerable above a pH of 6. that is.1). From this. is termed combined residuals. The current practice consists of intermittent chlorination upto 1 mg/l of free residual chlorine for 20-30 minutes. 5. This is because chlorine (HOCI) releases .is not as effective as HOCI(4). The question that needs an answer is the universal observation that chlorination of seawater. where the pH is in the range of 6 to 7. and other organic matter forming chlorinated compounds or oxidised products.

5 pH (Fig. HOCI + NH3 -+ NH 2CI + H20 HOCI +. The dissociation of HOBr to form H+ and OBr' (hypobromite ion) is also pH dependent. in once-through systems. Thus.0 to 8. Hence at the pH of seawater.+ H20 Similar equations can -bec~ri.6. HOBr and OBr' ion. Upto 8. chlorination leads to the formation of hypochlorous acid.final residual chlorine) in mgll.5) In Eq. proteins and humic acid. t is the contact time in hours and n is the slope of the curve that is obtained on plotting the experimentally determined chlorine demand at different time intervals vs.(minus) chlorine residual at the end of one hour).Nf!2CI -+ NHCI 2 + H20 (5. OCI'. The chlorine demand varies somewhat with the season and the sea currents and needs to be analytically determined at regular intervals so that the total chlorine dose needed can be evaluated. HOBr.4) . HOCI + NHtt2 :-+ NCI 3. The cumulative effect of the potentially carcinogenic chloroorganics is a matter of concern. Hence total residual chlorine in seawater always refers to a mixture of HOCI. HOCI reacts with both inorganic and organic nitrogenous compounds present in natural waters (a major fraction of the chlorine demand).S.42 Water Chemistry HOBr from bromide. 5. The majority of the reaction products are chi oro-organics (hydrocarb9~s. . K is the chlorine demand in mgll at the end of one hour (initial chlorine dose .8). nitrates. contact time in hours(4. OBr'.3) (5. at 9.S. While the reaction of HOCI with ammonia is comparatively fast. At a coastal power station this practice should be optimised depending upon the nature of the fouling community and the chlorine demand of the seawater in the intake area. is a successful method of controling marine biofouling(7). The product of chlorine demand and contact time is a characteristic of the water under examination and is given by.tten for organic nitrogen compounds.). aromatic acids etc. plus the bromamines. HOBr is a superior biocide as compared to HOCI. lot of care is to be exercised in regulating the chlorination practice so that the discharged water contains as little total residual chlorine as possible.1). that with organics is slower and depends upon the contract time. The formation of chloramines. As briefly mentioned aboye. Examples of such compounds are ammonia. Consenquently. stepwise is a follows. OCI' ion.2) (5. chloramines and bromamines.2 pH. phenols. amino acids. 90% of bromine is in the form of HOBr and the percentage drops to 10% only. which co-exist with chloramines. A significant development following chlorination of natural waters for industrial use. D is the final chlorine demand (initial chlorine dose . is its reactions with the ever increasing' number of man made chemicals of undetermined toxicity discharged into the aquatic environment. D= K t n (5. the chlorination of seawater which leads to HOBr. The reaction between chlorine and organic nitrogen is relatively slow. with the equilibrium shifting to a higher pH value.

The Tarapur Atomic Power Plant consumes 2500 . Branacles are one of the common macrofouiants and their response to chlorine has been well studied. Reduced marine phytoplankt~n productivity in chlorinated seawater has been observed.K. of chlorine everyday.5 to 3 mgll of free residual chlodne). that is vital to the growth of these organisms.Treatment of Natural Waters for Industrial Cooling 43 Turning to the biological aspects of chlorination. practised once in eight hours. Marine mussels.4 mgll of free residual chlorine) appears to be more effective in combating mussel fouling. Macrofouling by branacles and mussels have been the focus of many investigations. India(!I·12). including studies at Bombay and Kalpakkam. are the most important of the fouling organisms that restrict the cooling water flow.2 OPERATIONAL PRACTICE OF CHLORINATION IN POWER STATIONS· USE OF BROMINE The Central Electricity Generating Board (CEGB) U. c. Work on algae indicated that while the effect of chlorine is algistatic.lweek.. Mytilus virdi and Mytilus californicus. The duration of chlorination is 15-20 minutes in each shift of eight hours with 2-3 mg/l of residual chlorine at the condenser water box. According to the CEGB. The time to achieve a 100 percent kill has been related to the temperature and residual chlorine level through a generalised regression equation.ode for chlorination is as given below: Unless local pollution of seawater is severe it should be assumed that marine fouling is likely. they are (a) . Chlorine interferes with the process or thread of filament formation by the mussel larve. (d) Residual chlorine of 0. carried out a systematic study on various antifouling methodi-used in cooling water circuits. Each bay is subjected to a shock dose of chlorine that results in 2 to 3 mg/l residual chlorine for I hr. Chlorine injection must be such that residual chlorine is distributed uniformly throughout the intake water. (c) Chlorination plant must be ready before water is admitted to the circulating water culverts. Similarly reduced carbon uptake (using C-14) and depression of photosynthesis were noted. While all the seawater cooling systems are once-through. of late.5 mg/I of tOlal chlorine. In fact it is becoming the norm to use cooling towers to dissipate heat into the atmospheric environment. There are four bays at the intake. (b) A thorough census of fouling organisms must be carried out before the erection of a power station. a continuous chlorination level of (0. It has been realised. that of bromine is algicidal. They found that chlorination is the most economical method for combating all biogrowth in power station circulating water systems(13). the general effic~I'Y of chlorine as a bactericidal agent is universally accepted. a number of fresh water cooling systems are not. Eighty percent average mortality of Balanus larve was recorded after five minutes exposure to seawater at a chlorine level of 2. Thus.2 ppm must be maintained at the condenser outlet. typified by Mytilus edulis. that instead of intermittent moderate chlorination (2.3000 kg. 5.2 to 0.

Dispersed biological matter also makes the chlorination programme effective. Rapid decay of bromine and its compounds sllch as bromamines. discharged into the natural aquatic environment. where most of the cooling water is recycled between the cooling tower basin and the heat exchangers or condensers. for example.tnds) as a substitute tor chlorine is coming more and more into use(IS).:3 . It is shown that manganese fouling of 304 stainless steel (SS) condenser tubing is arrested on switching over to bromine based biocides(IS).. that algae and bacteria can be flocculated using cationic polymer.nitrilo propionamide are extremely potent broad spectrum microbiocides. Keeping the experience with seawater in mind. whose pH is maintained towards the alkaline side. the application of bromine (in the form of bromide or C?ther bromine cOqlpo\. essential that tt. dead or alive. Biofouling is again a problem area in these systems in which chlorination is invariably used to ~ombat(14). the cooling water dosed with this chemical can easily be detoxified before being. Under such conditions. once in a while additional biocides can also be used without economic penalty. Biocides used in water treatment programmes are mostly cationic surface active agents. In case. so that a balanced chemical conditioning is maintained in the recirculating cooling water. minimises the environmental impact ofthe biocide on the receiving aquatic eco-system. Thus they are less persistant than the corresponding chloramines. bromine is available in different chemical forms which can be added as a biocide. In addition. The compound is an oxidising type microbiocide and is unstable with increasing pH and temperature. Fresh make up water is added only to compensate for the evaportion losses from the cooling tower and the blow down is discharged into the aquatic environment. and the use of biocides can be eliminated. The efficacy of HOBr as a biocide over that of HOCI has been well established facilitating dose reduction. It has been found. form slime.the trend is towards a programme of chemical conditionirrg of the circulating water. Since. Thus. 2. their oxidative corrosion is much less than in the presence of HOCI. >J measurements with copper alloy condenser tubes such as Cu : Ni = 90 : 10 showed that in the presence HOBr.2-dibromo . Electrochemi .ey are dispersed in water using surface active agents. the required bromine biocides are not available. Micro organisms. In addition to HOBr. chlorination loses its efficacy and research was focussed on the use of alternative biocides. BCDMH and HOBr are about 100 times more effective than HOCl towards pseudomona in alkaline cooling waters. At about 2 mg/l equivalent of chlorine. as seen earlier. the reaction leading to the formation ofbromamines can be made reversible by lowering the pH. recourse carl be taken to adding a few mg/1 . It is. Equally effective are the bromamines.S • 8. it is a recirculating system. especially around pH 7.44 Water Chemistry recirculating systems.2. Recently it has been established that chlorination and the use of low molecular weight cationic polymers alone can control biofouling of cooling water systems. therefore. Brominated propionamides like. In fresh water cooling systems. which acts as material for cementing particles together. Bromine chemistry offers reduced corrosion and environmental hazard. One such compound is bromochloro dimethyl hydantion (BCDMH) which is commercially available. by allowing chlorine to interact easily with the binding material.

Treatment of Natural Waters for Industrial Cooling 45 (5 mgll) of sodium bromide to the recirculating cooling water (pH about 8 or more) and carrying out chlorination as usual. II' all these copper based alloys. When the need for total leak proof condensers arose. brass was used to serve as the material for the condenser and heat exchanger tubes. Admirality brass or Naval brass is used for fresh water systems. The compound is made use of in combination with a dispersant to enhance its penetration of algal and bacterial slime layers. on the spot intrusion of cooling water containing sodium chloride leads to equipment breakdowns such as a tube burst in the boiler or breakages of turbine parts in areas having contact with wet stream. but of late. Another equally good alloy is stainless steel. In extreme cases. fungi and bacteria. sometimes overlaid with materials like stainless steel and titanium. titanium (Ti) came into use as the tube material. there is no chemical treatment for erosion and corrosion prevention. Again stainless steel has no in-built resistance to biofouling. the damage was caused by local corrosive attack on the tubing. From the early stages. In most cases the tube sheet is of carbon steel. the chlorine will release bromine in the form of HOBr as an effective biocide. algae. it is necessary to add . is better suited. For seawater applications employing either Cu-Ni or Ti' or even SS. A prolonged search for leak dt'tcction and fixing becomes necessary. a chemical treatment was found that is effective against such types of attack. but is not much used in view of its high cost. Their effectiveness depends upon site specific studies and no generalisation can be made. When copper alloyed tubes were used. where water with a high salt content is used for cooling. The major part of the damage to condensers was substantively due to the corrosion of the condenser tubes. the release of cupric ions due to corrosion is considered to be a good antibiofouling measure. environmental considerations have imposed servre constraints on their large scale application. Manufacturers of cooling water chemicals offer a number of proprietory pjpcides. The 70 . in view of the toxicity of copper to such organisms. it would be appropriate to look briefly at the materials with which such treated water comes into contact.10 allo). These are recommended to be used once a week. while aluminium (AI) brass is the preferred material for seawater systems. Tin . However. have almost always given rise to serious effects in the operation of power stations(l6). The resistance to corrossion of copper alloyed tube materials in braekish or seawater is said to be due to the formation of a natural covering film of cuprous oxide. However. However. Leakages in condensers. If the thickness of this film is inadequate in aggressive cooling waters. especially some of the new stainless steels that were developed with this specific application in mind. Subsequently cupronickels were developed and the 90-10 alloy found wide applications in seawater systems. As in seawater chlorination. it has no resistance to biofouling.3 MATERIALS IN A COOLING WATER CIRCUIT Before considering the chemical treatment and conditioning of cooling water.organic biocides made a major entry into the markel. 5. immediate damage bears no relation to the possible consequential damage. Methylene bis-thiocyanate is an<'ther biocide that is effective against. with Al brass being a widely used material. while chlorination is suspended for that day.

Bostwick envisaged the iron additive acting as compensation for the loss of 'natural' iron which had been available from the water boxes prior to installation of cathodic protection.4 FERROUS SULPHATE INJECTION The use of ferrous sulphate as an inhibitor of the corrosion of aluminium brass was first described by Bostwick(l7). 5. He produced detailed statistical data relating to the addition of ferrous sulphate versus the number of tube failures(18. but for half an hour at a time. The main thing is that conditions of uniform distribution. However. What concentrations and sequences are finally chosen will depend on the organic matter and sulphide content in the cooling water. It is basically of no consequence whether these oxide layers are consciously produced.46 Water Chemistry agents which will create additional prote. the presence of ferrous oxide layers has proved most efficient in many respects. for example. ' Injection of the same concentration twice per day. Continuous injection to values in the 10 /lg/l range. an . Iron may also act as a cathodic inhibitor or can be incorporated into a cuprous oxide (Cu 20) film. or whether uncontrollably formtd. but there is still no agreement on the mechanism of protection. Of the many conceivable and proposed measures. Small quantities will be chosen as far as possible because of the formation of slime. good adhesion and reconstitution ofthe'film are maintained.ctive layers which are sufficiently strong and adhere over the internal tube surfaces.1f). since longer dwell times result in premature oxidation which from flaking Fe (III) compounds. especially during back washing of the condensers. The injection of concentrated FeS04 solution (21 percent FeS04' 20°C) should be effected shortly before entry of cooling seawater into the heat exchangers or condensers. This gives It a greater pllssivity. By way of explanation. In the case oflarge size condensers. This view implies that the iron film is effective in the commissioning stage of condenser operation and that there after iron neither contributes to the passivation action nor is necessary. this has not been realised in practice at all. With regard to development oflayers via ferrous sulphate injection. several procedures have proved successsful for continuous operation : Injection of 1 mgll Fe1+ in cooling water for the duration of one hourday. Ferrous sulphate dosing is now widely practised. by a mechanism similar to that found when iron or nickel are incorporated from cupro-nickel alloys. Other workers believe that a relatively thick film of hydrated ferric oxide if formed which reduces the erosive action of seawater and enables a protective film to form on the brass itself. One way to look at this situation is by considering the principle of Point of Zero Charge (PZC) of the original oxide layers and its interaction with iron hydrous oxides having a different PZC. by ferrous sulphate (FeS04) injection or by making use of sacrificial anodes. for example. via the corrosion of steel tubes in the cooling water feed lines. There may then be a possibility of reducing or discountinuing iron additions to the cooling water once service conditions are well established.

the layers show up as two lamellae on the metallographic picture. This ia due to the tendency of the layers to split on drying and peel off in some places. Automatic cleaning methods lead to a consolidation and homogeni~ation of the external covering layers. dosed with ferrous sulphate have been investigated(lO). The alloy underwent a uniform cathodicafly controlled corrosion and no alteration in the stress corrosion cracking suceptibility of the alloy was observed. tubes deprived of their own natural covering film. but has not found acceptance. The thickness and roughness of the films increases proportionally to the length of the cleaning interval. closely meshed layer of ferrous oxide. a cleaning period of only one hour at a time is acceptable.. There is also a body of opinion against the sponge ball cleaning after the treatment with ferrous sulphate. 5. i. Electrochemical measurements have shown that on Cu:Ni (90: 10). but also to condensers that were in service for sO. on account of the formation of natural oxide films. the crystalline content of which consists of gamma-FeO OH. There are difference of opinion with regard to the cleaning intervals for condenser tubes having ferrous sulphate injectiC'n. After a longer injection period.Treatment of Natural Waters for Industrial Cooling additional injection into the return water boxes can be advantageous. either under the influence of the electric field of the Cu 20 covering film with a positive Zeta potential.5 COOLING WATER TREATMENT Cooling water treatment of a power station or a heavy chemical industry is to be organised from the very inception(14). brown uniform layers of varying structure are formed on . Over the natural Cu 20 covering film is a homogeneous. glossy reddish-brown films with a thickness of only a very few microns appear. Unless the required site specific water quality assessment is carried out well ahead of time and suitable chemical . The thickness of these layers is 7S microns.e. Depending on the injection method.me years and which were damaged by pitting and erosive corrosion.the inner surfaces of the tubes after some weeks. Electrochemical characteristics of the corrossion of Ni-Resist type 2 alloy in seawater. In isolated cases. or by electrolytic precipitation on the cathode surface of the epitactic layer. the protection offered is meager (very thin layer) and hence it is not worthwhile to practise !his treatment. On continuous cleaning with sponge rubber balls or brushes. According to the results obtained by electron microscopy this hybrid oxide seems to occur as a thin intermediate layer to which adhesion-enhancing properties are ascribed. Ferrous sulphate treatment has been successfu)'y applied not only to brand new tubes. The procedure has been also advocated for Ti and SS tubes. Whilst some aim for a firmly adhering and consolidated external protective layer with continuous cleaning. It is therefore not expedient to inject FeS0 4 directly into pickled tubes. FeCu0 2 has also been radiographically diagnosed. 47 The incorporation of iron takes place through negatively or positively charged colloids of hydrated iron oxides. others are of the opinion that. It is desirable to inject ferrous sulphate throu~hout the operating period and at an increased level and frequency after a shut down maintenance.

in once-through cooling. the tower.JI-----7J " ~ Heat E)(changer ~ /" Fig... very little chemical treatment is made use for economic reasons. The combined loss due to evaporation. The cooling towers usually operate with concentration cycle in the range of 2 to 3. problems such as reduced flow in heat exchanger tubes.. would certainly crop up during operation of the plant (Fig...2). One can take any pair of ions in both streams to arrive at the concentration cycle. It is usual to take chloride ion ratios as chloride deposition is the least.. S. by adding the necessary coagulants(ll).. In view of the concentration of impurities in the cooling tower due to evaporation losses. (a) (b) Contr01 of biofouling by chlorination. In order to maintain an appropriate level of the chemicals. The first step has already been dealt with. Thus the most important part of the study is togather data on water quality.. Cooling Tower Makeup . the circulating water contains greater levels of both cations and anions as compared to the make up water. makes use of alum or ferric sulphate.. and Removal of suspended solids.48 Water Chemistry treatment procedures evolved. known as clarification. mechanical factors and blowdowil is made up by adding the requisite quality of fresh water. The preliminary steps in the treatment of raw water consists of.. The process. The open recirculating cooling water systems invariably have a cooling tower from which water is lost due to evaporation and mechanical dispersal due to the sprays in the tower. a part of the water is blown down from. The hydroxides of the trivalent ions.5. The suspended solids are removed usually with the help of a flocculator. over a two year period.... Of more interest are the recirculating systems with or without a cooling tower.. /' Water -T~IL"""""""'::__-"'::"/:.. This will result in concentration of impurities and intentionally added chemicals in the cooling tower water. failure of equipment etc.2 Important Problem Areas in Cooling Water System(l) As discussed in detail earlier. neutralise the surface charge of the suspended .. The ratio is known as the concentration cycle.

and soluble organic matter. It was sec. Na+. has been overcome to a large extent by the use of organic polyelectrolytes in conjunction with them.0 (in k.g.) and (c) Acting as nutlients to the biological species present in the system. Although organic in nature. Another problem is the carryover of the finely divided hydroxide flocs into the clarified effulent. silica. sulphate. different types of bacteria (sulphate reducers. (e. CaC0 3 : 0. etc. the use of polyelectrolytes does not add to the organic fouling of the treated water. presence of ions which cause precipitation etc.0 to 2.lacroflocs. thus aggravating the problem ofbiofouling. temperature etc. organic maiter etc. phosphate and sometimes silica contribute to this effect. Based cn thermal conductivity.callm. These compounds help in neutralisation of the surface charges of the suspended fine particles by the inorganic coagulants. In general scale forming salts have inverse solubility characteristics and tend to get precipitated when saturation is reached due to local changes.oC) Constituents like carbonate. The dissolved chemical constituents present in the cooling water could result in(l) : Interaction with materials of contruction leading to corrosion. Dissolved impurities. C03·2. These include temperature. etc. NH/. H2S. humic substances). NH 3.. The presence of (a) (b) (a) (b) . (c) Micro-organisms such as algae. He0 3·. the loss of heat transfer due to scaling has been estimated as. Also available arC! non-ionic or so called neutral polyelectrolytes. An important problem in flocculation. Reactions such as precipitation among themselves that could lead to scale formation (such reactions depend upon concentration. N0 3·. This has to be dewatered and disposed of.0 and CaS0 4 : 1. these are classified as cationic or anionic polyelectrolytes. The constituents present in water fall broadly under four categories: Suspended impurities like clay. Lesser quantities of inorganic coagulants have been found to be adequate. (d) Dissolved gases like 02' CO 2. This results in the formation ofmicroflocs and subsequenttly in r. Based on site specific experimentation. silica.5 to 1. Thes. arising out of the lise of inorganic coagulants alone.) and fungi. which is bulky due to a high content of water. The carry over problem is thus minimised.n that the use of polyelectrolytes reduced the volume of sludge by as much as 75 percent allowing it to be readily dewatered. Calcium. is the generation of sludge.2 to 0. iron bacteria. besides traces of iron. Mg2+. carbonate. concentration due to evaporation.e are water soluble. phosphate and organic compounds from cooling tower serve as nutrients for the micro-organisms. long chain polymers with attached active groups and having molecular weights in the range of 107 • The ionisation of the active group confers a charge on the bulky molecule as a whole. Si02 : 0.5.Treatment a/Natural Waters/or Industrial Cooling 49 particles and facilitate their agglomeration. Based on the sign of the charge. magnesium. a polyelectrolyte or a combination thereof is selected. Cl·.h. sulphate. such as Ca2+.S04·2. Such problems.

1 Deposit Formation and Control In a cooling water system. and CO 2 contribute to the increased corrosion of system surfaces.14). floes are formed which get deposited very loosely on the surfaces. e. These modified cryst . once the water is supersaturated with any scale forming salts. A cooling water treatment programme should effectively control the above mentioned deposition processes.:>n the temperature and pH of the water.1). mg/1. that contribute to scaling in cooling water systems is the degradation of metaphosphates to orthophosphates. which Jepends very much . Amongst the added chemicals. Presence of sparingly soluble salts (e.1 Solubility Trends among Scale Forming Calcium Salts. results in scaling (Table 5.. algae. Dissolved CO~ in the water. Dissolved 2 . Table 5. Temperature CaS0 4 anhyrous 0 40 100 High 2800 750 CaS04 0. is an extremely significant. surface active agents such as polyelectrolytes are classified as cationic. ls do not adhere to the surface on which they are first deposited. anionic and nonionic depending on the functional groups possessed by them. ° 5. Approximate solubilities. It is also possible that the surface active agents occupy lattice sites of the growing crystals resulting in the formation of distorted crystals having large internal stresses . . an efficient transfer of heat from process fluid to cooling water is possible.. These chemicals may increase the time of nucleation but cannot prevent it. Nucleation in a cooling water system occurs either in solution or on rough surfaces. As noted earlier.5 H2O V. Corrosion of constructio'n materials leads to the deposition of corrosion products (mainly different forms of iron oxides) on heat exchanger surfaces. etc... As a consequence of the absorption of surface active polymers on the suspended particles. Deposit of dead bacteria. CaS0 4 ) having inverse solubility.50 Water Chemistry ammonia or nitrate also contributes to the metabolic activity and can change the water chemistry of the system considerably. Deposition can be controlled during the crystal growth stage by use of surface active agents. CaC03• Crystals grow either in solution and subsequently get deposited or grow on the surface itself.g. factor in chemical reactions involving precipitation of calcium and magnesium salts as scales. Formation of crystals takes place initially by nucleation followed by crystal growth. also impair heat transfer. biofouling and scale formation. In general it is very difficult to predict in isolation the part played by the dissolved constituents in promoting corrosion.5.g. Sometimes one of the reactions can aggravate the other processes. when deposition on heat exchanger surfaces is minimised(l. High High 22{)0 CaS04 2H 2O 1775 2050 1700 90 50 15 CaC03 °c Crystallization of scale forming salts precedes the deposition step.

It is required to calculate pH of saturation (pHs) for calcium carbonate. e. Usually the former two indices are made lise of for on site evaluation of the scaling and corrosive tendency of natural cooling waters. while above 6 would result in scale dissolution. a value of 6 for RSI indicates stable water.Treatment of Natural Waters for Industrial Cooling 51 The effectiveness of the surface active agents is not the same for all types of deposit forming compounds. The Ryznar Stability Illdex is given by RSI =2 pHs . Since the solubility of calcium carbonate shows a decrease with increase in temperature. To predict the scale forming tendency of a cooling water with respect to calcium carbonate several teChniques are employed.g.8) Under this classification. The most common scale pJ. Thus it is obvious that when the circulating water has higher levels of calcium hardness and bicarbonate alkalinity. Sometimes the final deposit may result through an intermediate compound.6) Where pCa and pAlk are the negative logarithms of their respective concentrations (as in pH with respect of hydrogen ions). the inner surface of the heat exchanger will be prone to scale formation.S. rather than on the slightly corrosive side.2 Scaling Indices As against the principles of cooling water chemistry discussed so far. i. values less than 6 would lead to scaling.e. LSI =pH actual .e. Since temperature gradients are site and design specific. nomograms have been developed for the use as ready reckoners. This was an early way of cooling water treatment.9) Where pHc is the equilibrium pH based on total alkalinity.pHc (5.pKs) + pCa + p Alk (5. i. which is often adjusted to keep the cooling water in a slightly scale forming condition.esent in cooling water systems is calcium carbonate. The Langlier equation is formulated with pH of saturation (pHs) as. Mg (OH)2' The inhibitor chosen should be more effective for the intermediate compound than for the final product. S. The Puckorious Modified Stability Index is formulated as PSI = 2pHs . modern treatment programmes -depend upon inhibition of scaling as well as . the Ryznar (or stability) indeX: and the Puckorus (or modified stability) index(14). corrosion. The vari'ous surface active agents should be screened for their effectiveness for the different deposits encountered in the cooling water system. the foremost of which are the Langlier (or saturation) index. pHs =(pK2 . The calculation being involved.pH actual (5. The Langlier Index is then defined as. a variable in the operator's control is pH. derived from the decomposition of calcium bicarbonate that is normally present in natural waters. no scaling or corrosion. The former indicates a tendency for scaling while lateer signifies a tendency for corrosion by the cooling water.pHs (5.7) and can have a positive or negative value. let us see how the treatment programmes have evolved in practice. this problem becomes acute. pK2 and pKs are the second dissociation constant and the solubility product constant of calcium carbonate respectively.

the scales could contain silica (Si0 2) itself or in the presence of Mg appear as magnesium hydroxy silicate. it is possible that mixing of the acid may not be uniform. the possibility of calcium phosphate scal'!s also needs to be considered. polyaminopo)ycarboxylic acids such as ethylene diamine tetracacetie acid on its di sodium salt (EDTA) and polYll).e . The workers have to be given prope~ training in safety consciouness and remedies for treatment of acid burns must be available on hand. and more so during night shifts. Fortunately.• once a shift. polyelectro)ytes etc. given the fact that its solubility decreases with decrease in pH and increase in temperature . The other hardness ion. inorganic phosphates have been widely used as . particularly if the slopes in the cooling tower basin are not proper or altered by sedimentary deposits at selective locations. A useful guideline is to see that the product of ionic concentrations of calcium and sulphate does not exceed 5 x 105• There are two aspects for any cooling water treatment by chemical addition. These will be considered separately. Consequently when considering prevention of scaling. Such a situation could lead to acidulated water directly getting into the heat exchanger tubes. One is the need to prevent scale formations and other types of fouling. Depending upon the calcium.-orrosion inhibitors. For Ca and Mg.. both Langlier and Ryznar indices still serve as initial guidefines for 'evolving a proper chemical tteatment. level of sulphate need~ to be guarded against. figures occa"ionally as scales in combination with silicate. Since chlorination is effective at a lower pH. in addition to calcium carbonate and calcium sulphate.5. Concentrated sulphuric acid is used for this purpose and addition is usually done in the cooling tower basin.acids. In high silica waters. At present polyacrylates. Adequate controls need to be exercised by measuring pH at different locations of the cooling tower basin especially at the basin's outlets. magnesium. It must also be mentioned that handling of concentrated sulphuric acid is a hazard at all times. organophosphonate~. . As will be seen later. Addition of sulphuric acid to the cooling water automatically raises the It:vel of sulphate. i. copolymers of sulphuric and acrylic . Although there is a constant flow of water movement in the basin. To keep Ca in solution a little Jess than 5 mg/l o~ a polyacrylate with ~ molec':llar weight in the range of 1000 ·is sufficient.eric _phosphatl!s itke sodium hexameta phosphate have been made use of. 5. coupled with the need for reducing the bicarbonate alkalinity.ell as spot checks later. Both carbonate and sulphate scaling is . the other is to prevent or inhibit corrosion of the system materials. calcium carbonate is more insol'lble than calcium sulphate under SUGh conditions and thus will be deposited first. in proprietary combinations are available and are widely used for the inhibitation of sc~Je formation}21~:J). acid addition is a common practice. However. A good way to minimise' scale formation is to add chemicals that will keep tne sC'lle forming constitutetlts in solution.52 Water Chemistry corrosion by chemical additives.3 Chemical Additives Chlorination being verj' effective in the pH range of 6 to 7. acid addition should precede chlorination when practised on an intermittant basis. as v.

the general aspects of corrosion have been considered and the characteristics and causes of different types of corrosion described. At a concentration level of 0. have been used for this purpose. There is always a chance of these getting into the heat exchanger tubes and causing fouling. These polymers are also effective again.+ 2H+ --+ H2 (5. corrosion will be minimised(14). Due to the absence of a clarifier or its malfunction. The wooden planks in the cooling tower are subject to biodeterioration. it is preferred over AMP. Since HEDP does not have this disadvantage. use of dispersing chemicals and removal of sludge are some of the techniques employed for overcoming the problem. In many plants. A typical example is a fertiliser plant. The basin more or less acts as a trap for all sorts of insolubles and fine sediments are. The sludge so formed can be conveniently removed. Inorganic polyphosphates have been effectively replaced by organic phosphates and phosphate esters. where the ambient atmosphere around the cooling tower could contain ammonia and sulphur dioxide. The principle behind scale control by crystal modification was discussed earIier(14).5 to 2 mg!l they are very effective in modifying the cubic form of calcium carbonate to spherical sludge particles.10) Feo --+ Fe 2+ + 2e while the cathodic reaction is represented by 2e .Treatment of Natural Waters for Industrial Cooling 53 prevented. Changing local wind direction would result in these gases being blown into the cooling tower and there are many examples. Both these phosphonates have a tendency to dissolve copper from circuit materials. (5. Thus when these are added to prevent scaling. while zinc and polyphosphate are well known . Best known among the former are chromate and orthophosphate. chlorine could attack it and destroy its effectiveness. In Chapter No. One of earlier practices was to spray an aqueous solution of sodium pentachlorophenate on such surfaces. since AMP contains aminonitrogen. Thus one can have anodic inhibitors and cathodic inhibitors with which the cooling water system can be dosed. Periodic clean up of the basin.>t calcium sulphate and phosphate. Thus AMP addition to the cooling tower basin or any injection point has to be done out of phase with chlorination. To recapitulate briefly. The phosphonates are also taken up by the iron corrosion product that is always present in the system. some mud or silts will also get into the tower basin. the anodic reaction. in the case of iron is. where pH of the cooling water gets altered as a result.usually formed. it is necessary to add an inhibitor to minimise copper corrosion. provision of a side stream filter. As seen earlier.11 ) If one breaks or inhibits either. As the cooling tower is exposed to the environment the wind borne particulates get trapped. Sulphonated polystyrenes and polymalac acids which are water soluble polymers. or both the path ways.4. the location of the cooling tower is such that exhaust gases or those gases arising out of plant leaks get dissolved in the cooling tower spray and thus alter its chemistry. The former class are quite effective for Ca scale control. The frequently used among them are amino methylene phosphoni-:: acid (AMP) and I-hydroxy-ethylidine 1. I-diphosphonic acid (HEDP). thus reducing their effectiveness.

a coolin~ water treatment programme has to effectively counter biofouling.S.20 mg/I) and zinc (I . but at the samt time to control excessive scaling by use of chemicals Ii~e AMP. Venk. total phosphate levels can be upto 15 mg/I in the case of polyphosphates and I to 2 mg/l of zn is also added as a cathodic inhibitor. In fact chromate and polysilicate in combination offer excellent protection 10 steel. the pH is adjusted between 6 to 7 and chromate (20 . Venkataramani and A.:swarlu K.Venkateswarlu. but still suffers from the disadvantage that the limit of discharge of hel. Proprietary formulations ate available in the market. chromate was widely used untill recently. Programmable chemical addition anl1 frequent monitoring of chemical parameters are required. New york. These are es~entially extensions of the scale inhibition techniques discussed earlier. (J 972). Among the anodic inhibitors. While 'J. B.54 Water Chemistry cathodic inhibitors. the chromate treament is gradually going out of use. Thus a low chromate treatment. REFERENCES I. Programme to Control Biofouling at Madras Atomic Power Project.S. Since ninety percent of the industrial usage of water is for cooling. of the 2. Among other corrosion inhibitors mention has to be made of nitrates and orthosilicates on the anodic side and molybdates and polysilicates on the cathodic side.. and K.5).C. Central Board of Irrigation and Power. \-8.Radiatlon Protection. Hand Book of Chlorination. 5. This combination is one of the best availahle.. proc. New Delhi. J19th AlIlIll<ll Research Session. copper and aluminium components of the 'cooling water circuit. Water Chemistry in Thermal Power Stations. Viswanathan R. White G. (1982). (1975). . The idea is to inhibit corrosion by the formation of a fine scale in alkaline conditions(pH 7 to 8.ofworkshop on Water Chemistry in Thermal Power StatIOns. in fact a dinodic treatment has come into vogue.e.Sriraman. the treatment is known as dinodic. A variety of procedures are available Clnd many of these are site specific and dependent upon the water quality. Proc. It is very effective over a wide pH range and gives excellent protection to mild steel at concentration levels of 300 to 500 mg/l. (1981). such high concentrations could no longer be employed. 4. \warlu K.. Waste Water and Cooling Water. Current Chlodrination and Dechlorination Pratices in the Treatment of Potable Water.Zn. New Delhi. Proc. Van Nostrand Reinhold. Polyphosphates and aminomethylene phosphonate figure in this treatment. polyphosphate (10 . The later is preferred due to various reasons. 3. Efforts have been made to evolve a blowdown treatment process that either reduces chromate to trivalent chromium or recovers chromate by ion exchange. It has to be emphasised that cooHng water treatment In the alkaline region is much more delicate than the procedure in the 6-7 pH range and needs better chemical control. However. Ven'{8!. 9-12.3 mg/I) are added.S.this segment of water treatment has special importance and can in no case be neglected. (1983). When both are used in combination such as chromate . In view of the above difficulties. with restrictions on chromate discharge into the environment throughthe blowdown route becoming mandatory.K. Chemical Trt:atment for Indu~tnal Cooling Waters. Central Board of Irrigation and Power. Bull. Polyphosphate and zinc offer equivalent protection to steel only.5 mg/1. In this practice. while the possibility of Mg silicate scale is minimised by adding an acrylic polymer.25 mg/I). In conclusion. 21-22.S.'avalent chromium into the environment is 0. scaling and corrosion. A number of non-chromate treatments have been evolved(ll).

.ctlons. Crystal Morphology. (J 989). Manne BlOfouhng and Alhed Problems 10 the Condenser Coohng Systems of MAPS. ChemIcal Age of IlIdIG. (1961). InternatIOnal Conference on Coal F"ed PO\<l er Plants and the Aquatic EnVironment.J 8 Nair K V K . RD/LlM/496 13 Coughlan J and J W Whltehcuse.(I977).l. Power Engtneertng. 12-19 18 Borth R F a'nd H J Pryor. p 299 Venkate~warlu K Sand R Vlswanathan. (1990). (1980).4).498-499 Karande A A . Ge'leratlOn of Coolmg Water Treatment Calgon Corporation.. Pcnn-15230 USA Also see Matena/s Performance. Bromine Replaces ChlOrine In Coohng Water Treatment. Annual Meetlllg of the Nallonal Assoc. Chi on nation of Coohn. March. A Ne . CEGB (UK). Ad~ances tn the Cht'mlstf) of Alkahn" CoollIIg Water Treatment Calgon Coq:or?. NY. ed. (1968). June. 15-18 16 Papmarcos J . 8. Marine BlOfoultng and Its Chemical Control 10 Power Industry. The Effect of Organopho~phorus Compounds and Polymer~ on CaCO. Role of Iron In the Inhibition of CorrosIOn of Marine Heat Exchangers A Re\ lew. Pittsburgh.March (1990). "Electrochenucal CorrosIOn Charactenstlcs of NI-Reslstant type 2 In Sea Water Contatntng Ferrou~ Sulphate" Brlllsh CorroslGn Journal. PO" er June. (1975).lon. Power.1089-! 098 22 Boffardl B P and G W Schweitzer. Proc Env"onmental Impact of Water Chlorrnatlon. (1982). Kalr~kam. ElIgllleers. Chesapeake SCiellce 18. 17. Pa. 1980 GENERA.Trevo~e. The Protection of Copper by Ferrous Sulp . A Review of Impact of Chlorination Processes Upon Marine Ecosystem. 1984.ereln 15 Fellers B D • E L r iock dnd J C Conley. Chemlcul Business February . 102 14 Strau~s S D and P R PULkorlu~. 1-7 Da\ IS W P 'lnd D P Middaugh.61 20 Daud M B . (\ 989). UK. s-I to g-24 and rcference~ lh. 1973 17 BostWick TW. 3J3-307 21 Venkateswarlu K Sand B Venkataraman:. The SuppressIOn ofMus~cl fouhng by ChloTlnauon. Coohng Water Treatment for Control of Scahnll. (1969). 25(4). G Venkateswaran and K S Venkdteswarlu. CorrodlOn 5:ll'lIce. (19. Recent Trends 10 Industrial Water Treatment. 1988. (1988). Drew Chcnmal Co Boonton.Treatment of Natural Waters for Industrial Coolmg 55 6 6a Em "onmentallmpact of Water Chlorrnatlon. USA 24 DubIO L • (198D). July. Manne B lofnultng Re~earch. 7. COHoslOn.. A K and R VI~wanathan. Ind J Tech. Aspects of ChlOrine UtlhlatlOn 10 the United Ktngdom. ed Jolley R L • Oak Ridge. 30.USA 3 Pmlclples of IndustrialWarer Trearmellt (1977). 149 19 Pearson C • (1972). New York.44 23 Peters C Rand W R Holhngshad. Environmental Aspects Concerning the Large Scale U~e of ChlOrine to Combat Blofouhng and references theretn. (1973).ater Handbook (1979) McGraw-HIli Book Co .. Conden~er Tube DeSign Dm.. CorrosIOn. Gelleratlllg Board. 1982 7 8 9 K S • (1990).L REFERENCES I Handbook of Industrial Water COlldlllonlllg (1980). Jolley R L . Proc. Brlllsh CorrosIOn Journal. Ibid.-15230. USA 2 12 The Na/co ". Water A review of Literature on the Effects of ChloTlne on Aquattc Orgamsm... Oak Ridge. pp 39-41 STlTdman..the Need for an Integrated Apporach. I ~.. Sea Water chlOrination. Copenhagen August. 5)mposlum VII Venkatc~warlu J0 II Manne BlOlog\ ISSlled as a report b\ C"ntral EleclrtclI). N J USA . Proc 5pecIGIIsts Meettng on Martne BlOdeterroratlOn \<IlIh reference to pOl~er plant coo Illig s)stems BARC. 19(12).atlOn of CorrOSIO. ate AdditIOns. Fouhng. Betz LaboratoTies Inc . (1077).CEGB RD/LIM 269 Whitehouse J W. (1979). (1975). Pmsburgh Penn. 92-103 Holmes N J .

Raw water after proper pretreatment steps such as f1oculation. two plants based on different priniciples and techniques. especially carbon dioxide and oxygen.• dissolved solids. this' water is not fully demineralised. especially in the treatment of low level radioactive effluents. Hence the lower the lewel of impurities. chlorination etc. with permissible levels being specified. a water purification system. every unit of an electricity generating jr'dustry installs.Thus. At present a variety of resins serve the needs of industries as diverse as power generation to purification of life saving drugs. as part of its equipment. As noted in an earlier chapter. since by its very nature a boiler concentrates impurities. . Of course.6 DEMINERALISATION BY ION EXCHANGE The purity of water that is fed to a steam generating system is of utmost importance. Obviously. But this would mean. clarification. higher than normally expected. this applies equally rigorously to suspended solids and to an extent to dissolved gases. Reverse Osmosis is also a very useful technique in waste water treatment. The process of demineralisation( getting water free of all its dissolved cations and anions) squarely rests on ion exchange. is the source for the OM plant(l). if the raw water available to a power plant has a salt content. i. Use of semi permeable membrances by the reverse osmosis technique for water purification has become important. more commonly known as a Oimineralisation(OM) Plant(1). drinking water contains dissolved salts. it might be economically advantageous to have the Reverse Osmoss(RO) plant precede the OM plant.e . Synthetic ion exchange resins have become available over the last fifty years. This will reduce the load on the latter and enhance the useful service life of the costly resins. However. In fact water purification is the largest single application of the -ion exchange technique. Since the last two decades drinking water is being produced by this method. the better.

while NaOH is a strong base.1 ION EXCHANGE RESINS Natural zeolites of the type [Min (AI02)b cH 20] are known to possess ion exchange properties. By softening is meant thal hardness causing cations such as Ca 2+ and Mg2+ are replaced by Na+ in the water under treatment. 6. Divinyl benzene crosslinked with styrene forms the matrix for strong acid cation exchange r. Similarity.Demineralisation by Ion Exchange 57 In this chapter.WCI- Strong acid cation exchanger Strong base anion exchanger Strong base anion exch". Divinyl benzene crosslinked with acrylic or methyl acrylic acid forms the matrix for the weak acid cation exchange resins. These are weak base anion exchangers that can only function in an acidic medium.S03 gets fixed on to the matrix while H+ ions are retained as mobile exchangeable ions. while reverse osmosis is dealt with later on under Desalination. . were beiTlg used for water softening. The terms "strong" and "weak" have the same connotation as in the case of simple acids and bases. while HCI is a strong acid. The anion exchange resins are produced by chloromethylation followed by amination ofthe polymer matrix. The synthetic ion exchange resins developed during the thirties and forties are based on water insoluble organic pnlymer matrices. Since tetracovalent nitrogen is always +ve. The sui phonic acid group. The strong acid cation exchangers are produced by the sulphonation of the polymer skeleton. In fact. For example. They are essentially solid electrolytes and rt"ersibly exchange their mobile ions with ions of like charge from the surrounding liquid medium. ammonium hydroxide is a weak base.C1- I (CH3)2N. with exchangeable sites(l). -CH- I -CH- f -CH- f SO.esins and strong and weak base anion exchange resins. some of these materials ~old under the trade name ofPermutit.'W © I ~ CH 2 ~ CH 2 I (CH 3 )3W. Steam lvcomotives fill up such softened water at railway stations to avoid scale formation in their boiler internals.l~er Secondary and primary ammonium resins are also available.or CI-. propionic acid is a weak acid. This leads either to the formation of quarternary or tertiary ammoniacal nitrogen in the polymer matrix. It is the nature of the dissociating functional group in the resin that is indicated by these terms. In the weak . the application of ion exchange for water purification is discussed. The resin that has tertiary ammonical nitrogen needs protonation in the acid medium to act as an anion exchanger(l). the former would contain N+ in the matrix and is neutralised by a mobile anion such as OH.

a part of the anioic load is removed in the gas form reducing the load on the anion resin bed. Na+ + H+ -R4 W OH. than monovalent ions. reaction 6. For strong acid and strong base resins. H+ + Na+ <=> -RSOj'.1. The resin can then be regenerated by equilibration with a suitable acid or a base. Na+ + HCI <=> -RS0 3-. it is somewhat different. in the aqueous phase will be preferred by the resin phase. the selectivity for the ions commonly present in water is. . all the cationic impurities such as Na+. Since ion exchange is an electrostatic(ionic) phenomenon. which in turn acts as the driving force to push reactions in 6. taking commonly present ions in natural waters as examples: -RSOJ. Thus when ordinary water. Mg++ are exchanged for the hydrogen ions of the resin. But in practice. As a result.S) The reactions in equations 6.+ CI~ (6. say tap water. This causes a lot of bubble formation. When this is passed next through an anion exchanger. 6. When water is pass sed through the cation resin. -RSOj" . Obviously. usually by blowing air through it before it is led into the anion resin columns. the functional group is usually -COOH in place of -S03H. in principle. almost like frothing. because of the presence of bicarbonate and carbonate ions in natural waters.3 goes to completion instantaneously.2) -R4W. H+ + HCO)" ~ H2C0 3 ~ H 20 + CO 2 t (6.4 and 6.1 and 6.7 H20 (6. it is to be expected that multivalent ions rather. can be moved in the forward direction. H+ + NaCI -R4 N+.1) (6. the ion exchange capacity is exhausted in both the resin columns to the same extent. The total equivalents of cationic impurities are balanced by the total equivalents of anionic impurities in 'natural waters.+ NaCI (6.S being equilibrium processes.and sulphate are held by the exchanger. 6. The hydrogen ions interact with these anions and the resultant carbonic acid so formed decomposes into water and carbon dioxide. Thus there is a selectivity series. OH. all the anionic-impurities such as CI-. The hydrogen and hydroxyl ions-9(>mbine to form water molecules and the effluent becomes neutral water again.4) (6. is passed through a bed ofa cation exchanger. the ionic impurities in water are exchanged and retained in the resins.2 in a fast forward direction. the effluentwill be acidic.in turn.3) Since the dissociation constant of water is very small and as the reaction of H+ with OH. Ca++. Thus.58 Water Chemistry acid cation exchange resins. When all the exchange sites that originally held H+ or OHions are occupied b'y Na+ or a" (or any other cations or anions) respectively the resin is said to be exhausted.is extremely fast. It is necessary to degas this effluent. we have seen that it becomes acidic. in an acrylic -DVB matrix. 6.2.2 ION EXCHANGE PROCESS The exchange eqilibria can be illustrated by the following reactions. N0 3.6) Thus. releasing OH.CI-+ NaOH <=> -R4N+.Cl + OH- H+ + OH.

59 The strong acid and strong base resins function over the entire pH range of tbe medium. at least once in 24 hours. Other physical characteristics of the commercial ion exchangers are . Some of the relevant properties of the standard resins are given in Table 6. For . ' Another important property of the ion exchange resins' is the degree of cross linking. Commercially available resins have a range of crosslinking from 2 to 12.It also determines the pore or the channel size. the apparent wet density is about 0. Sulphonated resins are more resistant to osmotic shock than aminated resins (CER > AER). A good sample ofth~ resin contains not less than 70 percent of whole beads.S03H type resins.). the apparent wet density is again around 0. their unifonnity coefficient being 1. unifonnity co-efficient and the percentage of whole beads in the material(3).7 glm!. strong anions such as sulphate and chloride are most preferred by the weak base anion exchangers. This is known as the osmotic shock.Deminerallsation bi' Ion Exchange Fes". while that of anion exchange resins in general is somewhat lower than 5.7 glm!. which more or less corresponds to the percentage ofthe crosslinking agent. the capacity is always less than the value in the dry state. In practice it is expressed as milliequivalents per gram(meq/gm) of the dry resin.1. Resins with low cross linking experience this shock more than those with a high cross linking.As a corollary. The capacity is theoretically defined as the number of exchangeable sites present for one mole of the resin.0 meq/gm. while an anion exchanger would cycle between -OH form and -CI form. The capacity in the wet state is determined experimentally and it is usually of the order of 65 percent of its value in the dry state(3). while for the -COOH type it is about 0. For anion resins. viz. It is obvious that the greater the cross linking.density. effective bead size. 6. it experiences different cycles of treatment over prolonged periods. divinyl benezene present in the resin. t. The capacity of the weak acid cation resin is much higher than this. This has led to an important application in water treatment. Resistance to osmotic shock(resin beads should not crumble) is a very important criterion for judging resin performance.7(max. . the latter are brittle. Because the resins are always made use of in a wet condition. For strong acid cation resins.3 PROPERTIES OF10NeEXCHANGE RESINS A reference was made earlier to ion exchange capacity and its exhaustion. The weak acid cation exchange and the weak base anion exchange resin.85 glml. This leads to a periodic swelling and contraction of the resin beads. When the resin is in use.. whereby ions like sulphate and chloride are first removed by a weak base anion ( exchanger(since the medium at that point is gcing to be acidic as seen earlier) and tbe so-called weak anions such as silicate are taken up in a second column contaming a strong base anion exchanger. For example a cation exchange resin would be cycling between the -H form and the -Na form. however. > Ca2+ > Mgl+ > Na+ and Sulphate> chloride>Bicarbonate. the greater will be the mechanical strength of the resin and hence its swelling behaviour. function b~st in basic and acidic pH ranges respectively.0 meq/ gm. the capacity in the dry state could in principle reach 5.

9 Max.8 4. SBA: Strong Base Anion Exchanger. .The macroporus resins are opaque in appearance and exhibit a good resistance to osmotic shock. transparent and glassy in appearance. Two varieties of ion exchange resins are commercially available for water purification. clarified raw water. /CH) -N_. There are two. nics can easily pass through them and hence flows are not reduced in service.4 DEMINERALISATION OF NATURAL WATERS The feed to a demineralisation plant i<.6 0.1 to 1.II Usually Type II resins are used in water purification. since they are cheap.46 4.0 to 4. (a) the gel or the microporous type and (b) the macroreticular or macroporous type(3).1 are usually alkyl groups. WBA: Weak Base Anion Exchanger.9 ( 19 ) H+. They are classified on the basis of their porosity. WAC: Weak Acid Cation Exchanger. Type I and Type II. the groups attached to the nitrogeJ.Na+ ( 10 ) OH-_CI( 10) 0. SAC: Strong Acid Cation Exchanger. In Type I.5 In the table the abbreviations stand for. 6.0 nm. These organics subsequently decompose in the boiler.4 3. However. . Both have quarternary ammonium groups as the active exchange sites.38 to 0. The pores tend to get clogged with organics.5 1.45 0. As their name implies.N _ _ CH) 'CH 2 0H Type .60 Water Chemistry Table 6. The macroporous resins on the oth<.1 Characteristics of Standard Ion Exchange Resins(4) Type and functional ~rou2 Bead size (mm) Moisture content SAC _S0 3H SBA _N(CH 3)3 WAC _COOH WBA NHOH 0.3 Total exchange ca2acitx (eg/l) 1. free from chlorine . one of the groups is an alkanol thus. they do not effectively remove silica.50 (%) 4. recommended Tem2' (oC) Swelling (%) Na+_H+ ( 7 ) CI-_OH- 120 60 120 100 1. The former are clear.. types of strongly basic anion exchangers.r hand have pores whose diameter is of the order of several thousand angstroms with large surface areas( -100 m2/g).8 4. which are relatively large molecules.33 to 0..3 to 5. the pores have a small diameter. Large size neutral molecules such as org .4 to 4. while in Type II. and are also susceptible to organic fouling(l).2 to 4.36 to 0. The beads are spherical with a diameter ranging from 0._CH) ---CH ) Type • I ~CH) .45 to 0.

1 mg/I. The first contains a ~eak base anion(WBA) exchanger. but irreversible fouling of the resin. Silica is reduced to less than 0.02 mg/l. what one needs from that point would be a cation exchange column. The former has a better affinity for chloride. Anion Exchange For several years. while the second is made up of a sttrong base anion(SBA) exchanger. The removal of organic matter over a period of time is far from complete and leads to partial. the current practice is to have two anion exchange beds.Demineralisation by Ion Exchange 61 and nearly purified of organic and bilolgical rl1ateriai. which represents the total equivalents of these three anions. water technologists all over the world have been preoccupied by the problem of the fouling of strong base anion exchangers.0).4. height etc.(ofien referred to as bed) a de gasser where air is usually blown through the effluent to drive off carbon dioxide and an anion exchange bed. Some of the conclusions available in literature are(l). as the name implies. If this value is greater than that of bicarbonate. nitrate and sulphate. the organic content plays a significant part in the efficiency of the anion exchange. Macroporous exchangers of the corresponding variety do not show specially high fixation of organic matter I1S compared to gel type resins.1 Organic Load vs. in the raw water. (a) (b) In type I strong base anion resins. a mixture of cation and anion exchangers are in place. called a mixed bed wherein. The performance of a DM plant really depends upon the performance of the anion exchanger and that of the mixed resin bed. Hence it becomes necessary to add one more bed of ion exchangers. 6. The SBA bed which follows it will then effectively pick up silica and the effluent from this anion exchange bed will have a lowest specific conductivity and reduced silica slip. This additional bed improves the water purity and one can get water whose specific conductivity is less than 0.5. In several countries. are to be determined from what is known as negative M alkalinity. Hence type I strong base anion exchangers are not well suited for the treatment of water having a high organic load.1S/cm with a pH between 6. On the other hand. with the total electrolytes being less than 0. it is essential to have a WBA column. . Its bed volume. the fixation of organic matter depends upon the dried matter content of the resin. This conclusion is all the more true if the raw water contains detergents even at low concentrations of I mg/I. when type II strong base anion exchangers are used.5 ).1S/cm. the quality of water from anion bed outlet has sh()wn a distinct improvement for about the same conditions of organic and detergent fouling.5 to 7. its specific conductivity ranges from about 10 to 20 ). From the input water side. In practice. It has been more or less established by experience that the cation exchange part of the demineralisation process does not pose many problems. with the pH being in the alkaline range(upto 9. with facilities for regeneration of the spent resins(4). it was realised that the water effluent from the anion exchanger outlet was not pure enough. In principle. (c) (d) .

It has been shown theoretically. This difficulty can be eliminated by using hydrochloric acid as the cation resin regenerent. M'acroporous polystyrene weak base anion exchangers have their own limitations and have been shown to be fouled up by water heavily charged with organic matter. in the direction opposite to that selected for the exchange cycle. A strongly basic anion resin picks up acid in the form of the bisulphate ion which is easily hydrolysed later resulting in the leakage of acid into the treated water. Experience shows that the presence of a weak base anion exchanger with a reasonably dry solid content will protect the strong base exchange resin column that follows it.62 (e) Water Chemistry Investigations have indicated that condensation exchange resins(weak base type) perform well in water containing a high percentage of or. if the regeneration !s effected counter-current. The cause of the poor quality of the water coming out of the mixed bed Is contact with the sulphuric acid. K and the ratio R of H+ in the last layers of the resin bed to its total capacity.7) where S represents the total Na. a mixed bed of cation and anion exchange resins becomes essential. (Na)1 = S KR 1--lOO-R (6. unless a very large amount of regenerant-acid or alkali is used. it is evident that if R is close .ganic matter.2 Mixed Beds(MBs) In order to acheive the required quality of DM water as make up for the high pressure boilers. From eq. the bottom eXhaust~1 layers of the resins are more efficiently regenerated. This is known as 'co-current' regeneration. The strongly basic anion resins take up Hel as the chloride and the chloride form of the resin is not suspectible to hydrolysis which could lead to acid formation and its leakage. The mixed bed is to be used as a final polishing unit and should be operated with higher levels of regeneration. thus. (f) (g) 6. when the diffusion process has reached equilibrium. Apart from increased regeneration efficiency. Sodium leakage. 6. On the other hand. which is employed for regenerating the cation resin with some of the anion resin in the bed.(Na)\ is expressed in terms of this distribution coefficient. all well as in actual practice. 6.4.3 Regeneration Technique It is customary to effect regeneratiofl by passing the regenerant through the bed of ion exchange resins in the same direction as the raw water being treated(1.4. that if the co-current regeneration is effected (downward flow).l). it is known that the relative concentration of Na+ in the resin and in the liquid phase are not identical and their concentration ratio or distri~ution coefficient is a characteristic of the resin. With a strong acid cation exchange resin in service. that is. The plant should produce an effluent that is essentially neutral. the bottom layers of the exhausted columns are poorly regenerated.7. This process results in reducing the leakage of sodium to very low levels in the case of cation exchanger and of silica in the case of anion exchanger during the exchange cycle. economy in regeneration (in terms of consumption of chemicals) can be acheived by this technique.

It has been demonstrated that the performance of type II resin can be improved by the counter. Regeneration ofa mixed bed has been a challenge for a long time.6.6.1 Sodium Contamination in Mixed Bed Regeneration (Scbematic) This problem has been ingeniously overcome by introducing a layer ofin(!t resin with carefully selected buoyancy properties. -_. For an efficient in-situ regeneration of the resins. tv give the same result.. Due to improper seperation during regeneration. polystyrene) which possesses no ion exchange properties and is physically and chemically inert to most solvents and reagents. the quality of the treated water is not influenced by the nature of the influent water and by the regeneration rate. r-!-~- .:. if regeneration is made counter-current. . which cannot usually acheived in practice. so that it acts as buffer layer to seperate the two zones of active resins when the regeneration and rinse down cycles are operating (Fig.. particularly to those normally used for regene.current regeneration. t:lR/R'OH HR/R'OH NaR~===~ HR • • • •• • •• • ••• •• MIXED BED AFTER REGENERATION MIXED BED AFTER MIXING Fig... This improper regeneration results in reduced operational capacity (Na-slip) oftbe mixed beds cycle after cycle. a small layer ofcation exchange resin at the interface between the two resin phases is converted into the sodium form during the regeneration of the upper layer of anion exchange resin. Also a part of the cation exchange resin is present in the anion exchange resin bed and gets converted to the sodium form.2). the factor with maximum effect on water quality being the selected sodium leakage rate at which the cycle is stopped. With counter-current regeneration system. RIOH ~ ~ . extensive studies have been made on using the fluidised bed technique for demberalisation.~ NaR ••••••• : . Silica leakage from type II resin can be made to be on par with that of type I resins. This involves a careful selection of the density of the inert material and control of the density of the cation and anion 'exchange resins. Following the idea of counter-current regeneration. Water of very good quality can be obtained With counter-current regeneration. the last layers are that much nearer to a state of complete regeneration.(Fig. The inert material is an organic polymer(for example. whereas co-current systems require a finishing column.r:ation purposes(2) . In this process the raw water to be treated is passed upwards and regeneration is carried out by a downward flow of the regenerant. -... 6.. . This is however achieved by counter current regeneration..1).Demineralisation by Ion Exchange 6J to 100. the separation of the anion and cation resin should be perfect and clean.

Thus the former is thoroughly regenerated(I). while the other is a strong acid or base. which is lighter than the strong acid resin is placed at the top of the bed (Fig. During regeneration. 6. One of them is weak acid or base.3 Schematic Diagram of Stratified Bed .6. EXHAUSTION Raw water REGENERATION Regenerant out a:idic lbasic resin Strongly acdiclbasc resin Weak Treated water Regenerant in Fig. encountering first the strong acid resin. the weak acid resin.mRm!l6!l Anion exchange resin ~~~~j:== +Re.3).2 Schematic Diagram of 3-Resin Mixed Bed System Economy in the production of deionised water can be achieved by the use of stratified beds which consist of superimposed layers of resins of the same polarity. The counter-current regenerant flow will then pass upwards through the bed.64 Water Chemistry Raw water Mixed bed --W. 6. followed by weak acid resin.!enerant in Inert --111~=~=*=== ~ Regenerdnt resin out Cation_~~ exchange resin EXHAUSTtON REGENERATION Fig.

Resin fouling is a major irritant in OM plants(5). Both resins are fouled up by oil. comes along with regenerant chemicals. it is possible to calculate the permissible amount of silica and other solids in the treated water. For a good seperation between the two resins. At regeneration levels greater than 100 gm of NaOH per litre. To acheive this the so called thoroughfare system of regeneration can be used. This system involves passing the regenerant required for the pre('eding cation or anion units. the anion e"changers are fouled up by organics in addition to colloidal silica. It is important to remove as much silica from mixed resin as possible. acid wash (10 percent inhibited hydrochloric . temperature is also important when removal of silica from mixed resin bed is considered. the influence of temperature is pronounced. backwashing. the particle size range must be carefully selected. In addition. In the case of anion exchangers. from the preceding units. Once in way the cation exchanger is also fouled up by precipitates such as calcium sulphate. Thus. The sequential procedure includes. One often comes across fouling of the cation exchanger by iron.due to improper pretreatment procedures. This means that the flow pattern within the column should be optimum in order to have a clear seperation between the two resins during regeneration which necessitates a careful se!ection of the particle size of the two resins. As mentioned earlier. The performance of stratified beds also depends on a good seoeration between the two exchangers. The SiOiTOS ratio ". These impurities.ust be less than 20 percent. otherwise the low regeneration rates used entail a risk of fouling by silica. The quantity of the anion resin in the basic demineralised unit will be at least five to ten times the quantity of the corresponding resins in the mixed bed. To overcome the different fouling problems.Demineralisation by Ion Exchange 65 In comparision with a single exchanger(weak or strong) regenerated by counter-current flow. As such the regeneration level in the mixed bed will be correspondingly higher without any additional consumption ofregenerants. the shoner the cycle time and the higher the alkalinitynOS and total hardness/alkalinity ratios. type II resin can be used as a strong base exchanger. The ratio of weak acid( carboxylic) resin volume to total bed volume in the case of a stratified system will be larger. For example. firstly through the coresponding resins in the mixed bed. When this type of regeneration is used with either acid or alkali. particularly. silt and clay . it has become a practice to specify tbe iron and chlorine contents off-rCI used for regeneration. microbes. The quantity of water passing through a mixed bed unit per regeneration being known. and the efficiency of the process is improved in terms of less regenerant consumption. that can be taken care of by the mixed bed during normal operation. It has been mentioned that a high level of regeneration of the polishing mixed bed is desirable in order to ensure the highest possible quality of water. it is implicit that the mixed b~d be regenerated at the same time as the preceding cation or anion exchange column. cleaning up of the resin beds is required. since silica in the treated water is dependent upon the amount of silica left in the mixed bed after regeneration. stratified beds have a higher operating capacity per installed litre. which get in . maqganese and copper.grease. Less resin is therefore required to treat the same volume of water. commercial hydrochloric acid usually contains iron. iron.

Some special problems are also ~ncountered in the mechanics of demineralisation.66 Water Chemistry acid). It is also essential that the feed to the DM plant after pretreatment be free from any residual chlorin_" introduced earlier(6). The precoat filters are non-regenerable. contains alkafising additives such as ammonia. On the other h"nd the conductivity of the OM water for industtrial steam generation plants with a large quantity of make up water is an exceptionally important parameter. due to ion slip in the OM plant. in order to withstand the pressure and flow. if the condt'nsate. if the salinity of the cooling water exceeds 2000 mg/l.5 QUALITY OF DM WATER One can take a specific conductivity of 0. it is most essential to maintain the compactness of the resin bed at all times during regeneration and preferably during the service regime also. However. This is specially necessary.5% solution of formaldehyde. the purification system operates under a pressure much greater than that of the usual demineralisation plant. Condensate polishing is strongly advised. These slips do not have much influence on the feed water conductivity in condensate recycling power plants whose requirements of make up water are below I percent of the hourly steam output. However. Thus. In some condensate processing systems. As a result. Counter current flow units should be operated in such a way that sodium and silica end points for cation and anion units are not excecded. specific conductivities higher than 0. 15 percent NaCI solution mixed with 5 percent NaOH. In modern power stations. where the operation of the high presssure boiler and turbine requires the highest quality feed water. it is becoming a standard practice to include the polishing of the steam condensate(partly or even fully) by ion exchange resins(7. experience has shown that it is possible to acheive and maintain feed water conductivity below 0. In each case appropriate test procedures are available to judge the efficacy of the treatment.05 ~S/cm). due to the relative affinity of ammonium type of cations as compared to say that of sodium for the resin sites. Since large quantity of condensate need~ to be polished.07 ~S/cm and total metals around 2-3 ~g/1. attrition strength of the resin bead becomes an important criterion. Increased electrolyte input in this case invariably leads to . since condenser leaks result in an unacceptable level of impurity intrusions. the condensate polishing becomes a very complicated process. Any disturbance of the cation bed always leads to an unacceptable leakage of sodium. 6. or 15 percent NaCI solution mixed with 5 percent sodium hypochlorite (to give about 3 percent wtlv of free chlorine) and 0.1 ~S/cm as the basis for the Ol~ water and can be sure that a very low concentration of electrolytes are present (theoritical conductivity of water at 20 0C being 0.1 ~S/cm are often observed at the outlet of mixed bed filters. hydrazine or morpholine.8). In counter current flow units. if the steam condenser is cooled by bracki~h or sea water. If the condensate is near neutral. it is difficult to achieve a conductivity value as low as that mentioned above. very fine size resins(25 micron diameter) 'ire used as precoat materials on pressurised filter media before the deep bed polisher. Particle size and grading are also important to reduce pressure drops. the solution or solutions to be used for overcoming the problem of fouling depend upon the nature of fouling.

Power stations in India have been making attempts to improve the performance of DM plants. Trouble Shooting in demineralising Plants.25 0. Conductivity ~cm. (1979). Indo.19 0.5 6. Recent Trends in Industrial Water Treatment.7 6.No. Ibid. This emphasis is due partly to the installation of a number of once-through boilers in advanced countries and partly to the increasing requirements of steam purity for high pressure turbines.2 J.2 that only in case A and to some extent in case B is this specification met. Conductivity 0.5 0.8 13.0 7.2 presents data of some case studies carried out by the author in this context. conductivjty at tile anion exchanger outlet. Chemical No. Ion Exchange Resins for Water Purification: Properties and Characterisation. Central Board of Irrigation and Power. There is much room for improve.0 7..0 4.D. 1089-1098. Venkatatamani. twice that of the specifications usually given for that parameter.German Seminar on Performance of Thermal Power Plants.1S/cm. indicating that MB regeneration is being carried out in an efficient manner.42 0. D~mineralisation of Water: Principles. 5. Vol. in case B. Parameters 1. 13-20. P. May and September in the year of.S.8 6. 1 represents the Sp.1SIcm 3.3 7.C &: D represent the power stations under study. KVI-I to KVI-4. One way to assess this is to monitor critical chemical parameters of the mixed bed output water.K. It is usual for DM plant manufactures to claim a specification that the specific conductivity of the output water from the mixed bed is less than 0.25 0. Nair B.S.43 0.1.5 30 40 40 8. BARC-1364.0 2.0 6.M &: S represent January.No. It has often been said that the performance of a demineralisation plant is crucial to the over all water chemistry in a thermal power station. It is evident from Table 6.9 7.8 6. Production and Quality Control.40 J. 4. On the other hand. 57-66. 2. Table 6. New Delhi. Workshop on Water Chemistry in Thermal Power Stations.15 0.K. .S.9 S. Venkateswarulu K. REFERENCES 1. Output pH 6. 3. Bhabha Atomic Research Centre Report..S. (1983). and B. A. particularly in once-through boilers and superheaters.8 8.44 0.3 7. (1982). Input Sp. Table 6.Venkateswarly. Despite this.40 0.ment in performance in cases C and D. Investigation revealed that at B. Central Board of Irrigallon& Power.. Proc.2 Comparison of Mixed Bed. the MB performance is not far from optimum. (1987). Output Sp.36 0.15 0. Chemical Age of India. Proc. Boiler DM Water Makeup Consumption and Quality.8 6.8 6. Natarajan R. the anion bed was contaminated with some cation exchanger leading to the higher value.Demineralisation by Ion Exchange 67 damage.2 4.8 6.S.. 30.8 6.l) shows a high value of conductivity. Mathur and K. Performance(9) S.New Delhi. I. Venkateswarlu K. (1983).study. the anion exchanger effluent (S.. J A M B C S J M S J M S J D M S 4. Gokhale A.

8. (1983).. Water Chemistry Jha J. 7.B . (1983). Nandwani T. 47-56. From Raw Water to Pure Steam: Problems in Therml\l Power Stations. IS:/11970-1!J87.S. 187-192. 9. (1985). .." Ibid .68 6.. Corrosion and Maintenance. 67-79. Condensatc Polishing. 8. Venkatcswariu K... ..." Ibid .. Guide for Condensate Polishing (Power Plant).. New Dclhi. "Case Histories and Trouble Shooting in Water Chemistry at Thermal Power Statio. Burcau of Indian Standards ( 1987).

Incoloy-800 are employed as tube materials.Monel-400. the latter comprising of feed water. In fossil fuel fired boilers. Condenser tube materials used include brasses. This has been realized during the last 10 to 15 years. stainless steel atf(fT~ely titanium. The words boiler and stellm generator are synonimous. there is a marked tendency to eliminate copper alloys from the feed train. boiler water. the use of water to generate steam for running turbines of power plants is a most important activity. The steam turbine makes use of a variety of alloy steels. . If one has to meet this requirement. high temperatures and pressures are employed in the steam water circuit. the boiler tubes are usually of carbon steel. Whether the steam generated is from burning fossil fuels or from nuclear heat. For securing better therinal efficiencies. the steam quality is of utmost importance. In view of what was said in Chapter 4 and also because of t"le chemical incompatibility of copper with respect to carbon steel under the conditions of a steam-water circuit. though the former term finds a larger usage in fossil fuel fired power plants. or whether it is to be directly employed for steam cracking of naptha in fertiliser plants.7 WATER CHEMISTRY IN FOSSIL FUEL FIRED STEAM GENERATING UNITS 7. there is no alternative to a well considered and integrated water treatment programme at all steam utilities. in a full measure all over the world. In the case of nuclear steam generators.1.1 WATER SIDE CORROSION AND DEPOSITION PROBLEMS For a world in need of energy. 7. cupronickels. steam and condensate in contact with surfaces of different materials. while the latter term is frequently used in the nuclear power sector. stainless steel 304. A block diagram of the water and steam circuit is shown in Fig.

The subject matter in this book deals with the former rather than with the latter which is metallurgical in nature. If the film is damaged. The corrosion rate increases more rapidly with decrease in pH from 8.1I I 1. Consequently.0. than with increase in pH from 11. the efforts are directed towards * As the Expert Coordinalor for the study on water chemistry.5(3). the au.. corrosion is prevented or greatly minimised.hor was responsible for Coordinating al\ the technical work "arried out. This chapter is partly based on that experience. internal corrosion starts again. As long as the adherent film is there.5 to 10. Protection against internal corrosion by the boiler water is primarily provided by the thin magnetite (Fep4) film formed on the tube surfaces during the early stages of operation.1 A Simplified Water·Stea~ Circuit In a Power Plant In high pressure boilers that make use of fossil fuels. the failure of boiler tubes due to internal corrosion and external 'hot' corrosion. The corrosion of carbon steel is minimal in the pH range of 8. is of concern. . 7.0. Boiler tube failures result in reduced availability and reliability of the steam generating unit and impose an economic penalty.70 SUPERHEATER Water Chemistry CONDENSER ECONOMISER CONDENSATE STORAGE I CONDENSATE POLISHER (OPTIONAL) I I . the Central Board of Irrigation and Power conducted a five year research programme on water chemistry and boiler tube failures in thermal power stations across the country and published their findings in two reports*(I. ______ Fig.2). In India.

This type of attack is often called caustic gauging and the resulting failure is known as ductile failure. Of the various alloys present in the system. Fortunately. Consequently blisters appear on the boiler tube. specially copper alloys. This type of failure takes place not only with boiler tubes but also with tubes of the superheater and reheater( in units where they exist). This can be controlled (to values less than 5mg/l) by dosing with hydrazine. The hydrogen produced in corrosion process gets trapped in the film and diffuses into the metal.it is essential that the attemperator or desuperheating spray water be of high quality. resulting in contamination by raw water.5. Cu. In general. With increasing pressure~ the vapour phase carryover of sodium chlonde into the turbine and deposition . A more frequent type of failure of boiler tubes is due to internal corrosion that occurs in the low pH region. which ultimately burst. To avoid deposit formation in these sections.Water Chemistry in Fossil Fuel Fired Steam Generating Units 71 maintaining boiler water pH around 9 to 9. finally leading to tube rupture(4). As the preboiler section operates at relatively low pressure. While talking of water side corrosion. NaCI would also concentrate in the crevices of a boiler. The combined pressure exerted by hydrogen and methane within the metal results in grain boundary fracture. Ni and Zn which originate from the components bearing these metals in the preboiler section. The causative factors are pH and dissolved oxygen. the heat transfer from the fire side through the tube to the boiler water is reduced at such spots which becomes over heated.0 ± 0. the magnetite layer is partly destroyed and internal corrosion starts.!n other words. in the form of NaOH. This results in tube failure. stainless stocls are most susceptible to chloride attack. There it combines with carbon present in boiler steels and generates methane. When the pH is excessively high or low. Under high pH conditions. cooling tower water or sea water depending upon the location. throwing out bits of metal. wall thinning of the boiler tube at that point. The deposit analysis usually shows oxides of Fe. The cause of pH fluctuations can be traced to leakage in the power plant condenser. However. through stress corrosion cracking. gets concentrated in the pores resulting in metal wastage. chloride being a corrosion promoter. The internal deposits being poor thermal conductors. which may occur explosively.5. excess OH. the influence of the chloride ion has to be considered. the latter being more significant than the former(5). can also lead to'over heating of boiler tubes at the spots where such deposits exceed a certain thickness. Ultrasonic inspection might not reveal the troublelipot early enough to effect a tube replacement. the extent of stainless steel surfaces exposed to feed and boiler water and condensate fn a fossil fuel power plant is limited. just like NaOH. it is monitored and kept under control through blowdown. This will also help in minimising pitting corrosion. which frequently occurs close to the welds due to internal stresses at such points. Tube thinning is a characteristic of this class and could be detected earlier through ultrasonic inservice inspection. which is the modem practice the pH is maintained around 10. air ingress is often the cause of an increase in dissolved oxygen in the feed water. specially in tbe presence of dissolved oxygen. The actual range depends upon the nature ()f other constructional materials in the circuit. The internal deposits resulting therein cause tube failures. In all ferrous systems.

Recirculation drum type boilers with blowdown facilities were the first to appear on the scene. viz. Low pressure boilers are by convention those operating upto 15 to 20 kglcm 2 (-300 psig). serving as a source for ·both process heat and steam. it is condensed and the condensate forms the main bulk of feed water to the boiler.Thus sodium chloride and silica are to be looked at from a different view point. Above this working pressure. condensate polishing by mixed bed demineralisers has come into vogue.1 Low and Medium Pressure Boiler Water Treatment. Low and medium pressure boilers find extensive use in the chemical industry. the turbine.72 Water Chemistry on the turbine blades is a matter of serious concern. . these boiler internals are also susceptible to corrosion by dissolved carbon dioxide and oxygcn(7). The required feed water quality is not attainable by the conventional base exchange softening plant as the water has to be completely soft and clear. There were impro~ed designs over a period for increasing pressure. 7. . (b) Preventing deposit formation on heat transfer surfaces. In these there is no drum to hold boiler water with a higher content of dissolved solids than feed water nor is there a blowdown facility to regulate the chemistry. (c) Ensuring the quality of steam acceptable to the turbine. The high purity DM water serves only as a make-up to take care of losses( or more usu~lly the boiler blowdown). In addition to scaling.2. At a later date. However. The water quality requirem~nts changed as a result of this. but below 64 kglcm 2 (.000 kg/h. as is the behaviour of silica. The only way to control them in the steam fed to the turbine is to control them in the feed and boiler water<6).During the last 30 years the design of the boilers has undergone improvements in all directions. Boiler water chemical treatment and its control have evolved over the decades and the process is related to the increasing temperatures and pressures obtained in boilers. It may also be mentioned that stress corrosion cracking is a serious prqblem on the water side of nuclear powered boiling water reactors where stainless is used extensively. with the increasing technical requirement of a minimum amount of dissolved solids as practicable for feed water. After the steam loses most of its energy in driving a high pressure turbine. after being reheated and repressurised.The boilers operate at high heat transfer rates and have evaporation capacities in the range of 10. This group of boilers require almost zero TDS in feed water. A very large number of utilities use the condensate without further purification. as well as to changes in the boiler design itself. The two problems faced under such conditions are scaling und corrosi_on. 7.2 CHEMICAL TREATMENT OF WATER FOR INDUSTRIAL AND POWER PLANT BOILERS Boiler water chemical conditioning and its control is aimed at: (a) Avoiding internal boiler tube corrosion. once-through boilers or steam generators came up.900 psig) are the group of medium pressure boilers. necessitating a superior quality of feed water.

it is highly desirable that the amount dissolved or suspended solids in Sand C be close to zero. blowdown means loss of heat and improvement in feed water quality is more expensive. Table 7. Since alkalinity is a controlling parameter and an excess of it would lead to scaling. It is obvious from the above discussion that the amount of blowdown (in terms of a percentage) will be inversely related to the qUQlity of feed water. The formula applied is.1) Where B is the blowdown rate. Since the boiler is an evaporator. The bleed is known as blowdl'>Wn and is possible only in the case of drum type boilers. it is possible to maintain the above boiler water quality only by a process of feed and bleed. Earlier practices included acid dosing (as in the cooling water treatment) and lime soda softening.ExS(lnMJlh) c-s (7. Two cases in raw water quality may be distinguished: (a) Alkalinity in raw water is high and the total hardness less than the alkalinity. However. S is the amount of dissolved and suspended solids in mgll and C is the maximum permissible aruount of dissolved and suspended solids in mgll in the drain. If the blowdown works out to be greater than 10 percent it is necessary to install a more elaborate feed water purification system. E is the rate of evaporation. preferabley at S percent. one aspect of the boiler water treatment for low and medium pressures is to control alkalinity.8).while phosphate is a corrosion inhibitor.50 mg/l 30 . . The quantity of boiler water to be blown down can be calculated from the quality of feed water (that acts as a diluent) and the equilibrium quality of boiler water .1 Water Quality Specifications for Low Pressure Boilers(7) Total dissolved solids Total alkalinity Less than 3000 mgll 20% of the TDS (Less than 600 mgll as CaC03) 10 to 10. the increasing quality requirements have supplanted these procedures and the use of ion exchange resins in one way or another has become the common practice(7. that too at very high rates (as compared to a cooling tower). Sincp. B(lnMJlh).50 mgll pH Total hardness Sulphite Phosphate Sulphite is added for deoxygenation. As a rule of thumb one can say that if the blowdown can be maintained at below 10 percent. a normal base exchange softening system for feed water along with chemical conditioning is sufficient.5 Less than 5mgll as CaC03 30 . In fact.Water Chemistry in Fossil Fuel Fired Steam Generating Units 73 The boiler water quality in the boiler drum as specified for low pressure boilers is given in Table 7.that needs to be maintained despite evaporation.1. a balance is struck on the basis of cost effectiveness.

The cations tesponsible for hardaess viz. The carbonic acid formed. Both streams are mixed and led through a degasser. This procedure while being simple. This can be done either by the use of a thermal deacrator or by chemical dosing with a reductant. The exhausted resin is regenerated by one to four percent of mineral acids like hydrochloric or sulphuric acid. such as sodium sulphite. viz. .s 'an efficient method. does contribute to the total dissolved solids.g base anion exchanger in the chloride form. the soft water from the sodium form of the cation resin is fed to a stror. This method of treatment leaves the levels of sodium. The advantage lies in the regenerant. The effluents are easy to handle. The degasser used to remove carbon dioxide in the ion exchange set-up. One contains a strong acid cation exchanger in the bydrogen form. such circumstances is removed through a degasser. There would be no cation bed in the hydrogen form. As an alternative.2 Water Quality Limits (Max. Table 7.04 gm NaOH/l. As mentioned earlier. In the second case it becomes necessary to achieve partial demineralisation as well as softening. environmentally speaking(8.9). chloride and sulphate uneffected in the water. As mentioned earlier.. This i. 1 mvallkg of value = 40 "lg of CaC0 3/l or 0. the medium or intermediate pressure boilen are those that operate between 300 to 900 psig (20 to 64 kg/cm 2). By this process the total solids are reduced to an extent equivalent to the alkalinity in raw water. so that most of the dissolved oxygen is given off. it needs to be eliminated in the water circuit. Conductivity + lu/cm P value ++ mval/kg Silica mglkg Phosehate m~k& + ++ Working Pressure in kglcm2 20 10. these resins have -COOH as their functional group.and Na+ are released from the two columns respectively. The bicar.2. Ca++ and Mg++ are e:tchanged and replaced by H+ in the water under treatment. The total dissolved solids content is reduced by a factor corresponding to the removal of Ca and Mg carbonates and the product water is of low hardness and low alkalinity. as well as most of the hardness is permanent. while the other is loaded with a strong acid cation exchanger in the sodium form. This is usually realised through the use of two streams (independent and parallel) of ion exchange columns. Ca++ and Mg++ get exchanged in both the columns.000 12 70 10 -20 40 5000 6 64 30 15 2500 3 10 15 Sp. the dealkalisation is carried out by the use of a weak acid cation exchange resin in the hydrogen form. but energy input is needed. which is al~o softened. sodium chloride rather than acid.74 (b) Water Chemistry Alkalinity in raw water is high and the total hardness more than the alkalinity.bonate and carbonate ions are replaced by chloride. In the former case. Conductivity measured at 25°C after neutralisation with HCI with phenolphthalein as indicator. saturates the water stream with dissolved oxygen. The guideline values for the chemical quality of boiler water are given in Table 7. while H+ . the sulphite gets oxidised to sulphate leading to a low level of dissolved oxygen. the temperature of the water is raised and sprayed through a tower. Since this accelerates corrosion. In the first situation. On the other hand.) of Medium Pressure Boilers(lO) Chemical Parameters Sp. in chemical addition. The resins are regenerated by the usual procedures.

The best aqueous environment in which boiler steel can form and maintain a protective oxide layer that protects the metallic surface from further corrosion. as fears surfaced of hydrazine being a possible carcinogenic agent. The last one has FDA approval. A sudden switch over to polymer based treatment is not advisable without proper precautions like a heavy blowdown. a programme of using chelants like nitrilo tri acetic acid (NTA) and ethylene diamine tetra acetic acid (EDTA) to keep Ca and to some extent Mg.2. a) Drum type recirculating and (b) Once. saw dust. In low pressure boilers.through. 7. As seen earlier. is realised by maintaining a controlled degree of alkalinity with sodium hydroxide. lignin etc. reminiscent of cooling water treatment. These are boiler water (which boils).Water Chemistry in Fossil Fuel Fired Steam Generating Units 75 Working curves that relate the admissible levels of conductivity. started to make use of hydrazine to control dissolved oxygen. the sulphonated and the carbonxylated polymer along with a copolymer are being recommended for sludge conditioning in boilers upto 900 psig or even a little higher. At the required residuals of the chelants. carbohydrazide. methyl ethyl ketoxime and erythorbic acid. Fe and Cu in solution has been proposed. While problems crop up with such a type of control in high pressure systems.t incorporate sulphonic and carboxyiic functional groups are proving bettel than the earlier straight chain polymers such as polymethyl ~ethacrylate. Medium pressure boilers have also. The very fact that the p-alkakinity is allowed to be present in the boiler water means that NaOH is added and the system is under alkaline operation. In fact. Makeup water is the high purity water that comes from the demineralisation plant and as the name implies will take care of the losses due to blowdown and aflY other leaks. silica and p-alkalinity to the working pressure are available in literature. tanin. which allows its application in the food processing industry where steam comes in contact with food products. but monitoring of the chelant concentrations in boiler water is difficult. aided by the presence of sodium orthophosphate. There are other advantages as well.2 High Pressure Boiler Water Treatment All the boilers or steam generators operating above 64 kg/cm2 (900 psi g) come under the category of high pressure boilers. Among these are hydroquinone. Alternatively polymers have also gained attention as sludge dispersants. We are now in a position to consider . this treatment offers enough protection against corrosion. The blowdown is from the drum. diethyl hydxylamine.provided dissolved oxygen is controlled. New polymers t:19. Early dispersants include potato peels. scale and sludge problems are minimised. in other words its composition corresponds to boiler water at the time. a number of substitutes for hydrazine have come into the market. there are three varieties of water in the steam water circuit. Apart from steam. condensate water and feed water (condensate+makeup water). This chemical regime has been evolved to minimise the corrosion of iron and other ferrous alloys' in the boiler circuit that come into contact with water. hydrazine is a better dissolved oxygen scavenger than sodium sulphite and is widely used in high pressure systems. for boilers in the medium or intermediate pressure range. They are of two types. Subsequently synthetic polymers have been used to distort crystal growth. However.

a few mgn of residual phosphate as trisodium phosphate was also addeti to the boiler water. A number of inhibitors were tried and found unsatisfactory. improvements were made such as welding boiler drums and the eiimination of 'cold' work practices. if any hardness salts enter the feed train due to condenser tube leaks or contamination of makeup water. To combat the two corrosion problems mentione above. a pH range of 9.3 Referanee Data for Conventional Coordinated Phosphate Treatment pH Value 10. 10 20 40 80 100 .76 Water Chemistry different facets of water conditioning in the steam water circuit of high pressure boilers. In addition. On the design and fabricaton side.00 Working curves are available in Iiterature(11). This points to the need for very close control and monitoringJlf. As operating pressure increased. The observed pH has to be less than what would have been attained. Fifty years ago 'caustic embrittlement' was a major problem.90 11. This would be of use. As it is not advisable to have such a pH value in the presence of copper alloys in the circuit.0 was considered a!=ceptable. It is normally a pitting phenomenon and occurs underneath the deposits of boiler tube internal surfaces.35 10. where sodium salts are used in one or other form. The relevant data are given in Table 7.65 10. Due to high concentration factors. Prior to 1950. the process and the mechanism will be discussed in some detail. In boilers operating at pressures greater than 160 kglcm 2 (2300 psig) is the boiler water contains more than 3 mgll of caustic.in the boiler water.5 to 10. thus reducing the risk of 'caustic embrittlement and gauging'. The value of pH in boiler water is maintained by phosphate.05 10. A lower pH value ensures the absence of free alkali. this treatment was found to lead to two corrosion problems. Flashing of steam in and around the sensitive areas produced localised high concentrations of NaOH in the adjoining crevices. a different concept called the co-ordinated phosphate-pH control came into vogue forty years ago(I1). Metal wastage can be very rapid once caustic gauging starts. 'Caustic gauging' persists in modern high pressure boilers. in this type of boiler water treatment. It was commonly found in areas around the riveted seams of boiler drums and in the highly stressed areas where tubes were rolled into the drum. As this method continues to be in wide use even today. namely 'caustic embrittlement' and 'caustic gauging' of the boiler internals(4). Simply put. The first one was based on the presence of free caustic so that the boiler water is in the pH range of 10 to 11.3. Table 7. if an equivalent of Na3P04 alone was present in the water. its solubility in steam is such as to exceed the primary target. there is sufficient phosphate to prevent the formation of 'free caustic'.Na+ and OH. there were two types of chemical conditioning for boiler water in recirculation type boilers. This type of attack was due to concentration of alkali in certain locations of the boilers. NaOH is built up under the porous oxide deposit.

5. The addition of trisodium phosphate alone will produce OH.5 to 10.+ HPO-2 (7. It stands to reason that with increasing pH (excess of OH-) or increase in HPOi. the phosphate in solution is exclusively present as the monobasic ion. that in the pH range of9 to 11 more specifically 9. that the best way of chemical control is to add a mixture of trisodium phosphate and monosodium dihydrogen phosphat. Hence.due to a reversed hydrolysis reaction(I1).in the form ofNa2HP0 4 to the system.Water Chemistry in fossil Fuel Fired Steam Generating Units 77 Chemical control is maintained by adding trisodium phosphate mixed with Na2HP0 4 and NaH 2P0 4 and not by itself. as in fact.e.3-Coordinated phosphate pH control Is desirable where the makeup water is from the demineraliser plant.4. the only course open is to add HPOi. HPOi-It is this pH range that is specified in many boilers.from boiler water. PO402 4 3. the rate of conversion of the trisodium salt to the monosodium salt is increased and vice versa in case of pH rise. This is represented by.+ H2P0 4(7.4.concentration. HPOi.3 results in high phosphate values leading·to the distribution of the solute between boiler water and steam. Since the question of increase in pH does not arise. When boiler water pH fluctuates. Since many utilities use ammonium hydroxide as a pH or 80 83 .+ H <=> OH. Percentage of Different Species of Phosphate pH H2P04- Percentage of HPOi- 6 7 8 9 10 11 12 13 93 40 14 3 7 60 86 97 100 95 5 70 17 It is seen from Table 7. In the higher pressure range of boilers (175 kg/cm 2) chemical control by using data given in Table 7. In the theoretical formulations. Table 7. The guidelines are the Same as in Table 7. the reaction proceeds in the backward direction due to the mass action effect.5 is to be used. Table 7.4 pH vs. It is also observed from.4 gives the percentage of the three species of phosphate as a function of pH at 25°C.2) The degree to which this reaction proceeds depends upon the pH of the solution at equilibrium. For example.+ H20 <=> OH.3) Table 7. the whole exercise is to remove free OH. Alkaline -pH buffers other than phosphate in boiler water disturb the phosphate relationship. when pH drops due to condenser tube leaks. the ratio of these two salts is so adjusted as to bring the pH into the desired range. a lower level of phosphate is desirable and the data given in Table 7. the question of the hydrolysis ofHPOiis also to be looked into.

30 10. where hardness salts(Ca and Mg) are rigorously excluded. the presence of chloride in boiler water will lead to the buffer NH"OH . It then decreases gradually upto 210°C to a value of60 gm/IOOgm and falls sharply thereafter. Its interference in measured pH values after phosphate (tri and mono mixture) addition is to be carefully evaluated.15 9. A phenemenon encountered in phosphate treatment of boiler water is its hide-out(ll).mgll 1.0 2.20 10.02 10.80 10.0 24.0 30.5 . At 230°C it is only 20gmliOOgm of water.Reference Data for Low Level Coordinated Phosphate Treatment for High Pressure Boilen Phosphate. The hide-out is due to this retrograde solubility (Table7. Table 7.40 10.78 Water Chemistry Table 7. specially in high pressure boilers (where transport of NH 4CI into the steam introduces a further complication). to a value of around 94 gms/lOOgms of water.6).0 20.0 15. pH (25°C) 9. The solubility of trisodium phosphate increases with temperature upto 120°C. The 'free caustic' condition in boiler water is understood not only in terms of its possible concentration but also on the basis that free hydroxide serves no useful purpose in high pressure boilers.30 9.oC 38 65 93 120 150 Solubility (gm/IOO gm H2O) 20 45 70 94 82 65 60 18 7 177 204 232 260 .0 10. Thus one important conclusion is that chloride in boiler water is undesirable.0 • As a mixture of Na3P04 + Na2HPO. A variation of the coordinated phosphate pH control is known as the congruent pH-phosphate control.60 9.50 regulating agent.NH 4Cl.0 4.0 6.6 Solubility of Trisodium Phosphate as a Function of Temperature Temp. which employs a mixture of phosphates as mentioned earlier.

to ascertain the extent of hide-out and its implications. While alkalinity is a major factor to be properly controlled in the water steam circuit. the phosphate can be blown down and the treatment reverted to AVT.8 to 10. a number of utilities have operated under cyclic hide out without much damage to boiler tubes. The characteristics and behaviour of ammonia. Thus phosphate menitoring during load changes is very important for high pressure boilers. However the alkalinity that can be reached with ammonia and morpholine is lower and chemical control limits for pH are 9. which is undesirable. the alkalinity drops quickly. In fact. After the tube leak is plugged. A disadvantage of the AVT is the lack of buffering capacity. even if fresh water is used for tondenser cooling. The advantage of such an All Volatile Treatment (AVT) is that the reagents being volatile. the phosphate is redissolved with a reduction in boiler water pH. there is reluctance to use the potass. condensate polishing is mandatory. While morpho line is a component of AVT. Thus the amount of hydrazine to be dosed depends not only on its scavenging action for oxygen. this may result in free hydroxide. to reduce ~issolved oxygen to less than 10 ~g/l and maintain its pH in the alkaline range. It must be mentioned that sodium phosphate hide-out (crystallisation) can occur on the surfaces of boiler tubes. since it has a much higher solubility than the sodium salt at high temperatures. but also on its rate of decomposition under operating conditions. Condensate polishing will give some lead time to operators under the above circumstances.than with NaOH. There have been suggestions to make use of potassium phJsphate. it has been suggested that the chemical treatment be switched to coordinated phosphate addition. morpholine and hydrazine were considered in detail in Chapter 4. leading to elevation of the tube temperatures. Under operating conditions.0 in boiler water. To maintain the corrosion of the boiler at a very low rate the feed water is also specially chemically conditioned by hydrazine dosing. It is clear that the phosphate regime has no influence on the dissolved oxygen. tl Fuel Fired Steam Generating Units 79 Utility and laboratory studies indicate that the compound which crystallises out under hide-out conditions has a sodium to phosphate ratio of less than 3: 1.5 or more usually 9. specially if the condenser cooling water is brackish or seawater. While phosphate hide-out is not desirrable. will also go into the steam phase and get condensed along with it. in once-through boilers that operate only under AVT. Under such circumstances. control of dissolved oxygen and alkalinity by volatile chemicals like hydrazine and ammonium hydroxide or morpholine has beell considered(12). At high temperatures hydrazine also decomposes to ammonia and hydrogen.Water Chemistry in Fos . With increasing boiler pressures and the introduction of once-through boilers.. Although this has been tried(6).um salt as evidence shows that gauging type corrosion is more with KOH. Consequently.5 to 10. specially in nuclear power stations. it is equally important to control dissolved oxygen to avoid pitting corrosion. . When the plant load is reduced. Thus they give protection to the turbine and condenser surfaces in addition to the boiler internals (See Chapter 4). during condenser tube leaks. even if they are in a clean condition.

as failures in turbine components impose a greater economic penalty and unit unavailability. Steam side problems are dealt with in the next chapter. boiler and condenser sections. it is generally agreed that oxygen at the economiser inlet be less than 7 J.1g/1. there are other candidates for alkalinity control such as cyclohexylamine (CHA)and methoxypropylamine (MPA). are pH and dissolved oxygen. These amines have both hydrophobic as well as hydrophilic groups. 7. At the outset it should be mentioned that the earlier approach was to specify these chemical targets mainly based on corrosion control in the preboiler.1g/1.2. oxygen should not exceed 5J. Hence the steam purity has become the guiding principle. A study of the literature reveals that every organization basically agrees that the important parameters in feed water. the Central Electricity Generating Board (CEGB). the steam side corrosion and deposition problems have been found to be much more important than the water side corrosion in the other sections of the unit. USA. These are commercially available as blends under different trade names. oxygen should be less than 151lg/1. copper and nickel ::orrosion products a limit is sel by CEGB. advises that oxygen at the deaerator outlet be less than 7J. filming amines and oxygen scavengers are highly recommended. In other w0rds the specifications have been evolved mostly with respect to the water si1e corrosion. During operation about 10 to 30 mg/l (an average of 20 mg/l) of residual hydrazine would be able to keep oxygen within the specified limits. the use of filming amines such as octadecyl amine is on the . manufacturers etc. Electric P.1g/l. UK(14). In addition. In addition. USA. a combination of neutralising amines (for alkalinity control/neutralisation of CO2 in the boiler due to decomposition of organics). it should be less than 20 J. The monQmolecular film formed on the oxide surface inhibits bt~h low pH and oxygen attack but does not protect the pitted surfaces. considers dissolved oxygen as a primary target and specifies that at the economiser inlet. In fact. agrees with this low Iimit(J). For 200/210 MWe sets in India. it has been amply realised that this is not an appropriate approach.80 Water Chemistry ammonia continues to be made use of in several fossil fuel fired stations and in once-through steam generators. Boiler Water and Condensate Against the above background let us consider the optimum chemical regimes envisaged by different utilities.3 Chemical Regimes for Feed Water. CEGB further specifies that at the condensate extraction pump discharge (CEPD). Since this measure is to control the concentration of iron. the quality of feed and boiler water has to be upgraded. while at CEPD. in this respect also as a primary target. To achieve that type of purity. These figures are based on the de aeration capability of modern plants and are supplemented by the addition of hydrazine as oxygen scavenger. At the economizer . It is quite possible that MPA would playa leading role in AVT in the years to come. Combination of amines is also being practised in the condensate system.increase. During the last decade. In high pressure turbines.ower Research Institute (EPRI). Combustion Engineering (CE). for feed and boiler water and condensate in high pressure steam generating units. This ofcourse will automatically ensure that water side corrosion is minimised. For optimising protection. The current praQtice is to look at cycle chemistry from the stram side(lJ).1g/l(1S).

From the above resume. Recently EPRI (based on steam purity consideration) reduced the Cu limit to 2 ~g/l. This is the same limit as for makeup water. Thus their chemical regimes are equally important.1 200 20 0.8 to 7. The concentration of the alkalising agents and the specific conductivity should be consistent with this pH range.0 to 9. at the economiser inlet. it is evident that oxygen and its control is a very important chemical function in operating power plants. pH is another important specification of the feed water chemical reigme. Silica has not been included as a primary target in feed water either by CEGB or EPRI. In case condensate polishing is utilised.3. With both sodium and chloride being at low levels.6. while for all ferrous systems. but specify only Fe and Cu (10 ~gli each). It is noteworthy that pH has not been specified. Table 7.2.2 0. the pH range (at 25°C) specified by EPRI is 8. feed water is a mix of condensate (with or without polishing) and a relatively small amount of treated makeup water from the DM plant. '02 Sp. it is 9.3 . it is assumed that the pH will be in the neutral range of 6. conductivity ~s/cm Cation conductivity ~ stcm Cation conductivity ~stcm (if condensate polishing available) Makeup water (~gll) Condensate pump discharge (~gll) 5 5 10 3 3 10 300 0. Combustion Engineering mentions a limit of20 ~g/l for total silica. to make surt: that no other soluble impurities are getting into the boiler. As mentioned earlier.2 ~s/cm (EPRI). In view of the importance attached to corrosion of Fe and Cu components. silica should not exceed 10 ~g/l (EPRI).Water Chemistry in Fossil Fuel Fired Steam Generating Units 81 inlet these should not exceed a combined level of20 ~gll. The EPRI guidelines arc summarised in Table 7. On the other hand. For systems having both Fe and Cu.13) Chemical parameter Sodium Sodium (if condensate polishing available) Chloride Sulphate Silica TOC Dis. CE and ASME agree with this limit.7. at the polisher outlet.8 to 9.7 EPRI Guidelines for Makeup Water aDd Condensate(U. the cation conductivity of feed water at the economiser inlet should be less than 0.

Since the guidelines set by EPRI in 1986(15) have been evolved through a long process ofconsultation between experts. utilities and vendors.8.3 to 2. UK.hosphate treatment also. Table 7. Phosphate is given a. with a minimum of 5 mgll at 64 kglcm 2. (lower than CEGB value).. In case caustic soda alone is employed as the alkalising agent. Conductivity Cation conductivity Silica Units mgtl by wt as NaCI mgll by wt as NaOH at 25°C ~ s/cm at 25°C ~ s/cm at 25°C mgll by wt. for AVT. For the coordinated P.8. such as increasing blowdown and reducing pO\L'er can be taken within specified time limits.8 % 0. CEGB has separate specifications for the high pressure.3 mgtl.2 Less than 20 less than 6 0. they should be gh.s 2 to 4 mgll. As expected in boiler water in drum type units with or without reheat.82 Water Chemistry With the respect to boiler water of the drum type unit. since sodium compounds (as hydroxide or chloride) are major boiler tube and turbine blade corrodents. NaOH should be 1. Free caustic is not permitted at all. This is because of the fact.e. NaOH of 0.5 mgtl 9. However. The chloride specification shows a decrease from less than 6 mgll to less than 2 mgll with increase in pressure from 900 to 2350 psi (or 64 to 162 kg/cm 2). that mere caustic'addition is no longer practised. .CEGB. as sial - Higb Heat .5 x NaCI with min. which is to be reduced to a minimum of 2 mgll at 162 kglcrp2. enough weightage. the underlying arguments for the variation must be clearly spelt out.S times that ofNaCI. sodium concentration is specified as 5 to 2 mg/l. corrective action. its level is made dependent upon the level of chloride impurity as NaCl.high heat flux boilers (162 kg/cm2) cooled by seawater.0 to 9. the chloride levels are the same as with free caustic treatment. The same specifications hold for chloride as well.. as NaCI for all pressures. . . In the 64 to 162 kg/cm 2 pressure range. as given in Table 7. while silica and chloride should be less than 300 and SO ~gtl respectively. the sodium limits are very stringent.Primary targets Less than 0. The pH is mentioned as 9.5. while that of silica are from 3 to 0. pressure so that any situation can be monitored and analysed for target values.8 CEGB SpecificatioDs for Higb Pressure (162 Kg/cm1) Flux Boilers Cooled by Sea Water(J4) In Boiler Water Chloride Caustic Soda pH Sp. makes a clear distinction between units employing NaOH or NaOWPhosphate or AVT. in the author's opinion. Working curves have been developed by EPRI for different chemical contaminants vs. If others differ from these guidelines. the chloride level must be less than 0.5 1.2 mgll by weight. Sodium to phosphate molar ratio is in the range of 2.. Action levels have been prescribed so that when contaminants exceed target values beyond these'levels. comparable to the operating pressures given above by CEGB) the boiler water chemistry specifications appear to be slightly different(16).2 For 200/210 MWe units in India operating upto a pressure of 160 bar (i.

The question of caustic and phosphate treatment does not arise at all and OTs depend upon AVT only. At present. occasionally going as high as 3 J1s/cm. while in two others it was about IJ1s/cm. clearly demollstrYas the need to monitor the chemical parameters of different components of water as found in the steam generating system and understand the reasons for normal or abnormal varations.0). What was surprising was that at the remaining two stations. it was obvious that considerable improvement was needed. the chemical regime will be much more stringent.9. where the condensers are cooled by river or dam water. whilst the higher "level was a result of feed water contamination. . improved the feed water conductivity through a better leak-proof situation.Water Chemistry in Fossil Fuel Fired Steam Generating Units 83 A study on the feed water and boiler water characteristics of seven thermal power stations in India.Brass by Cu-Ni tuDes. is the one attached to the Fast Breeder Test Reactor at Kalpakkam. For example.spread over a realistic time span revealed the following features(l7). On comparing the above observed values with the specifications discussed earlier.4 J1s/cm). silica (10 to 20 J1g1I) and chloride (not detectable. The ratio varied from about 10 to 70.3 to 0. the specific conductivity of the feed water was above I J1 s/cm for most of the time. It is evident that for once-through boilers. without a drum and blowdown facility. at the sea water cooled station. its characteristics were also studied. The above discussion along with the examples. The problem of high feed water conductivity in the last two stations was traced to condensate contamination and remedial action in terms of cleaning and corrosion protection was initiated. Other characteristics of feed water studied were the pH (maintained between 8.cooled locations). The type of chemical treatment for feed and boiler water is often referred to as 'Zero Solids Treatment'. replacement of the AI. At a seawater cooled power station. The concentration factor between feed and boiler water was also studied in terms of the ratio of the respective specific conductivities.with ammonia (in most cases) or morpholine as the alkalising agent and hydrazine as the dissolved oxygen scavenger. Since feed water is a mix of condensate and makeup. except at the sea water . In only two out of the other six stations. The specifications for once-through boilers as stated by CEGB(l4) are given in Table 7. the feed water conductivity was higher than at the seawater cooled location. It was reasoned that the lower level was due to excessive blowdown. Operational experience on the ammonia cycle is very limited. although their condensers were being cooled by fresh water.S to 9. This was due to condenser tube leaks.only then can corrective action be initiated(18). Phosphate treatment was in vo~ue in all stations. Condensate polishing is mandatory and the alkali sing agents create special problems in terms of resin selectivity at times of condenser leakage. the feed water conductivity was lower (0. the only once-through boiler or steam geneator in India.

84

Water Chemistry
Table 7.9 CECB Primary Targets for Once-Through BoUers(14)

Parameter Cation conductivity 01 slcm at 25°C) pH at 25°C

Limit 0.1 9.0 - 9.3

Dissolved 02 (J.lgll)

15
5 5

Sodium (mgll by wt. as Na) Silica (mgll by wt. as Si02) Total Fe, Cu and Ni (mgll by wt. as Fe + Cu + Ni)

20
10
(3 as Cu)

Sampling Points Condensate polishing plant outlet After chemical dosing at the condensate polishing pl"nt outlet Final stage extraction pump discharge. Boiler inlet. Condensate polishing plant outlet. Condensate polishing plant outlet. Economiser inlet or boiler feed pump discharge.

In conclusion, it needs to be emphasised, that with increasing pressure of the operating units, the chemical conditioning procedures have undergone a change, both in character and rigour. Currently, the chemical targets in the water phase are derived from the chemical control requirements of the steam phase, which will be discussed in the next chapter.
REFERENCES 1. CBIP( 1988), "Investigation on Water Chemistry, Material Compatibility and Related Problems in Steam-Water Cycles of Thermal Power Stations". A project Completion Report, July 1988. Central Board of Irrigation & Power, New Delhi. India. 2. CBIP (1988), "Investigation on Boiler Tube Failures in Thermal Power Stations: A Project Completion Report, August, /988. Central/Board of Irrigation & Power, New Delhi, India. 3. Gabrielli F., F.R. Henry, R.C. Keistead, J.A. Ray and W.R. Sylvesta, (1978). Prevent Corrosion and Deposition Problems in High Pressure Boilers. Power, July 1978,8592. 4. Venkateswarlu K.S., (1979). Corrosion in Power Industry. Corrosion & Maintenance, 4,257-259. 5. Venkateswarlu K.S., (1988), Deoxygenation : An Essential Ingredient in Steam Generating Indqstry, Chemical Business. February. 6. Venkateswarlu K.S., (1984), Chemical Treatment of High Pressure Boiler Water to Ensure Steam Quality Requirements, Corrosion and Maintenance, 7. 177-182. 7. Deshpande K.V., (1992). Feed Water Tr:atment for Low Pressure Boilers. All India Convention on Industrial Water Treatment and Conservation. National Centre for Technical Development. Bombay, Nov. 1992. pp. H.l to H.3. 8. Mhetre S.N., (1992), Low Pressure Water Treatment: Cost Economics of Dealkalisers vs. Softners, Ibid., pp.OO.1 to 00.15. 9. Deshpande K.V., (1992), Dealkalisation for Small and Medium Pressure Boilers,lbid.• pp.I.l to 1.5. 10. VGB, FRG, (1972), Indicative Data for Water for Industrial Use, Vd TUV. Edition. April 1972,164-173. II. Klein H.A., (1962). Use of Coordinated Phosphate Treatment to Prevent Caustic Corrosion in High Pressure Boilers. Combustion, October 1962. 1 to 8.

Water Chemistry in Fossil Fuel Fired Steam Generating Units
12. 13. 14.

85

IS.

16.

17. 18.

Strauss S.D .• (l!)86). Advances in Chemical Water Treatment Improves Reliability of Steam Generating Systems. Power. October 1986. 15-20 and references therein. Strauss S.D .• (1988). Water Treatment Control and Instrumentation. Power (Special Section) May 1988. W.l-W.30 and references therein. CEGB. Generation Operation Memorandum 72 (1973). Chemical Control of Boiler Feed Water. Boiler Water and Saturated Steam for Drum-type and Once-through Boilers. Central Electricity Generating Board. U.K.• September.1973. 5-25. Aschoff A.F.• Y.H. Lee. D.M. Sopocy. and O. Jonas (1986). Interim Consensus Guidelines on Fossil Plant Cycle Chemistry. Electric Power Re.search Institute. EPRI CS 4629. June 1986. Gopal R.• (1983). Water Chemistry and its Control in Feed and Boiler Water. Proc. Wor/cshop on Water Chemistry itt Thermal Power Stations. 39-46. Central Board of Irrigation and Power. New Delhi. India. Venkateswarlu K.S .• (1985). From Raw-Water to Pure Steam: Problems in Thermal Power Stations. CorrosioR and Maintenance. 187-192. Straiss S.D .• (1990). Water-Chemistry Improvements Enhance Steam-System Reliability. Special Report Power (International Edition). Dec. 1990.27-32.

8

STEAM QUALITY REQUIREMENTS FOR HIGH PRESSURE TURBINES.~

Steam purity is an important criterion that has received considerable attention from industries in developed nations. The relative distribution of contaminants between boiler water and steam is a function of .emperature and pressure. At pressures in the 105 kg/cm2 (1500 psig) range or below. the steam solubility or vapourous carryover of the soluble contaminants. except that of silica. can be ignored at concentrations which are usually encountered in boiler water. In this range of temperatures and pressures, the salt content of the steam is essentially due to moisture entrainment of the steam. The solvation property of steam increases as the critical point and single fluid phase is approached. For very high pressure recirculating boilers 193 kg/cm2 (- 2750 psig), SO to 90 percent of boiler water soluble contaminants (mostly the sodium salts) are transferred to the steam phase and get deposited in the turbine with decrease in ste&m pressure. In supercritical pressure boilers copper transport and redeposition in the turbine is also a serious problem. The purity of inlet steam to the high pressure turbines is specified by leading manufacturers to be: Conductivity less than 0.3 micro siemens/cm with sodium and chloride less than 5 Jlg/l* (Table 8.l). Manufacturers and the organisations of electrical utilities give specifications for high pressure steam that differ slightly. Those listed in Table 8.1 illustrate the stringent requirements for the purity of HP steam. During the last few years, the tendency is to further tighten these specifications under normal operation. For example, MIs General Electric, USA puts the limit for sodium at 3 Jlgn and cation conductivity at 0.2 j.ls/cm, while MIs Allis Chalmers, USA gives a limit of 1 Jlg/l for copper. EPRI guidelines, on the other hand, are those evolved through comprehensive discussions(l).

*

Ilgll may be taken as equivalent to ppb.at such low levels

3 Limiting condItions of operations 2 weeks 24 hrs.5 In all drum type boilers. the feed and boiler water chemistry specificatiQns are arrived at by working backwards from steam quality requirements.0 0.g to drive a turbine or crack naphtha and whether it is to be superheated or not.3 to 0. To mention only a few. This is to prevent the moisture carryover of soluble impurities into the steam phase. As noted !n the previous chapter. The variations in steam quality are partly due to lack of stringent control on feed and boiler water quality due to a lack of sufficient appreciation of the basic chemistry involved in the high pressure steam-water cycle(3). As a result of this. As steam expands in the turbine. the stresses to which the components and parts of the system are subjected to during operation and chemical environment. All this is apart from mechanical carryover of impurities(Z). In fact steam quality has become a varying parameter in otherwise comparable high pressure turbines. lower quality steam leads to deposit formation in crevices and the consequent loss of thermodynamic efficiency as well as corrosion and erosion of the turbine parts. If the steam is to be super heated.1 High Pressure Steam Quality Specifications(1·S) Impurities in HP steam (~gll) Sodium Chloride Dis. means are provided in the drum to seperate the steam generated in the boiler·tubes from water. One can see this from solubility data represented on P. Thus one has. which is high quality steam. different impurities present in steam start separating out and get deposited in the turbine as the solubility of most compounds in dry steam decreases with pressure. Detailed studies have shown that reliable performance of high pressure steam turbines depends on the selection of its constructional materials. the seperation efficiency should be such that the moisture content is well below 0.5 percent of moisture can be tolerated. the control of steam chemistry/has not been achieved to the same extent. 10 to 20 5 to 10 5 to 10 10 to 20 10 to 30 30 to 100 10 to 20 20 to 50 0.5 to 1. This has-led to better steam quality.25 to 0. enthalpy. In the former case. 0. The required efficiency of this seperation depends to a great extent on the use to which the steam is put e. a n\lmber of problems have been experienced. At the same time considerable progress has been made in understanding the steam chemistry as it passes through the turbine(from high to intermediate to low pressures). 02 Silica Cu Fe Cation conductivity (~s/cm) Normal operation 87 6 5 10 10 2 20 0. T coordinates or a Mollier diagram (Chapter 4).Steam Quality Requirements for High Pressure Turbines Table 8. While design and availability of improved materials have reduced the contribution of the first two causative factors. From this it is deduced that the presence .2 percent. where the coordinates are entropy vs. 'saturated steam' and 'super heated steam'.

Besides sodium hydroxide. calcium aluminium hydroxy sulphate. oxides of copper a~d sodium sulphate are preferentially deposited in the HP and IPstages. when the pressure is reduced from 1176 to 1063 psia. Solubililty data ofNaOH and NaCI in steam illustrate this point very clearly(4). An extensively reported study in this context.l. sodium carbonate.l.g/I. The so-called 'Ray Diagram' of the carry over coefficients from water into the steam phase given by Martinova of the Moscow Power Institute.g/l (again in terms ofNa) over a narrow temperature range (327. IP and LP) of the turbine internals. is widely used to appreciate this aspect of steam chemistry (See Chapter 4). the concentration processes operate via deposit formation from super heated steam.5°C). (which represent some of the highly complex . wherein it was shown that concentrated caustic solutions were deposited in this turbine. The same is true for NaCl. the solubility ofNaOH in steam is 750 J.. As the density difference between the liquid and" vapour phase diminishes and the critical point is approached with dielectric constant of steam on the increse. sodium aluminium molybdenum silicate etc. the transport of materials to the vapour phase steadily increases. when the pressure is reduced to 1052 psia at a temperature of 316°C. evaporation and drying as well as adsorption or inotganic ion exchange on the metal oxide surfaces. Just how clean the steam entering the turbine should be and the mechanisms involved in stress corrosion cracking are still not fully appreciated. the solubility sharply decreases from 680 to 360 J. This would mean that NaOH in dry steam at high pressures ought to be much less. For very high pressure ( 190-200 kglcm2 drum pressure) recirculation boilers. In the case ofNael. is the failure of a turbine at Hinkly Point 'A' power station. It is evident that seperation of concentrated solution ofNaOH would adversely effect the turbine parts due to stress corrosion cracking. Chemical impurities such as NaOH or corrosion product oxides enter the steam phase from the water phase due to their differential solubility between the two phases. the construction materials can tolerate steam with low levels of impurities.gll ofNaOH is sufficient for the formation of an 80 percent solution ofNaOH in the intermediate pressure range(·I). Without such concentration mechanisms.88 Water Chemistry of just 10 J. Chemical analysis of the compounds in steam turbines has shown a wide variety and range of compounds such as potassium trisodium aluminium silicate.l. the vapour transport of sodium salt may approach 80 percent of the total solids carried.g/l (in terms of Na). It has been shown that iron oxide films concentrate impurities by a factor of 10 to 100 and this might alter the composition of the steam/water phase close to oxide interface.7°C to 325. Even though the impurity levels in the feed and boiler water are kept relatively low. sodium phosphate and iron oxides are known to get deposited on all tje three states (HP. which decreases sharply to 540 J.l. It is known that "dissociative hydrolysis" of sodium chloride into HCI and NaOH at the hillb temperature oxide surfaces results in the products as such being present in the IP and LP sections of the steam turbines. while silica & sodium chloride get preferentially deposited from the steam phase in the IPand LP sections(2). On the other hand. the concentration of such impurities in the steam phase within the turbine results in a host of problems. At 330°C and 1067 psia pressure. However.

6). for superheated/reheat steam is. in any 24 hour operating period at full power. It has been emphasised by Westinghouse Electric Corporation that. Table 8. If due to some reason or other. Analytical methods currently available are able to determine sodium in quantities " less than 5 J. for a two week operating period at full power.1g/l. low enough to guarantee that no deposition takes place of sodium hydroxide. Impurity concentration in dry steam should be below its solubility anywhere in the dry regions of the system (turbine)".1g/1. Table 8.Steam Quality Requirements for High Pressure Turbines 89 compounds present) on the oxide surfaces in steam turbines.1. Under such conditions. The best way to measure cation conductivity is to remove carbon dioxide by blowing pure dry nitrogen. the conductivity . these limits of sodium and chloride are exceeded during normal operation. . The most important cationic and anionic limits are for sodium and chloride. electrical utilities in USA and other advanced countries have realised that an improvement of steam purity is needed in several operating units inspite of the existence of well established boiler water specifications(5.2 lists some of the failures in turbine components and the suspected causes behind such events. The corresponding limit for chloride ior has also been specified to be less than 5 J.. Sodium and chloride should not each exceed a limit of 20 J. will avoid interference due to the presence of ammonia.2 Turbine Part Failures-US Industry Experlence(5) Failure HP Turbine bolts (steel) HP Discs (Ni Cr Mo) HP Blade (Springs) HP Inner cylinder (Cr MoV) LP Blades (SS) LP Blades (12 Cr hardened) Probable Cause High Na in steam High caustic in steam . Ion chromatography with ready to use cartridges for concentrating chloride in spot samples is also on the anvil. Cation conductivity rather than the total conductivity measurement. but will reflect the presence of carbon dioxide. some limiting conditions on operation have been suggested. Measurement of the conductivity of the steam condensate after passing through a cation exchanger. ferric sulphate etc(3).doHigh NaOH.1g11. On-line chloride analysels using solid state electrodes are available for such measurements. in addition to simple compounds such as sodium chloride.1gll in one calender or operating year.1g/l in one calender year or in one operating year. NaCI in steam Organic acids in steam Inorganic acids in steam After a detailed study. For normal operations. (a) The steam quality should be achievable. the sodium level has been specified to be less than 5 J. The philosophy behind the recommendations(l) as given in Table 8. sodium chloride or any other compound any where in the turbine. these impurities in steam might range from 5 to 10 J. (b) The specified limits should be measurable. is also used as an important specification. On the other hand.

as well as on the pH of the boiler water.2) 0. It may be noted that EPRI introduced a new chemical parameter. when the specification limits are exceeded duriAg normal operations(l). it is desirable to follow the guidelines. given in Table 8. as a result of the silica hide out phenomenon and in view of the complex silicate formation in turbine deposits.1s/cm Normal 5 3 10 3 0. Table 8. The limiting conditions are 0.. sulphate. However.1g/1 J.5 to 1.3 ""AI 5 3-6 10·20 3·6 A2 10 6-12 20-40 6-12 0. twice that noted earlier. EPRI guidelines are as given in Table 8. viz.55 . During adverse operating conditions it can range from 20 to 50 J'g/l during a 24 hour period and can be in the range of 10 to 20 J'g11 during a two week period.3 Maximum Permissible Concentration or Silica in Boiler Water.9 0.4 Guidelines for Reheat Steam(l) Parameter Sodium Chloride Silica Sulpl1ate Degassed cation conductivity Unit J.7 0.1g11 J. iCthe Target or 10 J.6 0.3 J'S/cm during normal operation. Action level 2 is 48 hrs. Since the distribution of silica between steam and boiler water depends upon pressure.0 0. Action level 1 is 2 weeks (14 days). While sodium and cation conductivity are to be monitored on-line (continuous).6 0. As far as reheat steam is concerned.1.4. Action level 3 is 8 hrs. " A 20 J'g/1limit for silica in steam has been in vogue for quite some time.) pH 9 4.90 Water Chemistry of the steam condensate must be less than 0. The limits under adverse conditions were given earlier in Table 8.0 A3 20 12 40 12 1. after which the persistence of abnormality cannot be tolerated for more than 1 hr and calls for an immediate shut down.5 1.55-1.10 pH 10 5. same as noted earlier. whose limits are as tight as that of chloride.7 1.1g11 J. table 8.28 0.5 J'S/cm for two weeks in a calendar or an operating year. and 0. EPRI guidelines prescribe Action Levels.0 J'S/cm for 24 hrs.3·0.3. chloride and silica are to be sampled once a shift..3 to 0.12 18() Dissolved oxygen is yet another impurity that has been specified to be less than 10 mg/l during normal operations. this'"limit has been lowered to 10 J'g/1 for reheat units.1g11 J.1g11 of Silica in Steam is to be Met Boiler Pressure kglcm 2 60 90 120 150 Boiler water silica in mgll (max. while sulphate can be measured once a day.

Table 8. The pattern resembles that found in utility turbines. Proc. The Mollier diagram has also been applied in these cases to deduce the level of impurities that could be tolerated in steam. UK requires the sampling of saturated steam. Steam expansion lines are to be drawn for different types of operation of an individual turbine. It is obvious that the above limits are less stringent than for high pressure steam (superheat/reheat) in utility turbines. because of this type of situation. EPRI recommends the monitoring of sodium and silica in saturated steam.7(550) 15 20 40 10 12 25 30 40 80 150 200 200 0. there is every likelihood of impurity ingress into the high pressure steam. Strauss S. it is meant. The recommended steam purity limits for industrial turbines using non-reheat steam are given in Table 8. (1983). This is primarily due to the differences in density between steam and entrained water droplets. Power. (c) The solubility value at the cross point is the impurity limit. Water Treatment Control and Instrumentation. CEGB.Lu. By different types. Prabhakara Rao A. (b) The solubilities of major chemical impurities ill" superheated steam are determined at the points where these lines cross the saturation line. Most of the industrial turbines require an improvement in steam purity. Jonas. lb. a recent survey indicated that blade deposits dominate the problem area followed by pitting.REFERENCES la. Similarly. It is only to be expected.F.• Y.5 0. 25-38.S Steam Purity Limits in Industry Temp.4(900) 38.5. one can tolerate a higher level of impurity. Central Board of Irrigation & Power. (1986). One of the lacunae noticed was the quality of attemperating water. whether the turbine is to be operated at low or high load etc. . Sampling and Analysis of Water/Steam in Power Plants. June 1986. May (Special Section) 1988. Indu~trial (a) 1\Jrbines(6) Cation conductivity TOC Ils/cm °c Pulp/paper Oil Waste Heat Non-reheat units Pressure kg/cm2(psig) Inlet chemical parameters (llglI ) Na Cl Si 400 450 315 33. Coming to the consideration of industrial turbines as distinct from utility turbines. New Delhi. that with decrease in pressure. Sopocy. The following procedure is recommended for using this diagram. W-I to W-30. Unless this is well controlled. India. However. this is specific to the turbine under consideration.7 1. EPRI CS-4629. In fact. Workshop on Water Chemistry in Thermal Power Stations. so that the extent of contamination can be monitored. D.H.5(475) 63.• (1988). 2.D .M. Aschoff A.Steam Quality ~equirements for High Pressure Turbines 91 The author's experience(7) with thermal power stations in India indicates that sufficient attention is not being paid to the chemical monitoring and control of steam chemistry. and corrosion induced cracking(6).5 . and O.. Interim Consensus Guidelines on Fossil Plant Cycle Chemistry. It is generally recognised that saturated steam is the most complex fluid to be sampled(1).

I-P. November 1992.C. All India Conference on Boiler Water Treatment.J. Water and Steam Quality for Maintenance of Generation Efficiency. 7a. New Delhi... October 1980. Bombay.A. From Raw Water to Pure Steam: Problems in Thermal Power Stations. Venkateswarlu K. 4. Water Chemistry Venkateswatlu K.. Potter and F. 7b.S. All India Conference on Water Chemistry for Industrial and TherfTIQl Power Station Boilers.92 3a. Lindsay. (1980).W. 9th International Conference on Properties of Steam. (1989). All India Convention on Industrial Water Treatment and Conservalioll. Chicago.1-1 to 1-6. Gould G. 3b. (I98S). Germany. 10nu 0. (1979). April 1981. Bombay.S. Institute of Energy Management. (1978).T.S. Venkateswarlu K.S. lonas 0.78-83. Corrosion and Maintenance. Power. April 1978. Steam Quality Requirements for High Pressure Turbines.. 6. . (1992). American Power Conferences. (1981). Venkat:swarlu K. Pocock.S. 187-192. May 1989. Activities of the International Association for the Properties of Steam.. Turbine Steam Purity. G-1I1 to G-III1. Evans. P. National Centre for Technical Development. W. Developing Steam Purity Limits for Industrial Turbines. P. S. Indian Institute of Plant Engineers. 1979. 'Update on Steam-Water Chemistry in Power Plants'.. 8. and N.

The author was associated with the Coordinated Research Programmes of the International Atomic Energy Agency on Reactor Water Chemistry and the material in this chapter is partly based on that experience. the deployment of nuclear power is through water cooled nuclear power reactors(1. since the ultimate aim is to generate steam that drives a turbille. the occupational exposure of workers. a turbine and a condenser are the major components. However. As far as this part of the operation' is concerned in which a steam generator. The all important issue in the safe operation of nuclear power reactors is the accidental release of radioactive fission products from the core and generation of activated corrosion products in the primary water coolant that flows through the reactor core and their redeposition(4). the use of high temperature-high pressure water cannot be avoided in any type of nuclear power plant. reduce the velocities of neutrons generated-in fission to thermal energies (0. . much more critical than the fossil fuel fired boiler tube integrity. the problems of water chemistry and material compatibility are essentially the same as in thermal power stations(3). Consequently. A sQlid like graphite can also act as a moderator or one can dispense with the moderator altogether as in fast reactors. superior materials like stainless steel and high nickel a~loy tubes are used in nuclear steam generators.9 SPECIAL PROBLEMS OF WATER CHEMISTRY AND MATERIAL COMPATIBILITY IN NUCLEAR POWER STATIONS At present and in the foreseeable future. As a moderator. In nuclear power plants. the hydrogen or deuterium atoms of the water molecule. H20ID 20 is made use of as a moderator and coolant.l). wherein the fission chain reaction is sustained by fast neutrons (-1 Mev). The nuclear steam generator tube integrity is however. both light and heavy water.025 ev) which makes the chain reaction feasible. It is equally important that during normal operation and maintenance. as any rupture in the former would lead to radio-active contamination of the steam water circuit.

The boiling waterreactors (BWRs) developed in USA. a boiling (. Usually 12 bundles are loaded into each of the . Water cooled nuclear reactors can be broadly divided into two groups: boiling water reactors and pressurised water reactors. While this type of. lower than the radiation exposure dose limits. At present in the nuclear power industry PWRIVVER is the dominant reactor. be kept to a minimum i.tory agencies. except that the water is not allowed to boil by the application of higher pressure. The high pressure coolant is fed to a steam generator on its tube side. The fuel elements consist of an array of fuel rods (7x7or 8x8). The fuel elements reside in the pressure tubes. part of the reactor water is fed to a secondary steam generator and the steam which is generated at low pressure is fed to an appopriate stage of the turQille. Here again the arrangement is the same as in western BWRs. " . The fuel is made up of natural U0 2 pellets clad in zircaloy. The core is surrounded by water. Rumania and S.plant is called PWR in western countries.lled calandria. The exhaust steam after condensing to water is purified through the use of deep bed demineralisers and fed back to the reactor through feed water heaters. A little pressure is applied to maintain the required circulation. The Indian nuclear power programme is based on this type of reactor.94 Water Chemistry operators and supervisiors. The nuclear core is again made up of low enriched U0 2 pellets encased in zircaloy tubes. The other group of water moderated and cooled reactors are known as pressurised water reactors (PWRS).e. The steam-moisture mixture is passed through moisture or steam seperators and the steam is then fed directly to a turbine. use graphite blo~ks is the moderator in which pressure tubes are embedded vertically. lined with stainless steel in whlch the nuclear fuel elements. In some of the BWR versions. which have been described as Pressurised Heavy Water Reactors (PHWRs)(S). CANDUlPHWR makes use ofzircaloy pressure tubes as fuel channels which are horizontally fixed in a vessel ca. make use of a pressure vessel. which are smaller in diameter than in BWRs. A third gruop of water reactors has been developed by Canada and are known as CANDU reactors. A!':8entina. The fuel rods are made of zircaloy tubes filled with low enriched uranium dioxide (V02) pellets and sealed at both ends. The steam generated is collected and fed to a turbine as in western BWRs. The fuel pin clusters or bundles are of much smaller length. it is known as VVER(6). in Russia and other states of the former Soviet Union and in eastern Europe. Jhe boiling water reactors developed in the former Soviet Union.Korea are the other countries interested in this type of power plant(6). This is filled with heavy water which acts as a moderator at about SOoC.sa). The Tarapur Atomic Power Station is an example of this type(s. than those in BWRs and PWRs.270°C) coolant. prescribed by International Commission for Radiological Protection and national regule. which acts both as a neutron moderator and as the name implies. leaving sufficient space for coolant water to flow through them and boil. Steam is generated on the shell side and the rest of the circuit is the same as in a thermal power station. in the form of a core of a particular geometrical configuration reside. The Chernobyl nuclear power station is an example of this type ofBWR and is known as RBMK(6).

In the Three Mile Island nuclear power station. A class of reactors developed in the UK.Water Chemistry and Material Compatibility 95 fuel channels.. without boiling. The highly exothermic reaction resulted in the production of hydrogen. special problems of water chemistry and material compatibility are further discussed. through which heavy water at high temperature (-275°C) and pressure flows as the heat transport fluid.3 years. The number of valves and joints is minimised to reduce repair work and materials with as Iowa Cobalt content as practicable are selected for reducing the radiation dose. Skilled maintenance personnel can work at their tasks for only a short period at a time. results in the activation. Unlike in thermal power stations. unit 4 (CN-4). either of a recirculating or once through type. The radiation exposure limits are such that a welding repair in a thermal power station which takes about an hour of a skilled technician's time might require as many as six welders of equivalent skill on the coolant circuit in a nuclear power station shortly after shut down. In fast reactors where there is no moderatot:and the fuel is of highly enriched Uranium and Plutonium.1) The hydrogen generated in massive quantities can lead to an explosion (muffied in the case ofTMI-2 and violent in the case ofChernobyl-4) and spread ofradioactivity(II). The outlets of all the fuel channels are combined and this hot heavy water then goes through the tube side of a steam generator. along with Co-58 and other radioactive products makes maintenance a serious problem. this problem is largely tackled in the primary system by a strict water chemistry control. The major concern even in minor accidents is the release of radioactive iodine and caesium (both fission products). The principal offender is Cobalt-60 (Co-60). which in turn is used as the heat source in a steam generator. Zr + 2HzO ~ ZrOz + 2Hz (9. unit 2 (TMI-2) and in the Chernobyl nuclear power station. the core can heat up very fast. Light water is used on the shell side to generate steam which is then fed to a turbine. Ultimately the coolant gases generate steam. Against the above background. transport and redeposition of corrosion products in nuclear power plants(7. The low level magnetite transport in the heat transfer circuit. In nuclear industry this has come to be known as the ¥an-Rem problem. which is of no consequence in thermal power stations. The major issue of concern is radioactivity. a strong gamma-ray (y-ray) emitter with a half life of -5. Apart from design and material selection. the heat of the compact core is removed by molten sodium. such a sharp and fast rise in clad temperature led to its chemical interaction with water. The deposition of this nuclide on out of core surfaces. Their chemical forms and hence their dispersal depends strongly on the water chemistry prevalent in . Minimising the Man-Rem problem is taken up from the stage of design and materials selection itself. makes use of gr~phite as the moderator and Carbon dioxidelHelium as the coolant. An equally important issue is the chemistry under accident conditions(lO). These reactors are the mainstay of the UK nuclear power industry. Maintenance of steady pH in a narrow range effectively controls mass transport during the operating cycle of a nuclear power station.1). Considerable effort of water chemistry control in nuclear power stations is focussed on to this issue(').

Radioactive corrosion products may be generated either directly or indirectly. so that activity build up on out-of-core surfaces can be kept to a minimum. Cobalt is a low level (ppm level) componen' of stainless steels. The ion exchange purification has to be dovetailed into the maintenance of the required concentration of boric acip in the moderator at any given time. oxygen and pH control additives such as hydrazine. (e) Containment of radiolysis products. VVERs do add ammonia as seen later on. S8Co is generated by fast neutron activation of s8Ni. A problem of water chemistry that is special to water moderated and water cooled reactors is the radiolysis of water(l2). A chemical additive which is not required in thermal power stations is boric acid. nickel alloys (a) . sSCo. Fe 30 4 . which gives rise to two issues.g. In the second case. corrosion would result in the release of neutron activation products from in-core structural materials. SICr.Co Z0 3) or mixed ferrites such as NiFe z0 4 or CoFe 20 4• The radioactivity is due to 60CO. Thus the main objectives of reactor water chemistry are. Since the bulk corrosion product is magnetite.ater that would result in enhanced corrosion. The stress corrosion cracking of l. If the water is heavy water as in PHWR. However. undergo neutron activation and get resuspended into the coolant(l3). This leads to the production of hydrogen and oxygen. Because of radiolysis.ainless steel pipin6 in BWRs is also a matter of serious concern. Reduction in the aggressive action of high temperature water towards the structural materials (stainless steel. (d) Prevention of fuel element surface fouling that could adversely affect heat transfer and corrosion.carboll steel. It is almost impossible to retube such a steam generator which will he radioactive due to the deposition of corrosion products on the tube side. the additional problem of recovery of Dz (a costly isotope) has to be tackled. Apart from S8CO.. (c) Prevention of the release of radioactivity into the environment. Another problem of serious concern is the rupture of a steam generator tube in PWRs and PHWRs.96 Water Chemistry that particular situation. the others are generated due to thermal neutron activation of the corresponding inactive isotopes of these elements. zircoloy and high nickel alloys like Monel. This chemical (B 20 3 dissolvrd in HzO or DzO) is widely employed in PWR/VVER/ PHWR as a neutron absorbing (control) material. corrosion products from out-of-core surfaces that get deposited on the incore surfaces. the other corrosion product oxides may be free (e. In the first instance. There is no addition of boric acid in a BWR. (b) Achievement of the lowest possible occupatio~al radiation exposure by minimising the ingress of incore impurities and out-of-core radioactivity build up. Inconel etc. s4Mn and s9Fe. ammonia 01' morpholine may not be added to the primary coolant system during operation.) to condition the chemistry environment such that the mass transport is minimal and in a specific direction. One aspect would be to ensure that the mixture does not explode. The other concern relates to the increased dissolved oxygen content of v.

Particulate matter is conventionally defined as that retained by a 0. as films. Source offission and a. It is desirable that all such variations be reflected in the evolution of any model for corrosion product transport(l4. Colloidal I Particulate species S. A simplified diagram of the processes described above is shown in Fig.I. followed by 5SCO.m)or colloidal «I J.) '" Reactor coolant water chemistry literature wideHy refers to this as 'crud'. Out of core A Out of core BB ! I I B REACTOR CORE ! 1. nickel and chromium species behave in the same way as the cobalt species. with respect to nucleation and precipitation. Corrosion and Deposition Process In Water Cooled Nuclear Power Reactor (Processes in AA and BB are same as indicated in A and B respectively.I. . AA COOLANT FLOW CANDUIPHWR Fig. It is also often assumed that iron. Therefore. corrosion product' I I .m) particulate species·. Deposition and incorporation of fission and activated corrosion products. Whiie the former group of alloys are extensively used.9. b..~. corrosion products I through getting activated I Soluble.I. Radioactive and non-radipactive corrosion products may be transported in the coollUlt both as truely soluble species. Neutron activation of I c.m microporous filter membrane. as welt as a high level (55 percent) constituent in hard facing materials such as stellite alloys. the soluble fraction will also contain some colloidal particulates in addition to the truely 'soluble' species. stellite is used only sparingly with relatively low incore surface area. Particulate corrosion J products deposit and reside in-core for a while.1. 15). Formation of ~ 4. Soluble and colloidal corrosion products flow I d. It has been suggested that most of the non-filterable 6OCO circulating in a PHWR coolant is colloidal in nature. this however. As mentioned earlier the principal concern is 6OCO. get activated and get released by exfoliation and/or by resuspention ~--------------~I ! Corrosion of system surface Deposition of corrosion prod. It is insoluble and hence.Water Chemistry and Material Compatibility 97 such as Monel-400 and Inconel-600. Neutron flux zone I a. Corrosion of I corrosion products I system surface I 3. is not borne out by experience. The behaviour of substituted ferrites is somewhat different from that of magnetite. The term appears to have originated in Canada and is reported to be an acronym for Canadian Reactor Unidentified Deposit. 9. is composed of both inertial as well as collodial particulates. Material that is not retained and which goes through the membrane is often classified as ·soluble'.. A contrary view is that true soluble Co transport is dominant when the crud levels are low.. as well as inertial (> 1 J.1.45 J. I ~ I 2.

The main chemical characteristics of the feed water and the boiling reactor water are more or less the same. 304L etc. The regimes in the primary heat transport system of water cooled reactors have been devised to meet this requirement. has colIected relevant information from different cvtlntries and tabulated the same for easy reference l19l • In boiling water reactors. viz. using as pure water as possible(s. a 'source term' and a 'recipient term' coexist which will ultimately result in the transport and deposition of radio nuclides. which is not acceptable.ziracaloy experiences the worst conditions.. with no chemical addition. This is to avoid the stress corrosion cracking (SCC) of stainless steel. Not only is the pressure vessel lined with SS. . Thus condensate polishing is mandatory.17. The specifications(61 for water quality in BWRs are given in Table 9. These two terms are inter-dependent. Development of pin holes or minor cracks in the fuel tube will lead to the release of fission products (like iodine and caesium) to the coolant. Any change in operational chemistry that affects the corrosion rate has an immediate impact on the 'recipient tel. Hydrogen embrittlement of zircaloy is another problem that has received considerable attention. The International Atomic Energy Agency. However. The failure of a pressure tube in one of the reactors at the Pickering Nuclear Generating Station. both hydrodynamic and radiation field wise the fuel cladding material. BWRs impose a severe restriction on chloride. it is apparent that in the reactor coolant circuit..) and the neutron absorption cross section of Zr is very low. when one speaks of fuel performance in nuclear reactors. Hence. control of corrosion will lead to the control of the entire activity transport process. one is actually discussing the Zr clad integrity.radioactivation and the deposition of radioactive 9SZr on out of core surfaces is not a matter (If concern. Fortunately.minimising corrosion with a consequential reduction of material transport through the core. as welI as the relatively thick pressure tubes in PHWRs. The coolant chemistry in BWR adopts a hands-off policy. As the reactor oxygen level IS an equilibrium value depending on the reactor operating power. viz. Canada is suspected to be partly due to hydrogen percolation into zircaloy pressure tube under special stress conditions. Internal hydriding.98 Water Chemistry From the above discussion.n' and a delayed efrect on 'source term'. stress corrosion cracking due to pellet clad mechanical interaction coupled with the chemical interaction between fission product iodine and Zr are some of the reasons ascribed to clad failure both in BWRs and PWRs/PHWRs(181. Consequently. Pipe rupture accidents due to (SSe) have been experienced in BWRs. In the harsh environment of the reactor core. but the primary piping is also of this material (steam lines are of carbon steel). It was found that this is affected more from 'inside attack' than from the outer coolant.a).1. one has no control over this parameter. A wide variety of analytical techniques have been applied in chemical laboratories of nuclear power stations to monitor and control water chemistry.) besides zircaloy. Consequently. Differences are essentially due to the concentration factor. In fact. what is of significance is the integrity of the thin fuel tubes. the dominant material is stainless steel (304. the corrosion resistance of zircaloys (zircaloy-2 and 4)is very good(16.17.

"'IWR! o· NO . feed water dissolved oxygen is not expected to exceed 14 1Lg/1 in Tarapur.0 8. .1 1.l.l.0 200 NS 4000 NS NS NS • NS • NS 4000 13 NS 2 NS RBMK RW FW 0.S/cm pH a 25°C Chloride J.g/l Iron J.9.2 \' \ 1 " 3 2 1) "'- -~ !J"'"-- _ ~ z~ -2 ~3 ".15 NS NS NS 25 3 RW 1.ll) and the interrelationship is shown in Fig. This can be achieved by the injection of hydrogen into the coolent water.9. In reactor water an equilibrium level of .2 Stress Corrosion Cracking of Stainless Steel-Influence-Chloride and .1 Feed and Reactor Water Specifications for BWRs(6) Chemical Units 2arameter Sp. Conductivity J.wS 1 0 \ \ 2 .l.2 200 FW 0.2.2 2 Z.1 6. Dissolved Oxygen(lO) One way to reduce dissloved oxygen in a radiation environment is to promote the radiation induced back reaction.Wat" Chemistry and Material Compatibility Table 9.0 7. .400 1Lg/1 would be prevalent due to radiolysis and stripping.I~ .g/l C022er NS: Not Specified GE VGS 99 FW 0.z 3' 2 1 1~ 03 01 10 CHLORIDE mgtl 100 1000 Fig.l..AILURE 100 FGURES tlEMJ'M tfJM8ER a: SP£CIMlNS 100 2\ \ 2 n.8 NS RW 1.l.l. The see propensity of austenitic stainless steel in relation to chloride and dissolved oxygen in water has been thoroughly studied(lO. '.5 6. H0 2 and H20 2• the precursors of t1101ecular oxv!!en.g/l Silica J.g/l Oxygen J. Production of oxygen can be suppre~sed through a chain reaction which rapidly eliminates OH.g/l J.5 4 l00(CI+F) NS NS 1000 NS 60 200 50 2 • Though not specified.

. serve as precoat filters. in-situ radiolysis of ammonia generates the hydrogen required to keep the level of oxygen low. an alkaline pH condition is to be maintained to minimise the corrosion. a set of calculations based on room temperature pH measurement of boric acid-LiOH . (as 7LiOH). India). Reactor water purification is the key to adequate cooiant chemistry control in BWRs.2 and 9. Full flow condensate polishing is mandatory. This type of chemistry cO!1trol. These resins mixed with binders in a slurry and cast over porous surface. to control reactivity. called Hydrogen Water Chemistry(2J). one can see the difficulties involveu in maintaining such constant ratios over prolonged periods. The primary coolant chemistry of PWRIVVER is more complicated than that of BWRs(6). The normal clean up flow is about 2 percent of the feed water flow at full power. preceded by cellulose and/or Powdex* precoat filters.3(6).4) (9. is gradually being introduced in BWRs (though not at Tarapur.4 has been found to be optimum.1 is acheived by adjusting the boron to potassium ratio. VVERs employ a mixture ofKOH and NH 40H. a sort of buffering action prevails. using deep mixed bed ion exchange resins. anion exchange resins made in very fine particle size.mixtures is made use of. • POWDEX is a brand name for cation &. The primary coolant. 02 and H2 back to water. the chain reaction will lead to the reconversion of the stable radiolysis products. in VVERs. The variations could be from 0 to 1200 mg!l measured in terms of boron. A pH (300°C) value of 6.4 throughout the cycle. even in a boiling (consequent stripping of hydrogen) condition of the coolant. diverted to the purification plant is at a high temperature and pressure. It is usual to reduce the temperature. Since this range of pH calmot be directly measured in a reactor system at 300°C. While PWRs make use of lithium hydroxide. On the other hand. Here. A specific feature of the chemistry is the presence of boric acid over a wide range of concentrations. The chemical specifications for the reactor coolant water in PWRs and VVERs are given in Tables 9. In PWRs. for BWRs.3) (9.2) (9. A decontamination factor not less than lOis acheived. The presence -of boric acid makes it aU the more necessary to add an alkltli. A coordinated boron to Li ratio has been evolved to acheive pH (300°C) of 6. PWRs differ from VVERs in the nature of the alkalising agent. a low level of dissolved oxygen is maintained by injecting hydrogen. but purify at a relatively high pressure so as to maintain the desired high purification flow rate through mixed bed demineralisers. Laboratory as well as large scale demonstration experimems have shown this to be feasible.9 to 7. A boron level upto 400mg!l could be encountered under shut down conditions. H z0 2. Since the mixture is a ~ombination of a strong and a weak base.100 Water Chemistry H2 + OH H + H0 2 ~ HzO + H H 20 2 (9.9 to 7. as stated earlier. Similarly in VVERs a pH (260°C) of 7. Considering that a part of the rractor water is constantly purified by ion exchange. At operating temperatures (270°C-to 320°C).5) H+02~~ ~ H + H Z02 ~ H20 + OH Eventually.

Inconel-690 is a tube material that is showing great promise.400 Reactor Water Quality Specifications(6) Chemical Parameters pH at 25°C KOH as K+ Unit Value 6. In early designs of drum type steam generators. A portion of the carbon steel section of the feed water piping experienced severe tPinning from the inside. The nuclear industry has been conditioned over the years to have dissolved oxygen at levels less than 10 !lg/l in the feed water to the steam generators.7 .0 5 30 to 60 In-situ equilibrium values Remarks H3B03 NH3 Hydrogen mglkg glkg mglkg cm3/kg (at STP) Water chemistry on the steam generating side of PWR/VVER is the same as in fossil fuel fired power stations(9). with additional content of Cr.5 o to 8.1S/cm cm3/kg (at STP) J. Water (non-radioactive.Water Chemistry and Material Compatibility Table 9. the tubes were of a high nickel alloy.or AVT is employed.2 . Stainless steel has also been used as the tube material.4 0. which escaped in-service inspection.35 5 150 150 101 Remarks Depends upon H 3B0 3 and 7LiOH concentration mgll mgll J.2.5 6.40 25 .10. 1986 in a nuclear power plant opearated by the Virginia Power Company. a relatively low nickel alloy. Due to the configuration in that section of the piping turbulence was the main culprit.9-7. In several cases.3 VVER . the nuclear heat transport system is coupled to a oncethrough steam generator.1g11 ~~Il As for pH at 25°C During power operation with H2 as above Table 9. with zero solids treatment and condensate polishing.1g11 J. However an accident in December.2 PWR Reactor Water Quality Specifications(') Chemical Parameters pH at 25°C pH at 300°C Boric acid as boron 7LiOH as 7Li Sp. Coordinated phosphate. In the initial stages of the investigation although .2 1 . Inconel-600. Conductivity at 25°C Hydrogen Oxygen Chloride Fluoride Unit Value 4. The pipe line suffered a guillotine failure. USA has revived arguments against such low levels.0 2 to 16.1200 0. Based on long term experience. the present trend is towards the use of Incoloy~800.as it is in the secondary circuit) flashed to steam.

102

Water Chemistry

the low level of dissolved oxygen was blamed for not providing enough of the protective magnetite layer, a full investigation, showed this to be unsubstantiated. The reason for this is that just as on the primary side, dissolved oxygen is to be rigorously controlled on the secondary side as wel~. The history of PWR steam generator corrosion is a good example of all the major problems in any steam raising circuit(9). The study led to an understanding of the complexity of the water-steam system at high temperatures vs material compatibility. Phosphate chemistry works well at relatively low temperatures. Temperature increase leads to phosphate hide-out, which results in alkaline stress corrosion and phosphate induced thinning where local boiling temperatures are aroung 280°C. Removal of phosphate, without rigorous removal of chloride, produces excessive corrosion of carbon steel causing tube denting in the baffle plate region. This situation gets further aggravated, if copper alloys and a higher level of dissolved oxygen are present. It could even lead to tube pitting. On the other hand, the advantages of AVT are off set by its inability to provide buffering action in the event of condenser tube leaks, especially if the condenser is cooled by sea water. AVT is also not really compatible with the presence of copper alloys and poses problems in condensate polishing. A boiler water treatment that is being tried out in conjuction With AVT is the addition ofboric acid,which is a very weak acid at high temperatures. Its action in reducing corrosion damage results from the incorporation of boron in the thin corrosion films, making them more protective. The water chemistry in CANDU/PHWR group of reactors(S.6) is in some ways simpler than that ofPWR/VVER. However, the use of heavy water as the coolant and moderator imposes special restrictions on operations, sampling and analysis as the presence of the radioactive isotope, tritium(3H) poses an additional inhalation hazard and spillage of the expensive heavy water has to be avoided. As mentioned earlier, Canada and India are the countries where these reactors are tl,e base for nuclear power. All these units are of the pressure tube type, • emplo) mg zircaloy-2 clad natural uranium dioxide fuel and using heavy water as the moderator as well as the coolant. The latter is in seperate circulating systems that operate under different conditions of temperatrue, pressure and chemistry. The primary heat transport system is comprised of multi metal surfaces, the major components being carbon steel,zircaloy-2 and Monel-400 or Incaloy-800. The objective b\!hind coolant system chemistry is the same as in all other nuclear power reactors,viz.,to minimise the out of core radiation fields by minimising the processes of corrosion and erosion of the heat transfer surfaces(8,H). A prerequisite for achievir.g this objective is, "Hot Conditioning," of the primary heat transport system during its light water commissioning stage. After cleaning and de greasing the system surfaces, water maintained at pH 10 (by LiOH) and deoxygenated (by hydrazine) is circulated in the system in the temperature range of 220°C-240°C for about 10 days. Such a procedure results in the formation of a thin protective layer of magnetite (Fe304) especially on carbon steel surfaces(5). This minimise's further corrosion of the structural materials and acts as a check on crud inventory. The steady state crud concentration values /lave been observed to be -0.0 I mg/l, with some transient values during star~ up and cool do .... n operations. The integrity of the magnetite

Water Chemistry and Material Compatibility

103

film is due to a well regulated coolant chemistry and consequently results in a low level of the activity transport. This contributes to low out of core radiation fields(4). As compared to PWRs or VVERs, the advantage of PHWRs stems from their different moderator system in which boron is added rather than to the coolant. This simplifies the coolant chemistry and in general permits a higher operating pH which is mostly kept constant at 10.2 ± 0.2 (as measured at 25°C) by the addition ofLiOH. The specific conductivity of the coolant normally ranges between 15 to 30 j.ls/cm. A pH of 10.2 at 25°C due to LiOH addition alone means apH of7.4 at 270°C - 280°C which is generally the operating temperature in PHWRs. In terms of magnetite solubility the pH and the temperature regimes ensure that the solubility of magnetite is almost minimum. Actually it is a little towards the right hand side of the minimum in the solubility vs. pH (280°C) curve for Fe30 4 (Fig.4.4). With a positive temperature coefficient, the magnetite solubility increases in the coolant channel from the inlet to the outlet, thus reducing the chance of deposition on the fuel clad surface. It may be mentioned that the adsorption of Co (II) on magnetite is maximum and constant in the pH range. This would mean that the Co adsorbed by the magnetite layer on the fuel clad surfaces has a chance to get activated. On the other hand,with the solubility gradient of magnetite in a fuel channel, Co(II) is expected to be in the suspended or soluble form in the coolant. In short, the operating pH takes care of the integrity of the magnetite film formed during hot conditioning/normal operation. It also keeps the magnetite solubility in the appopritate direction and ensures a lower residence time for Co (II) in the core(14). Another chemical control that is strictly adhered to is that of dissolved oxygen in the coolant. In a closed system, water radiolysis leads to generation of hydroxyl radicals which end up as dissolved oxygen. The Primary Heat Transport (PHT) system in earlier PHWRs had a large surface area ofMonel-400 (steam generator tubes) in contact with the coolant 020. The corrQ,$iqn of this alloy at high temperatures is adversely influenced by dissolved oxygen. In view of the high Ni content 'If this alloy, Monel surfaces are one of the major sources of cobalt in the system,. Thus it is essential to maintain a low level of dissolved oxygen (10 ).1g/l), so as to minimise the corrosion of Monel and hence the input of cobalt. Hydroxyl radicals can be scavenged by increasing the partial pressure of dissolved hydrogen in the coolant. In PHWRs, hydrogen injection to a level of 10 to 15 em 3/kg of 020 at STP has been found to keep dissolved oxygen at -10 ).1g/1. It is also to be noted that hydrogen addition to the coolant does not influence the solubility of magnetite, since the solubility is dependent on the cube root of hydrogen partial pressure(14). Following the development and good performance ofIncoloy-800 as the steam generatcr tube material, Monel-400 is being substituted with this alloy. Incoloy-SOO is not all that susceptible to dissolved oxygen transients at hi~h temperatures and having a lower Ni content, will have less cobalt inventory. The third aspect of the coolant chemistry in CANOUlPHWRs relates to its purification. A part of the coolant (1 % of coolant inventory) is withdrawn from

104

Water Chemistry

the circuit. cooled and then passed through a filter and mixed resin bed. In order to keep the pH of the coolant constant, the Li form of the cation exchanger is employed. while aD (02H)form of the anionic resin ensures no degradation of isotopic purity. The use of organic ion exchangers is a cause for a chemical transient. since the intrusion of any of the resin into the system will upset the chemistry due to their thermal and radiation degradation. This is true for all types of reactors. Against the above background. the experience of coolant chemistry in CANDUlPHWRs has been very satisfactory. Chemical transients are rare. The radiation fields around the steam generator cabinets. measured 24 hours after a shut down are fairly low and constant. On-line 'Y-monitoring of the outer surfaces of primary piping (over the insulation) indicates that the major contributory radionuclide to the radiation field is 6OCO and occassionally,fission products as in other reactor types(4). The replacement of Monel-400 by Incaloy-800 is expected to further reduce the radiation field build up on the out-of-core surfaces that was observed earlier. Models for activity transport have been developed(8). Typical specifications for the chemical control of the heavy water coolant are given in Table 9.4.
Table 9.4 Chemical Control Specifications for PUT System in PUWRs(14) Parameter/ Constituent Isotopic purity Sp. Conductivity Sampling frequency 3/week 3/week Range/ limit 95% min. 30 micro Siemens/cm Remarks From reactivity considerations. Specific conductivity limited by the concentration of lithium hydroxide (LiOH) maintained in the coolant for keeping iis pH within specified limits. Adjusted with lithium hydroxide (LiOH). This is the optimum pH range for least corrosion of the carbon steel in the system To minimise possible stress corrosion. Higher concentration of fluoride can have a corrosive effect on zircaloy tubes and fuel cladding.

IIday

Between 9.5 - 10.5

Chloride Fluoride

3/week IImonth

0.3 mgll 0.5 mgll

Contd.

Other important chemical parameters are the isotopic purity and chloride. India).Lg/1 during steady operation· Dissolved D2 lIweek Between 3 . This gas is circulated through catalytic recombiners. Two signigicant developments are worth noting in this context. "BOIL". the latter because the system components have stainless steel surfaces.4 (Contd. for steady operation Dissolved Oxygen 3/week 10 f. An in. if condensate polishing is also practised. (such as MAPS at Kalpakkam. Boron Trioxide dissolved in Dp is added for reactivity control and the required concentration is maintained by a by-pass ion exchange unit. A VT is being employed with morpho line as the alkalising agent. stimulates the build up of chloride in different parts of the secondary circuit due to seawater leaks in the condenser(25).20 mg/l ofD2 at STP Maintained by injecting hydrogen to the system when pressurised.Water Chemistry and Material Compatibility Table 9. • If the limit exceeds the value. This poses problems. as would be the case at a seawater cooled power station. The radiolysis of heavy wl!ter releases D2 and 02 into the He cover gas of the moderator system. it shall be brought back below the limit in 72 hours. there are bound to be condenser tube leaks.l:ractive software code. so that the concentration never exceeds four percent vN (Volume of D2tTotal volume of cover gas).1 mg/~ 105 Remarks Circulating crud gets activated in the core and will get deposited on the fuel bundles and on the PHT system surface. It is possible to establish the leak rate by measuring the chloride concentration twice in succession over a period of time in the steam generator and feeding that data to the code. failing which the reactor shall be shutdown. Both will lead to problems of activity transport. The heavy water moderator that fills the calandria is in a seperate low temperature (-50°C) circuit. The resulting determination of the leak rate helps the operators to . Higher values of oxygen damages the protective magnetic layer and increases the corrosion of boiler tubes specially of Monel-400.) Parameter/ Constituent Crud Sampling frequency IIweek Range/ limit 0. In the secondary system of all CANDU/PHWRs. that also takes care of the purification. Since the condenser tubes are of AI-brass and there is heavy biofouling.

it is minimal untill morpholine saturation occurs.).but in research reactors as well. it is anticipated that the performance of the condensate polishing unit would be poorer in the presence of morpholine than that in the presence of ammonia under the same conditions of resin quality. the retention of sodium in the resin is highly dependent on the ratio of Na to MOR~ The chloride slip is indirectly controlled by morpholine absorption by the bed. Magnesium was later hydrolysed in the resin pores.106 initiate corrective action. lfater Chemistry The other development relates to the performance of the condensate polishing unit (CPU)(16). For a similar purpose Israel developed a carbon fibre filter material. In 1961. A m4tg nesium loaded weak acid cation exchange resin was developed to clean the treavy water of its turbidity and associated radioactivity. as against ammonia (0. The turbidity was idel'\(ified as Bayerite aging to Gibsite and t!te colloid was negatively charged. If the coolant is alkaline as in CANDU/PHWR. as well as a biocide to primary coolant water (H 20) of the CIRUS reactor in India. reduced the chromate to trivalent chromium. The severe nuclear reactor accidents in NR. PWRNVER situation depends on the pH at that time. When the contaminated heavy water was passed through such a special ion exchange resin bed. which got precipitated as its hydrous oxide on the aluminium clad of the metal fuel. This led to the formation of alummium hydrous oxide turbidity in the heavy water coolant. thus solving the root cause of the problem(17).5 mg. and di sodium salt of EDTA was used to clean up the coolant channels and fuel clad surfaces. As the selectivity coefficient of morpholine (MOR) over sodium on the resin is rather poor. Hence.X. TMI-2 and Chemobyl-4 have . the aluminium cladding of the fuel bundles in the DHRUVA reactor in India was getting eroded and corroded at a rapid rate. if it is a BWR neutral coolant. the turbidity was removed and the clean heavy water returned to the reactor(18). a considerable fraction of iodine will De in the form of 12 and hence will volatalise. where the primary coolant water (H 20ID 20) spills out of the circuit. In lccidental situations. A mixture of hydrogen peroxid\. Radiolytically' produced H radicals. its chemical condition at that time determines the chemical nature of the volatile radioactive fission products such as iodine and the release behaviour into the containment atmosphere. Water Chemistry and corrosion problems are experienced not only in power reactors. The impact of morpholine is both direct and indirect. A couple of examples will illustrate the point. which is determined by the ratio of lithum to boric acid. 300 mgtl of potassium chromate was added as a corrosion inhibitor. This results in lesser effluent volume from the polishing bed prior to Its saturation with morpholine. The concentration of morpholine is higher (2-3mgll) for a given pH. the ratio in the mixed bed and regeneration characteristics. On the other hand. when the effects of water radiolysis '\fere not fully appreciated in large systems.' Chromate was also removed from the system. due to vibrational problems. most of the iodine will be retained in the aqueous phase as iodide. This caused pressure drops and reduced the flow of the coolant leading to fuel failures. In 1985.l.

Thl. the temperature of zirconium cladding of th(. If the environment is inerted. 3. In the absence of mixing and large containment volumes. 3. The possibility of the rupture of pressure tubes is always a real one. (Here 2H 20 + C ~ 2H2 + CO 2 H20 + C ~ H2 + CO 3H 10 + 2Al ~ 3H 1 + AlP3 2H 20 + Zr ~ 2H2 + Zr0 2 3H 20 + 2Cr ~ 3H 2 + Cr 20) 4H 20 + 3Fe ~ 4H2 + Fc 30 4 2H20+U~2H2+U02 H20 + U0 2 ~ More volatile U bearing species. Chemical reactions excluding 3 and 7 played important role in CN-4. The net result in all cases except 8 and 9 is the production of hydrogen. H20 + Fission products ~ More volatile species. several interactions get initiated at fast rates.ls. This is the temperature required for the initiation of the self sustaining stage of the zirconium-steam reaction No.. there is a chance for a hydroge. H20 signifies water and lor steam depending upon the situation). The individual accident scenario will determine the extent to whict. 6. 4. Hydrogen explosion was one of the cau~s for the breach of the containment in Chernobyl-4. directly or indirectly those chemical'reactions of No. 5. In the special case of 2.reactions. In such a situation. while reactions 4. Once the irradiated fuel is exposed to the hot steltm environment in an accident situation. The consequent pressure build up coupled with a further rise in temperature can lead to the deformation of the zirconium fuel and pressure tubes (coolant tubes) in the reactor. 2. affected fuel elements can go up within a few minutes to about 1030 °c due to decay heat.4. chemical speciation of fission products will depend upon their interaction with steam. 8. 8 and 9 and possibly Sand 6 were of significance in TMI-2. 9. 7 and 9 were reported to have influenced the course of the accident in NRX. Since chemical species in the vapour phase and their transport rates are . The temperature of the core materials will continue to rapidly increase to levels much higher than in the normal operating mode. when water/steam comes into contact with very hot surfaces. these processes are: 1. In the case of loss of coolant. This exothermic process results in the production of large amounts of hydrogen as wen as a further rise in temperature. Consequently. it would be a mixture of combustible gases. With increasing temperatures. On the other hand. the steam-hydrogen mixture enters the restricted volume in the reactor vault which houses important equipment. the above chemical processes involving high temperature water/steam proceed(29). monitOring of hydrogen and oxygen in such restricted volumes on a continuous basis as well as installation of catalytierecombiners a$ additi~nal back up safety featutes are expected to mitigate this risk.9 will strongly influence'the radioactive "Source Term".Water Chemistry and Material Compatibility 107 brought the role of water and steam chemistry in aggravating the effects into sharp focus(10). 7. build-up and its possible deflagration(29).

5a. Role of Water Chemistry in Corrosion Control. 5. the major contributor to the ruthenium bearing'species is from ruthenium gas. and K.S.S.Reliability. Venkateswarn. P. Corrosion release-The Primary Process in Activity Transport. March. Venkateswarlu K. June. Vienna.R. 15-41. Nanjudeswaran and K.Lawrence. K. The total ruthenium content in vapour phase has been shown to be maximum in a steam rich vapour. Proc.V. San Minato. REFERENCES 1. Venkateswarlu K. IAEA-TECDOC-429.S. Water Chemistry Experience at Tarapur Atomic Power Station and Rajasthan Atomic Power Station. Vienna. Research and Development in Regard to Water Chemistry and Associated Areas in Nuclear Power Stations. Deposition and Decontamination in Water Cooled Nuclear Power Reactors. Symposium on Corrosion and its Control in Power and Chemical Industries. 4.Water chemistry specifications and their control.S . April 1988. pp.S. Vol. 6.V. such as the one at Chemobyl-4. Department of Atomic Energy. and B. For example. (1981). 7. April 1981. pp. it has been shown by calculations that in a hydrogen rich environment. Reactor Water Chemistry Relevant to Coolant-Cladding Interaction.• (1980). pp.K. (steam to hydrogen ratio) on the nature of the chemical species and their relative amounts in the gas phase. the presence of hydrogen generated in an accident will have a significant impact on the chemical speciation of fission products.K. Proc. Budapest. Committee on Steam and Water Chemistry (COSWAC). Topical Meeting on Water Chemistry in Nuclear P'<Jwer Stations. Department of Atomic Energy. and K. Indian Experience with Radionuclide Trasnport.Nair.193-203. Proc. the possibility of molybdenum fractionating from the other constituents of the metallic inclusions present in irradiated fuel. Lister D. Bombay. Tokyo. V-]-] to V-l-]4. Joshi N. Board of Research in Nuclear Sciences.Das. It decreases progressively with increasing hydrogen content. lAEA Coordinated Research Programme Meeting on "Reactor Water Chemistry Relevent to Coolant-Cladding Interactions. Karkhanavala M. pp.J08 Water Chemistry expected to be influenced by the vapour phase composition. Italy.D. (1982). Symposium 3. P. (1981). Indo-German Seminar on Operation of Nuclear Power Plants. India.. G. PP. (1988).200-209. Proc.2] 3-243. D. 8.K. P. Narasimhan S. IAEA. Theoretical studies using estimated thermodynamic data for the vapour species and the condensed phases enable predictions to be made on the influence of variable vapour composition.341-360.119-130. Germany. International Congress. IAEA (1987). An Overview of Water Chemistry Experience and Crud Input Control at Tarapur Atomic Power Station. T. June 1984. Japan Atomic Industrial Forum.Nandwani. Thermodynamic calculations indicate(30). (1984). (1977). Mathur. . The above discussion clearly brings out the added importance of water and steam chemistry vis-a-vis the special problems that are encountered in the safe operation of nuclear power reactors.. Venkateswarlu. International Atomic Energy Agency.K. This is a function of the hydrogen to steam ratio in the case of severe nuclear reactor accidents. 1977 • pp. Proc. Julich.B.B. IWGFPT/ll.Mathur. October ]981.Venkateswarlu. IAEA Sumposium on Water Chemistry in Nuclear Power Plants.. 2. Proc. Mathur P.C.S. Corrosion and Compatibility of Materials in Nuclear Power Stations. Venkateswarlu.Venkateswarlu. Role of Water Chemistry in Relation to Corrosion and Activity Transport in PHWRs. India.lI. IAEA Specialists meeting on the Influence of Water Chemistry on Fuel Fladding. CHEM TECH '80. Narasimhan. Venkateswarlu K.S. 3.S.. December 1982.A. "Proc. S. (1982). 1980. JAIF lnter-national Conference on Water Chemistry in Nuclear Power Plants. K..

S. . November 1986. pp.. R.(1988).70-73.P. pp.V. (1987). M. 11. C.BARC. Rodliffe R. Vienna.W.. Head. Venkateswaran G. Reactor Water Chemistry Relevant to Coolant-Cladding Interaction. Simpson. pp. CEN Cad an. Vol. (1982). Mahal. June-I 977 .. (1986). April 1988. 23. Ramshesh V.191-198. CRP Meeting on Investigation of Fuel Element Cladding Interaction with Water Coolant in Power Reactors. Naik M. Corrosion.S. NEDO-23631.L. Topical Meeting on Water Chemistry in Nuclear Power Stations. Roy P.153. Bombay.S.E. pp. Symposium on Corrosion and its Control in Power and Chemical Industries. Elek A... 17a. Proc.. Cowan R. Vienna.. International Atomic Energy Agency.I. 109 Garnsey R. France. TECDOC-429. Proc.v. Radiolytic Gas Generation During Normal and Accident Situations. Coolant Chemistry in Press uri sed Heavy Water Reactors: The Indian Experience.105 . (1988). Venkateswarlu K. pp. June 1988. Japan Atomic Industrial Forum. October 1985.L. Heidelberg.. Polley and E. pp. H. IAEA. US Experience with Hydrogen Water Chemistry in BWRs. S. pp. Water and Steam Chemistry Under Accident Conditions of Water Cooled Nuclear Reactors. 10... Reactor Water Chemistry Relevant to Coolant . Tokyo.19-25. Proc. 21. International Atomic energy Agency. Proc. IAEA Specialists Meeting on Environmental Factors Causing Pipe Cracks and Degradition in Primary System Components. 17. Water Chemistry Control for MlDimising Activity Transport and Radiation Field Build up Around Primary Coolant Circuits of Nuclear Power Reactors. Lee Williams W.19-67. October 1980. Venkateswarlu K.Mechanica Le(ters I.pp. Mathur P. Venkateswarlu K. Ibid. (1981). 14. Pellet-Cladding Interactions.A. Ibid.K. (1986).. 12. April 1981. Indig. Scientific Basis for the Choice of Primary/Secondary Water Chemistry. and G.Venkataswarlu. Paul A.. 15.S. Eiliott. WACOLIN. 24. Studies on Providing a Better Water Chemistry Environment to Minimise Stress Corrosion Cracking in BWR Primary System Piping.V. and H. .. and Venkateswaran G.164. Cowan R.TECDOC-429. (1977). Evaluation of and Improvemf'nts in the Performance of Zircaloy Cladding During and After its Residence in Water Cooled Nuclear Power Reactors.H. Venkateswarlu K. Material Behaviour in Nuclear Reactor Water Systems".81-104. Johanneson. Thornton.. 19. 13.S.. ppJ-l-1 to 1-1-21..Water Chemistry and Material Compatibility 9.V. Department of Atomic Energy. pp. Ibid" pp. (1986). 165-214. India.S. pp. IAEA Coordinated Research Programme.Cladding Interacton. and G.S.S. and J. J.R. Modeling the Behaviour of Corrosion Products in the Primary Heat Transfer Circuits of Pressurised Water Reactors. Ishigure K. Chloride and Caustic Stress Corrosion of Avstenitic Stainless Steel in Hot Water and Steam.C. Analytical Techniques for Monitoring Water Chemistry. An Overview of Corrosion Problems Encountered in Reactor Core Materials. JAIF International Conference on Water Chemistry in Nuclear Power Plants. (1987).S. Proc. (August 1957). IAEA Technical Committee Meeting on External Cladding Corrosion in Water Power Reactors. (1981). Gadiyar.. 16. A Review of Models Describing the Behaviour of Corrosion Products in Primary Heat Transfer Circuits of BWRs. (1986). 104-111.' " J.C.i 63. (1985). 333-340. BWR Coolant Oxygen Control. IAEA . M.Venkateswaran. Committee on Steam and Water Chemistry (COSWAC). Ibid. Vienna. Sundaram c. Hydrogen Generation Through Zr-Steam Reaction and Related Safety Problems Under Accident Conditions. Germany. and K. 13.67-73. Narasimhan S.. Res. (1957)... Venkateswarlu K. Ibid. (1980). International Atomic Energy Agency.L. 20. 18. (1988). Venkateswaran. (1987).R.. 22. IAEA. Narasimhan. Ruiz. 307-314. and O.

(1986). V. International Atomic Bnergy Agency.. Nuclear Technology. Venkatesw!. and K. 28. Symposium on. 26b.S.1963). Evaluation of. . How CIR Team Solved Corrosion Deposition Problems. and K. pp.. Velumurusan. VoU. Water Chemistry Narasimhan S. Vonkatoswaran. London. Venkateswarlu K. pp.V.S. Shankar. S. BNES Symposium on Water Chemistry fQr Nuclear Energy Systems-4.27·30. (Winter.S.loled 10 StJj. Narasimhan S.. 30. Krishna Rao. North Arnerican Chemical Consros. 26a. Venkateswarlu.S. Proc.V.Condensate Demineralisation Using Morpholine form of the Cation Exchanger. Surya Rao V. 82. S. Possiblo Molybderium Practionation from Ru. 1986. Toronto.217. Venkatelwarhl.. Tokyo.Japan Atomic lndustri&l Forum. Proc. November. British Nuclear Enersy Society. and K. 29. Shankar. 363·367. K. Rao and O. April. An Assessment of Hydrogen Dependent Safety Issues in PHWRs". Modoling of Water Chemistry Regime in the Secondary System of PHWRs.K. P. June 1988. Narasimhan. U. pp.rlu and K.V. Removal of AI Turbidity from Heavy Water Reactors by Precipitation Ion Exchange Using Magnesium Hydroxido. Hydrogen Issues r..J10 25. J. Venkateswaran and M. 27.1 OS· II O. Kumbhar A. R.219. (1986).R.S. Condensale Polishing Under AVT (Morpholine) Situation: Performance Monitorins and Diagnostic Techniques.K. pp. Mathur. Venkateswarlu. and K. Venkateswarlu K.S.. S. Rangarajan. (1963). (1988). O.I)' In Nue/. Ranganathnn Rllo (1988).S.ar Power Plants. pp. Pd and Rh in Severe Reactor Accident•. MEA Technical Commillee Meeling or. JAiF International Conference on Water Chemistry in Nuclear Power Plants. Tokyo. Nuclear Reactor Severe Accident Chemistry. Venkatoswarlu. Ibid. Canadian Nlldear Technology. (1986). Vienna. Ramshesh. (1088)..243·250. Kothare.R. 19GG. Bhardwaj S.V.S. V.

any treatment programme cannot be generalised. of temperature gradients of above 50°C per km depth. Some of the important geothermal locations in India{l) are given in Table 10.water circuit. which interacts with the materials of construction of the steam . and are given below: (a) Hoi waler fields. however. The complex water chemistry of the hot geothermal fluid. being near about 85°C) the geothermal wells can gener'lte steam. energy resources not based on fossil fuels. although the surface tel1)perature is a little above 80°C. In some of the locations like Puga. A wide gap. in wide areas with moderately high temperature gradients of 30 to 50°C per km depth having surface temperatures below 100°C. The hostile working environment mars the reliability of the equipment.10 GEOTHERMAL POWER AND WATER CHEMISTRY The utilisation of geothermal energy is extremely important in the quest for . There are two broad categories of geothermal wlter-steam sources. in view of the height (the boiling point of water' at th~t height. Ste~m (b) fields in narrow zones. Since the chemical composition of geothermal waters is site-specific. having surface temperatures above 100°C. is a major cause for the under utililsation of this energy resourc~.1. They are classified on the basis of thermal gradients in a volume of the earth over and above the normal heat flow.exists between the availability of this energy source and the amount that is being turned into process or space heat or electricity. .

Technology.2 CHEMICAL COMPOSITION OF GEOTHERMAL WATERS The dissolved solid content of geothermal waters ranges from that of ordinary well water upto concentrated solutions as high as 40 percent by weight(4). Academic press (1992)..3). is the only one in USA where dry steam forms the dominent resource. 2nd Edition. The growth of installed capacity (MWe) of geothermal power world wide upto 1990 is given in Table 10. wherein the hot water is used for space h~ating. Its combined output in 1990 was about 1770 MWe. Usually potassium and calcium chlorides are also present. New Zealand. hot house cultivation. supply of low process heat and recovery of chemicals like borax. though to a much lesser extent. pp 323·360. Table 10. Japan. Silica in . The principal constituent is sodium chloride. in a few instances. 10.112 Table It.7.1 GEOTHERMAL ENERGY UTILISATION One can visualise two main types of utilisation of geothermal energy on the above basis<2. Italy. Vo!. The figures (oJ: USA are given in brackets. the next in importance being bicarbonate.1 Growth orthe IDstalled Capacity (MWe) or Geothermal Power Year MWe Year MWe 1910 1916 1935 1940 1955 0 8 56 250 380 1965 1975 1980+ 1990+ 1995+ (projected) 575 1290 3888 (1444)+ 5827 (2770)+ 8967 (3170)+ +From "Geothermal Resources". Thus chloride is the main anionic constituent.l Geothermal LocatioiDs iD IDdia(l) Name and Location Manikaran (HP) Jumnotri (UP) Tapoban (UP) Surajkund (Bihar) Sirguja (MP) Khorkum (J&K) Highest Temp. While the projected increase in installed capacity (MWe) between 1990 to 1995 is modest in the case of Italy and Mexico. Mexico. Name and Location at surface °C Puga(J&K) 82· Agnigundala (AP) 80 Rajawa.2.Encyclopedia o(Physical Science &. The Geysers geothermal field with several wells in California. (J&K) 80 Chongo (J&K) Duchin (J&K) Nulna (J&K) 78 78 78 10. Phillipines and USA are among the countries that generate electricity from geothermal sources. One is essentially electrical energy generation using dry steam. or more usually a steam water mixture. in the Phillipines it is expected to rise sharply from about 890 MWe in 1990 tQ 2165 MWe in 1995. at surface °C Water Chemistry 100 90 89 88 88 85 Highest Temp. The other type is a mixed system.

USA Raykjanes. The pH of geothermal waters is determined by different equilibria in different locations.Geothermal Power and Water Chemistry 113 the form silicic acid is present in the range of 200 to 600 mgll. EI Salvador Carro Prieto.000 29. Usually geothermal waters are free from oxygen and as such chloride induced stress corrosion is not problem. %) NaCI KCI CaCI 2 H2Si03 72 10 0.5 10 11 9 Weitap. The pH and the electrolytic composition exercise a profound influence on the corrosion and material compatibility of geothermal waters.000 26 2 4 2 2 15. Copper or cupronickels are not compatible with H 2S. Wt. Stress corrosion cracking is also possible. Table 10. The other components are HzS. However.000 20. a number of gases are released.3 CORROSION AND MATERIAL COMPATIBILITY The corrosion of equipment used in the production of power from geothermal water or steam or for hot water distribution is generally due to the hot electrolyte solution entained in the steam.3 Composition of Some Geothermal Fluids(8) Location Components (Appr. NZ Otake. Published values range from 4.5 Total dissolved solids (mg/I) 3.5. 10. Japan Broadlands. Some typical compositions of geothermal fluids are given in Tables 10.800 23 4. if air gets in.000 19 3. Mexico East Mesa.1. but it is leached slowly from silicified rocks.3 and 10. high surface corrosion rates prevail.800 7 8 6 5 9 16 The total chloride and TDS vary considerably not only from region to region but even within the region itself. HzS contamination and the possible presence of oxygen(5).4. HzS in the steam or liquid phase causes micro cracks on the surface of steels. The concentrations of both fluoride and bisulphate under saturation conditions in these fluids is inversely related to the calcium concentration. Iceland 62 65 82 78 72 72 1. such as Lake Marvin in Iceland HzS is one of the major components. The concentration of fluoride in geothermal brines is limited by the solubility of calcium fluoride(CaF z)' Fluoride is readily leached from rhyolite.CH4 • Hz and NH 3 • In some fields. NZ Ahuaehipan.9 to 9. accounting for about 90 percent or more by volume of the non-condensible gases. A major component is carbon dioxide.000 24. . as it does in many situations and if the waters are acidic. When geothermal water flashes to steam. The general corrosion characteristics of geothermal fluids are given in Table 10.

.6 --------- 28 ~ . .7 630 586 57 61 42612 4153 49 5347 2.....9 6.0-5.16 Otake The Geysers Wairakei Steam dominated resources.6-8.5 21 217p 103 7.9 24 45-74 41 110 6 205 Steam dominated resources.8 16.2 1385 5 14100 2716 2. ~ ~ n ::s~ <. Steam dominated resources.6 0. 8.0 1500 7.. ~ .5 2...0 3260 1933 • 3.3 9710 0.0 I.:.0-5.7 222 36... 4.l HCO l (mg/l) Sol.. .2-8..4 Characteristics of Some Geothermal SteaDl and Water Phases(4) Location Ahuachapan Cerro Prieto Larderello Matsukawa Nature of the fluid Turbine inlet steam Separated water Turbine inlet steam Separated water Turbine inlet steam Separated water Turbine inlet steam Separated waier Condensate Turbine inlet steam Separated water Condensate Turbine inlet steam Separated water Turbine inlet steam Separated water Temp pH H 2S CO 2 CI- °C 156 156 160 160-180 183 147 25-47 127 127 26-42 171 101-175 101-175 4.. Table 10..NH/NH4+ 0.7 148 006 194 1.6 46 3.4 5.

(in addition to being corrosive). The corrosion monitoring system utilises several techniques to determine corrosion rates and aMlyse data.5 THE H1S PROBLEM For the abacement of H2S. carbon steel valves and elbows have a short in-service life. at The Geysers. 10. At locations where saturated steam is fed to the turbine. without measures for abatement of HlS indicated that. The electro-chemical method employs the linear polarization technique for r!lpid corrosion rate determination. cracking of 12 percent Cr. carbon steel has been found to be satisfactory. pitting and crevice corrosion suceptibility. Electro-resistence methods are also employed.g. e. Additionally pipe and plate-tvpe "oupons are incorporated as corrosion monitors in in-plant systems. Use of special materials such as carbon steel clad with SS 316 as turbine blades. initially. for the determination of passivity. as compared with high pressure steam from conventional boilers. In such cases.4 CORROSION MONITORING The Geysers geothermal power plant is the largest in the onwards a programme of corrosion monitoring and H 2S abatement was implemented. Consequently. corrosion monitoring in the hot condensate in three units.Geothermal Power and Water Chemistry Table 10. For steam lines. Sulphide induced stress cracking of high strength casing in the pumps used to extract geothermal fluids from underground have been frequent. showed a marked improvement.ristics or Geothermal Fluids(5) Corrosive Phase Liquids Water-Steam Water-Steam Water-Steam Steam Condensate com~nents 115 acidic oxygen 02 and CIH2S H2S H2S and 02 Materials in contact steels steels steels steels Tempered steel (turbine blades) steels Type of Corrosion Surface Surface Stress Stress fatigue surface Corrosion experienced in geothermal power plants may be summarised as follows(6): As the two phase fluid is quite erosive. It measures the potential osciJIation on electrodes. thicker and heavier blades are found to be necessary. blade cracking is not a problem. steel turbine blades has been reporteq. worl~ and from 1972 10. <a) Stainless steels and Al alloys are only partly passive (b) Pitting and crevice corrosion susceptibility of stainless steel is small < c) At is susceptible to erosion-corrrosion in areas of high turbulent flow (d) Corrosion rates are strongly dependent on condensate velocity. at The Geysers(7). Uneler the same conditions. due to turbulence induced erosion at these points. the cold condensate imparted some susceptibility to lItainJess steel for pitting and crevice corrosion.5 Corrosion Charade. As ~entioned earlier. where the steam is dry. provided air (oxygen) in-leakage is prevented. In The Geysers power plant(7). Geothermal steam has been observed to cause a sharp reduction in the fatigue endurance limit of turbine blades. with or without crevices or pits. direct contact condensers ..

4 0.1 To overcome the corrosion problems caused by H 2S contamination. The shell side of the heat exchanger is made of SS 304 and the tubes are of titanium.6 304 416 6061 3003 304 316 *Erosion. 10.1 to 0. On the other hand aluminium alloys showed a better performance. This is indicated by data in Table 10.1 0.8 0.116 Water Chemistry were used where steam from the turbine exhaust was mixed directly with cooling water. a new method for its removal is now being practised at The Geysers. The overall performance of the system has been satisfactory. SS SS Al AI Hot Hot Hot Hot Cold Cold SS SS 7. Efficient removal of H2S dependes upon high pH. One demonstration process uses CuS04 scrubbing. The following advantages are expected.1 to 0.4 to 2.4 0. in miles per year( m p y) With iron catalyst Without iron catal~st 0. Table 10. The Electric Power Research Institute and the Department of Energy.5 to 2. Here the non-condensible gases are seperated from the condensate. copper content.5 0. The other process is based on condensation and re-evaporation of the steam in a single heat exchanger.5 * 0. USA have evaluated two methods for H2S abatement in ali geothermal power plants. Unit 15 is equipped with surface condensers using SS 304 and a Streinford system designed to acheive more than 90 percent H 2S remova!. (a) (b) Turbine blade failure caused by fatigue corrosion due to H 2S can be controlled Turbine efficiency is increased by reducing boric acid deposits on turbine blades.6 TURBINE STRUCTURALS It was mentioned earlier that turbine blades exhibit fatigue corrosion in the . In this process the non-condensible gases are directed to a unit where H 2S is oxidised by sodium vanadate at pH 9 to elemental sulphur and water. the corrosion monitoring programme showed substantially increased corrosion rates on stainless steels exposed to the hot condensate treated with the iron catalyst. To compound this situation.6 Corrosion Studies with Reference to HzS Abatement by Iron Catalyst(5) Probe Condensate Corrosion rate.5 0. to oxidise H 2S to elemental sulphur. But later on the level of H 2S in steam from new reservoirs being higher the catalyst could not be regenerated quickly enough and the sludge caused severe operating problems. Both depend upon an upstream removal of H 2S.6.5 0.5 2.5 0. containing ferric sulphate as a catalyst. contact time and pressure.

the blades and other surfaces are susceptible to erosion in the presence offNlt moving water droplets in the steam. Hence it is preferrable to purge the turbine internals with a stream of hot nitrogen with suitable venting. The scale formation affects ev~ry aspect of the plant from the production . The inner surfaces of the condensers are therefore' protected with a coating of epoxy resins or aluminium spray. in its ferritic form.5 percent pure aluminium has been suggested for the inner cooler tubes. °C 70 100 125 100 to 200 Cu& alloys 0. in this condition.7. The erosion-corrosion rates at the turbine rotor and casing and nozzle diapharm at Matsukawa.3-0.1 0 0. The latter material is said to be r.7 Sureace Corrosion rates (MIBlYear) of Materials in Contact with Geotbermal Fluids(8) Geothermal fluid Condenste Aerated steam Well head flushed water Well head flushed steam Tllnp. By a proper choice of the speed of the turbine blade tip. during a shut down air ingress might occur. Table 10. However.1 0. the alloy enjoys immunity provided that chlorides are present in quantities less than 10 mg/l in residual water droplets of the steam.3-6 Ferretic Austenitic Steel Steel 0. which. it IS appropriate to mention that in addition to the problems of corrosion. This is specially so when wet steam under a pressure ofS kg/cm2 (100 psig) in the temperature range of 175 to 315 0 C is made use of. th.3 0 It is evident that the condenser tubes cannot be of Cu or Ni alloys.5 0.3-10 0. due to the presence ofH2S and oxygen.3-4 Ni& Monel 0.7 CONDENSERS From a corrosion view point highly adverse conditions exist in the condenser and gas extraction equipment of a geothermal turbine.. At this point. However. Surface corrosion rates reported for several candidate materials for the condenser tubes are shown in Table 10.1 0 0. Surface corrosion will be exhibited by steels in contact with the condensate from the steam flashed i~ the unit.: utilisation of geothermal waters will also lead to a lot of scaling and deposition on surfaces.4'-4 8·10 1 1·4 Carbon Steel 3-4 18-20 0.Geothermal Power and Water Chemistry 117 presence of H2 S. The internal parts of a turbine are normally resistant to attack from geothermal steam. 10. as in many fossil fuel fired power plants. Chrome iron (12 percent Cr) in the hardened or martensitic state is susceptible to stress corrosion cracking in the presence of geothermal steam. Japan ( which has acidic water and H2S) were computed to be about 20 mil/y. Thus softened and tempered stainless steel is being increasingly used for turbine blades. this risk is minimised.2-5 10-40 0. On the other hand. in the presence of non-condensable gases remaining in the turbine will lead to serious corrosion. while 99. Austenitic steels arc recommended for use as gas extraction rotors.liltant to geothermal steam except at high temperatures.

This would.composition . because the working fluid is contam. Fan coil units are conventional copper tube units with aluminium fins. Extensive field testing is require. CO 2 apparently produced dezincification of even low zinc brasses in high velocity regions. well head temperatures are less than the boiling point of water.118 Waler Chemistry reservoir to the reinjection system. Operational experience shows t\1at copper fan coils and tubes give good services in low chloride neutral pH waters free of oxygen. In such cases. but can be used for space and process heating. The data for NaCl . . making them very prone to scaling. It is evident ffom the information presented in this chapter.inated to a high degree with gases and dissolved solids<8l. 10. completely eliminates the problem of corrosion in turbines. As regards prevention of scaling. however. a binary cycle is proposed wherein the geothermal water circulating through a heat of exchanger. When the geothermal water temperature is not much above 100°C. the problems due to water and saturated steam chemistry are more severe than inlfossil fuel fired plants.including reinjection of the spent fluids.transfers energy to an organic liquid with a low boiling point like isobutane. Another approach is to 'sludge scaling'. Recent studies report the use of a direct contact heat exchanger to overcome scaling problems due to the high salt content of geothermal waters. Heat exchangers are of the shell and tube variety using carbon steel shell and copper tubes. A set of pressurevolume . Experience at Klal'1ath Falls indicated that when H2S is greater than 0. the low temperature geothermal water produces excessive scaling on copper tubes leading to under deposit attack. in which finely divided silica is added to the geothermal fluid to promote silica precipitation. In many cases. Here the Iburied supply pipe is of carbon steel.d. this will probably be the main application sinee.S DIRECT USE OF GEOTHERMAL WATERS At temperatures lower than 100°C at the well head. Use of organic polymers as antiscaling agents is being tried out.50. require the handling of high levels of suspended solids.H20 analysed by the International Association for the Properities of Steam will serve as a model in this context. It may become necessary to clean up the deposits on turbine blades and valves. In India. This type of approach through a binary cycle. it is impractical to produce steam by flashing. Nevertheless problems arose because of CO 2 and H 2S content.temperature .000 mg/l of dissolved solids. The materials to be used in the heat transport system in such cases could be the same as at Klamath Falls. The Salton Sea (USA) geothermal waters have an average of2. The rate f)f scale build up and corrosion inside the steam turbines used in flash cycles is not generally known. geothermal waters are not suitable for electricity generation.1 mg/l. that in the utilisation of geothermal water/steam resources for the generation of electricity or process heat. USA.0 reduces the polymerisation of silica and supresses the precipitation of CaC0 3 and metal sulphides. scaling is only due to calcium carbonate and silica. The vapour pressure of gaseous isobutane so generated will be enough to drive a turbine and can later be condensed by surface water.energy data is required for predicting the conditions of minimum scaling and optimum operating conditions. with a cooling tower. lowering of the pH to 3.

Cramer.E. Geothermal Power Plant Corrosion Experience . Institute of Energy Management. (1980). March 1981. Materials Performance. (1976). 2. India. . All India Conference on Corrosion Control. Anlikcr. Ellis II P.• (1981). Corrosion and Material Comratibility Problems in the Utilisation of Geothermal Energy.A Global Survey. Geothermal Energy Utilisation. (1980). September 1980. CQrrosion Monitoring in the Cooling System of the Geysers Geothermal Plant..Geothermal Power and Water Chemistry 119 REFERENCES 1. February 1982. Spon Ltd . Bombay. 8. Power. NCST (I97~). July 1980. and S. H-I to H-9. New York. (1977). New Delhi. ArrTlstead H. Cartee J. National Committee on Science & Technology.• 1978. Materials Perforn. Wahl E. John Wiley. Rank I. Kekuksa. Venkateswarlu K.A.E and D.C. 5. Corrosion Problems Come into Focus as Interest in Geothermal Energy Grows. 7.84-87. Pruce L. 9-16.P. and G. Geothermal Energy. Geothermal Energy Utilisation. 3.ance. (1982). 4.S . July 1976. Field Corrosion Tests in Brine Environments of the Salton Sea Geothermal Resource Area. Materials Performance.M. (1978).M. 6. 1977 .H .. E & EN.

dissolved oxygen. Since steam is under high pressure and at a high temperature. Chemical specifications are maintained by anatysing samples from various points in the system. reliable sampling. obtaining bL ratory an>tlyses and (a) .1 WATER AND STEAM CHEMISTRY MONITORING An effective programme of water the steam chemistry monitoring as the basis for exercising the necessary chemical control requires. preferably by on-line instrumentation are conductivity. chloride and silica. and by dosing appropriate amounts of various chemicals. pressure reducers and sample coolers form part of steam analysis instrumentation(l). it is desirable that direct sampling and continuous instrumental analysIs of the steam samples from predetermined turbine extraction stages be adopted. good· laboratory facilities. In order to evalute the steam chemistry. the power plants are deficient to the extent that. United States surveys showed that while more data on the chemical quality of steam and water are required at more frequent intervals. (b) Effectiveness of most of the on-line analysers is compromised by crud deposition in the sampling lines/nozzles and (c) A significant fraction of the analysers are not in use. the major chemical parameters which one monitors. One or more of the important on-line analysers do not exist in a majority of stations. a dedicated Chemistry Task Force and on-line analysers with low maintenance problems(l). The manual method of taking samples.11 ANALYTICAL TECHNIQUES FOR WATER CHEMISTRY MONITORING AND CONTROL 11. For prevention or minimising the corrosion in the steam water circuits of a power plant. sodium. pH.

humidity and temperature might interfere with the caliberation exercise. In the conductivity meters. adequate flow ensures that the chance of a blockage is minimised. The measurement also has to be compensated for the temperature of the sample. it is unlikely that any reasonable sampling frequency could keep specifications to within limits during transient operation or during periods of condenser leakage. the signal is amplified and measured on the scale in terms of specific conductivity values. with single phase fluids such as feed and boiler water (i.4). The cleanliness of the conductivity cell. The basic principle involves the generation of a current when an AC voltage is impressed upon two electrodes immersed in the cqueous test solutions. the quality of water in different sections of the power plant can be judged.Water Chemistry Monitoring and Control 121 adjusting chemical addition rates in order to correct deviations from the specifications is probably satisfactory for steady state operation of earlier designs.2°C. specially the electrode surfaces is very important. Water chemistry monitoring in a power plant might involve as many as 25 source points from which either the samples are drawn on the spot or sampling lines routed to a central sampling station. Sample nozzles must be kept clean and they will have to extend within the flow-line in an inward direction. one also measures "Cation Conductivity" wherein all the cations in the sample are removed by . On the other hand. cells with an appropriate cell constant are used. The lowest theoriticallimit of specific conductivity for water is about 0. so that the bulk fluid is sampled.05 J. However.1s/cm at 25°C Taking this as a reference. analysis and addition scheme. electronically and all conductivity measurements are reported at 25°C. A very reliable indicator of water purity is its conductivity. As mentioned in Chapter 6 specific conductivity measurements are also made use of in monitoring the performance of OM plants. The cell constant of the electrode cell is very important and depending upon the range of specific conductivity to be measured. There is scope for improvement in sampling of superhead steam. Very good online instrumentation is available and it is becoming a standard practice to install a number of conductivity probes specially in the hotwell section so that early warning of condenser tube leakage is available in the control room. analytical methods in the laboratory based on chemical and instrumental techniques as well as on-line monitoring for different chemical parameters are described. Modern instrumentation measures conductivity automatically with temperature compensation. This calls for a sophisticated design of the entire chemical control system and more importantly reliable maintenance(3.e.. One should always bear in mind that external factors such as dust. Reliable and reproducible sample collection is an essential condition. In this chapter. A two phase system like that of saturated steam poses difficulties in terms of sampling (as opposed to sample) reproducibility. boiler blowdown) condensate and superheated steam. the most reliable means of achieving an efficient control is by a completely automated chemical sampling. In case of long sample lines leading to a sampling station. For modern units. In addition to measuring the specific conductivity. The problem of sampling superheated steam at the turbine in-let is very exacting and the stearn purity so monitored will be the reference point for any other chemical control. The current is measured by an AC bridge.this doubt on sampling integrity is absent. It is best to cool the sample to 25 ± 0.

Hence a BWR power station laboratory has to analyse a comparatively larger number of samples for chloride than in other stations. Ion selective electrodes. installed in the condenser hot well will suppliment the conductivity instrumentation in detecting the condenser tube leak at a very early stage. especially in boning water nuclear power reactors. Commercial instruments having working range from 0. Another important instrumental measurement is the alkalinity of the boiler water. and COz ingress in laboratory measurements. Not only liquid junction but also solid state ion specific electrodes are in use for the determination of chloride. One of the alkaline conditioning agents used in boilers is ammonium hydroxide. Chloride can also be determined in the laboratory. It is desirable to know the sodium level in feed water. The cleanliness of the on-line as well as the laboratory electrode surface is an important parameter in this context. If the sample is degassed (free from COz) after it is put through the cation exchanger. for which pH monitoring is essential. using Hgl+ . Recourse has been taken to make measurements with chloride ion specific electrodes. the Central Electricity Generating Board. UK envisages the determination of the Na balance in the entire water steam cycle. This is possibly due to poor response of the on-line electrodes. as measured in the laboratory is different from on-line measurements. On-line sodium analysers are available in the market. At sea water cooled power stations such on-line probes. On-line instrumentation gives the pH indication in the control room. India has developed a PVC coated wire electrode containing red HgS . In several power stations it has been noticed that pH.Fe)+ . Sodium limits in steam have been revised to values as low as 3 J1g/l.05 J1g/l of Na. special precautions recommended include low sample flow. Of the various reference electrodes and junctions available for continuous monitoring. In view of the volatility of ammonium chloride. On-line sodium analysers are in service in the Madras Atomic Power Station. As with specific conductivity measurement. With this system. temperature compensation is a must. It is a less reliable parameter for high purity feed water as compared to specific conductivity. MIS Bharat Heavy Electricals Ltd ( R&D Unit). Lower concentration level measurements are possible in combination with an ion chromatograph. it is possible to measure chloride at level of as low as 5 J1g/l.HglCl z as the sensor with Hg . one opinion is that the presenCt' of . it is called "Degassed Cation Conductivity".HgS04 as the reference electrode. Once-through boiler operators only make use of this reagent. calomel (HgzClz)or silver-silver chloride (Ag-AgCI) electrodes with fritjunction and lID saturated KCI reference solutions give good results.122 Water Chemistry passing it through a H+ form of the cation exchanger.1 to 1000 J1gn are available. sensitive to H+ can also be made use of for pH measurements. In fact. electrode arrangement in parallel pairs and special electrode construction to minimise streaming potentials. Equally important is the chloride content of feed water. On-line instrumentation is also employed. 1 in a flowing sample.eNS' procedure. The sodium ion specific electrode is capable of detecting 0. though it is some what less reliable than conductivity measurement.

The colorimetric procedure recommended by AS ME that depends upon the formation of the blue heteropoly silicomolybdate can be used to measure silica upto 20 J. This i~ amplified and measured. 'thus creating a potential c>r C\llTent in proportion to its concentration. Through this additional step.2) The minimum detectable limit is 0.This results in the formation of soluble nOH. In the laboratory. In addition.005 mg/I. The resultant pH change in the probe develops a potential which can be measured and used for judging the partial pressure of ammonia. These are based on the development of a potential or I current directly proportional to oxygen concentration in water.00$ msll. if 10 cm cells aro uscd. silica and copper. on-line instrumentation has been developed for the measurement of dissolved oxygen. it is Ildvised to concentrate the blue colour by extracting it into a small quantity of an organic mixture (cyclohexanol and amyl alcohol in the volume ratio of 1:9) containing 0. colloidal or 'non-reactive" silica is monitored by the use of a turbidimeter based on the principle of light scattering. To measure reactive silica a number of we't chemical methods are available.on in high purity water. The oxygen dllS()lved in the sample diffuses through the membrane. On-line analysers for silica are now commercially available. .lg/l. Several such instruments' are available in the market. However the limit of detection ill 0.1) (J 1. the silica level of the DM water from the mixed bed is an important guide in assessing the performance of the anion exchange resins. is due to the added ammonia. Another important constituent which must bel monito:ed is silica. The specific conductivity of this solution is directly related to dissolved oxy. Silver or platinum serves as the cathode material. in such a situation. Another method of determining dissolved oxygen is by its fast "aotion with metallic thallium (TI). the distribution of silica between water and steam phase depends upon the temperatures and pressures of the two phases. Hence. while lead is used as the anode. concentrations .-+ 40HPb + 40H. thero is a speicific need to monitor this additive in different sections of the water and steam cycle. In the laboratory.One such analyser is based on a probe which responds to the partial pressure of ammonia across a gas permeable membran. The electrode reactions are: At the cathode : At the anode Oa + 2H20 + 4e.2 M Aliquat 336. aased on electrochemical techniques.-+ PbOa ?" 2H20 + 4e(11. The Coulometric method can allo be adopted as an on-line technique. the well established Winkler's test procedure. very strict limits are imposed on silica levels in high pressure steam. On-line ammonia analysers are becoming usefuI. As seen oarlier. An oxygen analyser should find a place in the main condenser area at the discharge of the condensate pump. using colorimetry with 5 cm absorpotion cells will lead to a detectable limit of 0. It mllY be mentioned that MIS BHEL (R & D Unit) have developed and introduced lnto eIle market a combined on-line analyser for chloride. The electrodes are seperated by an oxygen permeable membrane..Wilter Chemistry Monitoring and Control 123 chloride in steam. Since 'Silica from steam has a tendency to deposit on turbine blades. Since most of the power station laboratories have 1 cm cells.001 mg/l.

124

Water Chemistry

of silica lower than 10 J.lg/l can be measured even with 1 em cells. In both steam and feed water. copper has been specified to be kept at very low levels (2 and 10 J.lglJ). The extractive photometric determination using Neocupron reagent can detect a level of 20 J.lgn with 1 cm cells. Use of 10 cm cells or alternatively a copper ion selective electrode gives a det~ction level of 1 J.lg/l under ideal conditions. Other instruments useful in a power station laboratory are the flame photometer and atomic absorption spectrophotometer. Ion chromatograph is proving to be a very useful addition to the range of equipment.

11.2 AUTOMATED CHEMISTRY MONITORING AND CONTROL
On-lint: chemical instrumentation can be integrated into an automated system for chemical monitoring and control. For steam generators making use of nuclear heat. the main requirements of such a system are (a) (b) An ability to control the chemistry in the All Volatile Treatment (AVT) mode for long periods. Reliable detection of condenser leaks and if the leak is large enough. initiation of automatic control of the boiler water chemistry by using phosphate treatment in case of recirculating drum type units and An ability to log data and provide the chemist with a summary of post incident steam generator conditions at regular intervals or to diagnose the system chemistry behaviour.

(c)

For meeting the above needs. modern power station designs incorporate a dedicated mini computer as the basic component(5). Chemical analysis information is fed to it by commercial on-line analysers located at strategic points in the steam/water circuit. Acting on information from these analysers. the computer actuates valves which control the additiol1 of appropriate chemicals at the correct dosing points. For example. operation of the phosphate system is such that the automatic addition of phosphate to the boiler will begin when a condenser cooling sea water leak is confirmed by a signal from the sodium analysers. The computer controls the phosphate addition by feed back information supplied by on-line analysers measuring the phosphate concentration and pH of the composite boiler blowdown. In addition to initiating stipulated chemical dosing. the computer has to log and display data from all on-line analysers. interpret.give alarms and execute preventive action to correct offnormal trends in water chemistry. For the instrumental and automated chemical control system. using a computer to operate satisfactorily. a number of on-line analysers and probes are needed. These are in addition to the ones described earlier. viz.,hydrazine analyser amd a phosphate analyser(S). The computer should be dedicated and possess the following functional abilities:

Waler Chemistry Monitoring and Control
(a) (b) (c)

125

Acquisition of data from all the chemical analysers on the secondary side Automatic calibration of the analysers for ensuring accurate measurements and to detect instrument malfunction, Monitoring for all the system's alarm devices for diagnostic purposes these include temperature and flow indicators on analyser feed lines, flow switches on chemical dosing tanks and other pertinent indicators associated with the steam generator Detection of a condenser leak via the sodium ion analysers The starting and maintenance of phosphate treatment upon the detection of a significant condenser leak Storage and organization of a twenty four hour history of the analyser date and the sections ofthe.controller for display on the CRT screen in a numeric or plotted form; a printed copy unit for selecte1 permanent paper recor?s is also desirable and Direct digital control of the hydrazine and pH Control loops, if desired.

(d) ( e)

(f)

(g)

Two sodium ion analysers are required to be installed for the purpose of rapidly detecting condenser cooling water leakage. One signal per minute from both instruments could be sent to the computer where the following logic sequence is enacted: (a) (b) Temperature and flow rate of the sample to each instrument is checked If the temperature and flow rate of the sample to the analyser are within specification limits,the data from the analyser are examined to determine, if an abnormally high level of sodium exists in the condensate, An affirmative answer by one or both analysers initiates automatic instrument calibration and

(c) (d)

If water calibration, both analysers reconfirm the high sodium level and temperature and flow rate of the sample to each are acceptable, a leak is declared detected and phosphate addition begins auto~atically. The process of the above logic sequence for positive detection of condenser leak takes about 10 minutes.

11.3 SAMPLE CONDITIONING PHILOSOPHY
Analysers based on electrochemical principles, such as those for measuring pH, conductivity, dissolved oxygen and hydrazine can provide adequate accuracy only if the sample is maintained at a constant temperature. For this purpose it is recommended that each sample is cooled to a constant temperature (20 0 C or

2S°C).
For an efficient chemical control,it is essential that the sample flow to the analysers is always maintained. To make the computer aware of any discrepancy in this respect, Chromel-Alumel thermocouples and flow indicator tramsmitters are needed to be installed ahead of each analyser. Abnormal signals from them will alert the computer to the doubtful integrity of the signal from the associated analyser.

126

Water Chemistry

In conclusion, it can be said that on-line monitoring of chemical parameters and their automatic contjol through a computer. will go a long way in providing reliable operation of the high temperature and high pressure steam generating system. whether in the fossil fuel fired or nuclear heated sesments of the electric power industry.
,UlfEReNCeS 1. Venkatcsswarlu K.S., (198\), Water lind Steam Quality, for Mllintenance of Oeneration Efficiency, Proc. All India Canference on Water Chemistry for Industrial and Thermal Power Slatio"s Boile,s, 0.\/1 to 0-1111. Indian Institute oi Plant Engineers. New Delhi. 2. Venkateswarlu K.S .• (1982). Feed Water Quality Control for Fossil Fuel Fired and Nuclear Boilers. Proc. Seminar of Instrumenl Society ofAmerica (Bombay Chapter). " JNTEQ. 6-13. Nov.1911l. 3. Strauss S.D.• (1988). Water Treatment Control and Instrumentation. Power (Special $e13tion) May 198B. W.1610 W.30. 4. Jonas 0 .• (1989), Developing Steam Purity Limits for Industrial Turbines. Power. May 1989.78-83. . 5. Venkateswarlu K.S .• (1988). Chemical Instrumentation Needs of Modern Steam Oener/lting System. Chemical Busi",ss. 24-26. June 1988.

In addition . to make it fit for drinking.. uptake of soil moisture by the roots of a plant etc. are the passage of water through cell walls.Sourirajan. The standards for drinking water u!> set by the World Health Organisation are detailed in Chapter 2.12 DESALINATION.. Osmosis is the process whereby. has this to say about Reverse Osmosis . RO finds wide ranging application in waste water treatment and consequential abatement of pollution and water reuse(l. Removing the dissolved salts from brackish or seawater to make the water acceptable for drinking is popularly known as Desalination. In the context of water scarcity in many parts of world and public concern on the quality of our environment. but also in both rural and urban areas of the developing countries. Reverse Osmosis (RO) stands out as the one that gained wide acceptance and appIication(l).l). The Technology Missison on Drinking Water launched by the Government of India has RO as one of the metbods for providing clean and safe drinking water in rural India. This flow or diffusion of water i~ basically due to the difference in the [otal solvation energy on either side of the membrane and the flow will result in the equalisation of energy on . has made great strides during the last 30 years. However. Examples of Osmosis. the science of water purification. S. Among these new technologies. when two s~lutions having different concentrations of an electrolyte (such as NaCl) are seperated by a semi-permeable membrane. This continues untill the concentration of the dissolved solute on both sides becomes equal. who along with his colleagues has pioneered this technique. the effective utilisation of RO for the water treatment problem alone would make the social relevance of RO. pure water from the solution having lower concentration of the electrolyte flows across the membrane into the one at higher concentration. EFFLUENT TREATMENT AND WATER CONSERVATION The availability of clean drinking water is still a major problem not only in the semi-arid and desert regions of the world. second to none".

one can say its osmotic pressure is of the order of 25 kg/cm2 (350 psi). These two are opposing effects. A andlor (1lP . Thus. one uses a term. As the name implies Reverse Osmosis (RO). it would be appropriate to relate it in terms of a pressure and this is called the osmotic pressure. while t has to be decreased.7 kg/cm2 (1 Opsi)..Lill) t Water flux through the membrane.000 mg/l. like seawater. These factors have to be optimised to suit the electrolyte concentrations in the water resource. which indicates the amount of electrolyte left behind in terms of a percentage.g. cm). Again onO. as well as the quantum of drinking water needed per day. the Rejection Levels of monovalent cations and anions (e. To quantify. potassium. while the viscosity of water decreases with increase in temperature. The expression governing the flux of water (WF) across the membrane is given by.) is about 0. Mg. Sulphate) are about 93-95 . It is also dependent upon temperature. The effect of temperature is not noted in the above expression.1) In the above equation. a small part of the electrolytes also get transported. a pressure in excess of25 kg/cm2 has to be applied in order to over come its osmotic pressure and start giving a reverse flow of desalinated water across the membrane. But in reality. WF IlP Lill A t K If one wants to increase WF . 'Rejection Level'. only pure water gets transferred across the membrane. fluoride) are about 90-92 percent while those of divalent ions (Ca. By exerting hydrostatic pressure on the side of the solution :laving a high concel~tration of electrolytes. (kg/cm2) Differential of the osmotic pressure. This flow will increase with an increasing positive difference between the applied pressure on the sea water side and 25 kg/cm2. has to optimise. is the opposite of this process.an) have to be increased. In an ideal situation. . This phenomenon can be easily demonstrated in the laboratory. The required technology has been well developed during the last 25 years(4). As an approximation. Thus at higher temperatures. The translation of this principle to large scale application is what makes RO so attractive to desalination and effiuent treatment. since basically energy terms are involved. Cons~quently for the desalination of sea water. Thus it is possible to transfer pure water from a salt solution. the flow due to osmosis is at first stopped and then reversed at a higher pressure. RO membranes are sensitive to temperature. sodium. Membrane thickness (in microns). Since seawater has a TDS of about 35. Differential of the applied pressure. it is noted that the osmotic pressure of a solution having 1000 mg/l of dissolved salts (NaCI etc. across a membrane by application of the required pressure.128 Water Chemistry both sides. the membrane performance deterioates while the water flux across th~ membrane increases. (kg/cm2) Membrane area {in sq. W F =KA (1lP. chloride. Since there is a flow in one direction. Membrane constant. (12.

so that they concentrate quickly in the feed side of RO unit. the use of a fine 5 micron catridge filter. In addition to normal clarifying and filtration procedures. is on the lower side as compared to the other two geometries. In the hollow fibre RO Unit. On the chemistry side. Here again. To prevent the precipitation of calcium sulphate. The three layers are then wound cylindrically over a plastic tube through which the purified water flows out. (It may be recalled that the hot primary coolant flows through the U tubes and steam is generated on the shell side). spiral wound and hollow fibres.Desalination. It was noted earlier that for both calcium and sulphate. the rejection level is very high. The output of the tubular configuration. A good surface to volume ratio is available and is not affected by suspended solids or turbulance. the water is dosed . These are known as asymmetric membranes. Once the saturation solubility is exceeded. the later two configurations have found wide application in the water industry. the feed water flows around them. are packed in a U shape in a cylindrical pressure vessel. suspended material is a serious threat. extremely thin strands of a hollow membrane. Another popular configuration is known as the 'HoJ]ow fibre'. Suspended solids have to be removed from raw water to the maximum possible extent. but the configuration is susceptible to fouling by suspended solids. Most of the membrane have pore sizes around 5 Angstrom units and thickness of about 100 microns. This configuration bears a close resemblence to nuclear steam generators with a U shape bundle of tubes fixed in a cylindrical vessel. One can conceive the spiral wound geometry as a rolled sandwich. while the product water comes out of the fibres. The membrane configuration is placed in a suitable pressure vessel (cylindrical) made of stainless steel or fibre reinforced plastic. which is also bulky. prominent among them being tubular. The feed water flows from one end of the pressure vessel to the other and the product (purified water) comes out of the plastic tube along the central axis of the membrane configuration. calcium sulphate precipitates out. The plastic tube has perforations on it to allow this to happen. A sheet material that acts as a water carrier is sandwiched between two membrane layers. As we saw in the beginning. calcium salts (bicarbonate and sulphate) pose a serious scaling threat. While RO is a physical process.10 Angstrom units. The membranes have been made use of in several geometrical configurations. being 95 percent. an excellent ratio of surface to volume is acheived. Effluent Treatment and Water Conservation 129 percent. water chemistry comes in because of the feed water (raw water). The counter treatment procedures are essentially the same as discussed under cooling water treatment. Subsequently thin film composite membranes have been developed and these have helped in reducing the operating pressure. Of these. The sandwich layers are seperated by a plastic netting. The earlier type of membranes had a tight but thin surface layer backed up by a thick porous substrate. It is selfevident that with RO pore sizes in the range of 5 . The rejection of electrolytes occurs at the thin surface layer and the porous layer acts only as a support. As the name implies. just before the water enters the RO unit is being advocated. raw water contains all sorts of impurities and some of these affect the efficiency of RO.

Iron and manganese present in raw water have a tendency to get partially oxidised at neutral pH values and the oxidised forms. Fe (III) and Mn (III) might hydrolyse and precipitate. this break even point is reached when the TOS in the raw water is ~1600mg/l as CaC0 3. able to overcome this problem. From a chemical point . In this respect cellulose acetate membranes are somewhat better than the polyamide type. this break even point has been reduced to 1100 mg/l expressed as CaC03 .. before public distribution is therefore an important requirement when RO is used for rural water supply. For domestic consumption. the membranes deteriorate much quicker. The acid dosing referred to above will bl. it has been shown that operating costs. The membranes are also subject to biofouling.With marked improvements in membrane performance and technology. but this is prevented by acid dosing that is done for other reasons mentioned above. This would call for the establislunent oflocal chemical testing facilities. However. while the scaling of calcium bicarbonate il prevented by keeping the Langlier Index in the negative range (acid dosing). the residual chemicals must conform to the tolerances prescribed by WHO for drinking water. but also t~eir dispos~l. Once again chlorination ofraw water is the only remedy. as otherwise the membrane will get damaged by chlorine interaction. the residual chlorine needs to be removed before the raw water enters the RO unit. Howev~r. the membrane increases with temperature. Product 4nalysis.130 Water Chemllt1'Jl with sodium hexa metaphosphate. Economies dictate the utility of a RO unit.of view.us resource. where the daily as well as seasonal fluctuations in temperature are wide. based on simple procedures. One should bear in mind.ly see the limitation it imposes in arid zon:s. Another aspect is the treatment to be applied to a shearn of industrial effluent or waste .1 EFFLUENT TREATMENT AND \VATER CONSERVATION In view of the very large volumes of water employed by industry. In conclusion it can be inferred that RO offers an attractive route for rural water supply and it is also an attractive precourser to a full scale OM plant. it is but natural that attention is paid to two aspects at the back end of any process using such water. the priority is to conserve it. One can eui. As noted earlier the membrane performance is affected by temperature. It is pertinent to point out that the type ofchemical treatment noted above is for industrial water (either directiy used or fed to a OM plant for further purification). not only the cost of regene18nt chemicals used in the OM. when it is coupled to a demineralisation plant for producing high purity water. particularly in terms of the savings effected on regenerant chemicals is such that a break even point can be realised. U~ually RO operates best at 2S oC. While the water flux across. Since water is a precio. It is obvious that the capital cost will increase when RO is added. 12. On the other hand cellulose acetate membranes are suscetidble to hydrolysis.

1 Tolerence Limits for Discharge as per Indian Standards (IS: 2490.Part 1. econcmiser. In the power generation sector. with due regard to pollution control.1 0. for reuse. Table 12. Effluent Treatment and Water Conservation 131 water. ion exchange.01 50 350 20 45 ]00 ]0 As mentioned in the begining. a 210 MW unit consisting of a drum (normal level) with water wall boiler tubes. In this section. 1981) Constituent! earameters Suspended solids mg/l Dissolved solids mg/l pH Chloride mg/l Sulphate mg/l Zinc mg/l Lead mg/l Mercury mg/l Ammonical nitrogen BOD Oil & grease mg/l Temeerature °c Surface Effluent Di~charge to Public sewer Irri~ation 100 2100 5. as much as 50-60 percent of the water can be recovered and recycled. 1000 1000 IS 200 2100 5. of course have a much greater holding capacity.C. before it is discharged into the environment.5 600 1000 0. without recycling or r~use are given in Table 12. reverse osmosis and even distillation are made use of to meet the treatment requirements. filtration.5 . Apart from legal requirements on the effluent discharges. Unlike the similarities in the quality of water needed by industry. pulp and paper and steel. As such universally applicable effluent treatment procedures are not avaiable. General techniques such as precipitation. Thus industrial effluent or waste water discharge into the environment is as much of a moral issue as one of law and chemistry.5 .6).1981).Desalinarion. specially the core industries like power. It has been estimated that in the production of industrial alcohol. The full steam water circuit will. The tolerance limits of some of the parameters set by the Indian Standards (IS :2490. leading to hazardous consequences. Ii few illustrative examples of effluent treatment in some . before the waste water is either discharged into the environment or reused.01 50 30 10 40 1 0.0 1000 1000 5 600 2100 6. viscose rayon. it is al~o unethical to discharge such waste water which an unsuspecting public might come into contact with and some times even make use of it. superheater and reheater have a water holding capacity of about 320 cubic meters.9. fertilisers and steel.1 (5).9. The water requirements of some of these. The best way is to reclaim as much water as possible even though it may not be of the same quality as the input. parI I.2(5. for the discharges to the environment are given in Table 12. the effluents generated by an industry are specific to it . large volumes of water are used by industry.

The waste water in power stations could be the boiler blowdown and the cooling tower basin (if it exists) blowdown waters. when river. the heavy water is reused. The utilisation of chalk which is a b) product of the ammonium sulphate production process by Gujarat State Fertiliser ':orporation 4 India is a good example(7). Special instrumentation is available to detect heavy water spill!> and recovery systems from the ambient atmosphere are installed to recover as much of it as possible. either thermal or nuclear. Use of sulphuric acid in place of hydrochloric acid. In modern fertiliser plants. On the other hand. in view of the need for discharging "as Iowa radioactivity" as possible (ALARA criterion). Reverse Osmosis is fInding increasing application in such situations.300 It is important to realise. lake or sea water is used for this p':rpose. If cooling towers are employed for condenser cooling.the blowdown from boiling water reactors.6) Industry Fertilisers (Ammonia) a) b) c) Gas based Naphtha based 10 Cubic meters of water used per ton of the product 17 Fuel 011 based d) Coal based Fertilisers (Urea) Petrochemicals (Gasoline) Cement by wet process Chrome leather industrial alcohol Viscose rayon Pulp and paper Integrated steel plants 24 69 6 25 12 32 65 160 275 150 . generally reduces the effluent load. by ion exchange and effluent is re~ycled. A slurry of chalk fills a pond .effulent trealment is one of the important activities. is purified of its radioactive constituents present at a low level.2 Water Requirements for Industrial Operations(5. there will be some loss of water due to evaporation. water conservation and its reuse. an integrated approach is adopted for effluent treatment. water is recirculated to a very lar~e extent. it is directly discharged in·to a large water body after passing through the condenser. Afler upgrading.132 Water Chemistry industries are reviewed. For example. that in power stations. In all nuclear power stations. Simple treatment will make these volumes of water environmentally safe and reusable. or discharged into the aqueous environment. The effluents that really need a treatment in a power station are the acidic arid alkaline regenerative waste streams coming out of the demineralisation plants. Neutralisation and dilution ponds are available adjacent to the DM plant and usually a treated and neutral effluent water is discharged into the environment. Table 12. Water conservation is best seen in nuclear power reactors using heavy water as the moderator and coolant.

3. In the steam reformers.3 Water Consumption in a Shore Based Steel Plant(8) Process Power generation Blast furnace Rolling mills Strel making Coke maki. On the other hand. Of course.1 1. The advantage lies in the effluents getting dIscharged into the sea.0 5. where naphtha is cracked. the mineral value could be recovered in the form of diammonium phosphate. Consequently material compatibility problems arise that are similar to other situations.0 Distribution as percent Sea water Fresh water 37.5 to 2 percent of ammonium sulphate. this would mean that chalk pond water might con tam 1. contaminated process condensate from an ammonium sulphate plant is used. the temperature and the process of carbonisation and the recovery of ammonia. in addition to power generation in its captive plant(8).4. as much as 60 percent of the total water requirement at a shore based steel plant is met by sea water. effluents and suspended solids constitute the bulk of pollutants.8 14.2 5. where sea water is used. where the dilution factor is very high. wherein it is used for coke making. By making use ofthis m a phosphoric acid plant. Thus the chalk pond serves simulataneously as a neutralisation facility for both acidic and alkaline effluents by using a by product.9 11.9 9.1 10.5 59. The volume and composition of effluents arising out of a coking plant are dependent upon the nature of the coal. Chemical and organic contamination is also a common factor in the waste water from tlhe coke oven batteries.4 5. the water coming out of the units contains fine carbon particles.by using a drum filter and the water is reused. To save on fresh water. Even in making the chalk slurry. The ammonia and carbon dioxide generated are stripped and recycled.7 3. scrubbing of blast furnace gases.3' 2. The acidulated effluent is returned to the chalk pond.Desalination. The average percentage distribution of water usage at a shore based plant is given in Table 12. Effluent Treatment and Water Conservation 133 known as the chalk pond. A representative range of contaminants from a coke oven plant is given in Table 12. These include corrosion and marine biofouling. In the steel industry.7 1.5 10.0 0.7 3.8 7.3 7. One of the largest consumers of water per ton of the product is the steel industry. while the treated effluent could be used as make up to the cooling tower. rolling etc.lg Sintering Miscellaneous Total % of the total 47. ammoniacal effluents from ammonia and urea plants are also fed to the chalk pond.7 0. In some plants ammonia and urea bearing effulents are mixed and subjected to thermal hydrolysis at 200°C under pressure with steam.7 40.9 4.. steel making.7 100. These are collected. cooling condensers anc other odd jobs. . Table 12.6 8.5 Thus. The water from this pond is utilised in the phosphoric acid plant for fume scrubbing (which makes it acidic). and functions as a mediunl for water cycling. saline water is also used (in part) at shore based steel plants.

before the water is reused. A number of techniques such as ion exchange. Water washing of the residual gas gives an effluent that is almost free from ammonia. Table 11.134 Wa. followed by fast oxidation. The process is based on the observation that dissolved or fmely dispersed organic compounds in waste water can be hydrolysed and oxidised by bubbling compressed air or high pressure oxygen at elevated temperatures(upto 320°C) and pressures (210 kglcm 2). The lean solution so produced is recycled into the process. A few examples are given in Table 12.4 Chemical Contaminants in the Waste Water from a Coke Oven Plant(') Chemical Constituent Free Ammonia as NH) Ammonium compounds as NH) Chloride as HCI Thiocyanate as CNS Thiosulphate as S Chemical oxygen demand Range in mg/I 20-500 100-3000 500-9000 100-600 100-1000 3000 Ammonia is removed from the coke oven gas by contacting it countercurrently with a solution of phosphoric acid in a two stage spray type absorber.5(10). have been developed to remove the other pollutants. which slows down with time. electrolysis. There is an induction period. petrochemicals. Among different processes. dye-stuffs etc. After oxidation in a reactor (30 to.5 Examples of the Efficacy of Wet' Air Oxidation(IO) Contaminants in Waste Waters Acrylonitrile Amines t-Butyl alcohol €arbon tetrachloride Dye stuffs (composite) Epoxy resins Formaldehyde Herbicides (composite) Monoethanol amine Pesticides (composite) Phenols Polythylene Polyglycerine Sulphides Efficiency (as percentage) for COD TOC . 60 mm) the waste water stream is cooled and depressurised. The efficiency of the process is judged by the percentage reduction acheived in the COD and Total Organic Carbon (TOC) levels of the waste water. require treatment procedures that will effectively destroy the organic contaminants before such waters are reused or discharged into the environment. adsorption on high surface area. The behaviour is typical of a free radical initiated process. pesticides. Waste waters from organic chemical industries such as refineries. 65 ·94 86 91 99 94 86 97 88 79 97 97 89 98 90 83 .e. Chemistry Table 12. synthetic polymers etc. plastics. W AO is self sustaining at Chemical Oxygen Demand (COD) levels greater than 15 gil. Wet Air Oxidation (WAO) of the organics has gained favour<8).

12. the paper and pulp industry is one of the very large consumers of water per ton of the product. Wet Air Oxidation can also be adopted to these wastes. Pati! R. 8. Because of the decreasing availability and increasing cost of Water for industrial activities... lignin precipitates out and is adsorbed on the cellulosic matrix. Corrosion and Maintenance. The cellulosic material is suspended in water.I G. Reverse Osmosis has Come to Stay on its Own Merit for Problem Waters. 1992. The Iingin containing waste water is then allowed to mix with this. November. Experience With the Sophisl1cated Instruments for Monitoring of Effluents. K. Ibid. Gandhi M. Subramanian.lO. Misra B.:". 1992. Reverse Osmosis for Water and Waste Water Treatment.8.M. (1981). DesaI R. GC. which is then 'acidified (less than pH 2). 4 .20. 3. Bombay. Corrosion and Maintenance. November. BB. ~n.6. (1992). • ". November. National Centre for Technical Development.. PiIlai. November. nearly 70 percent reduction has been observed for both COD and colour. (1992). 5. 1992.D. 6.' Khopkar.I . which will in additi~n. there is a neec! to explore alternate techniques. Q. Smhamahapatra P..2. Ibid. 2. it is very essential to recycle as much waste Water as possible by a proper choice of effluent treatment. All India Convention on Industrial Water Treatment and Conservation.6.A.siderably reduce the discharge of pollutants into the environment. A recent process developed in India(ll) makes use of the plant's waste cellulosic material as the medium for lignin adsorption under acidic conditions. and P.1992.. Zero Effluent Approach for Fertiliser Plants. November. Mayor L. .P. 211.~ . G. Thus the process offers a good alternative to other chemical processes. (1992). REFERENCES I.l GC.N.D.I . During pulping and bleaching processes.E. Effluent Treatment and Water Conservation 135 An added benefit of WAO is its ability for recovering some inorganic chemicals like sodium carbonate (from black liquor in paper and pulp industry) ammonium sulphate (from coke oven scrub liquids) and chromium (from sludges of glue manufacture ).K.000 mg/l of lime) and coagulation with alum and ferric alum.BB.. and S.. 8. Water Management Practices in Fertilizer Industry. 7. Because of the cost of chemicals specially in the coagulation process. E. Doshi A. (1992). The chief among them are massive lime treatment (doses ranging from 3000 to 10. lignin and its degradation products are released which are resistant to biodegradation..K. and T. 1992. (1985).Q. 4. A number of chemical processes have been developed to overcome this problem. Modern Processes for Treatment of Input and Waste WaterReverse Osmosis and Membrane Technologies. thus freeing the waste wate~ of its contaminants.l .l . Under these conditions.M. Water and Effluent Management Technologies in Integrated Steel Plants.Desalination. 1992.. 221 -232. Ibid.N. As noted in Table 12. The acidity which is around a pH of 2 is determined by the zeta potential of the cellulosic fibres. Sukumaran Nair M. Ibid. Role of Membrane Processes in Treatment of Industrial Effluents..Ibid. At an initial COD to fibre ratio of I. (1992). Proc. November..P. (1992).

M. and P.1992. R. M. Panda. Ravindranath K. 171. All India Convention on Industrial Water Treatment and Conservation. 4. S. Pant.. (1985).Y.J. Wet Air Oxidation of Toxic Industrial Waste Water. Wet Air OXIdation of Hazardous Organics in Waste Water.S. Proc. I I.IS. Canney. Paul. Misra. November. and A. National Centre for Technical Development. S. 10.. .G.I . . Environmental Progress. De. and S. Islam S.I . A. . (1992). Removal of Colour and COD of Pulp and Paper Pulp Effluents by Lignin Removal Process. Sekar.L. Y. Water Chemistry' Randall T.136 9.9. Ibid. (1992). November. Bombay. 1992.

60 Density of Water. 28. 38. 43. 45 Conductivity Cation. 45. 97 Cupronickel. 100. JJ3. 61. 106. 57 Strong Acid. 33.89. 93.121 Cooling Tower.86. 69. 135 Chloramines. 102. 76 Calcium. 41.70 LP.INDEX Algae. 24. 54 Quality. 103. 7. 59. 80. 130 Carbon Steel.97. 73. 99. 115 Caustic. 66. 122 Chlorination. 105 Dielectric Constant of Water. 43 Biofouling. 59. 48 Monitoring. 122 Recirculating. 48. 21. 95. 80 Degausser. 57. 61. 3. 578. 88 Cation Exchange. 23. 101.38. 90. 46. 80. 94 Ground Water Qualit). 79. 74 Demineralisation. 117 Acidic. 99. 133 Feed Water Quality. 72 Boiler Water. 35. 128. 95 Dissolved.117 Desalination. 78. 80. 96. 33 Dissociation Constant of Water. 70. 60. 79. 70. 75. 3. 74. U5-Jl8 Incaloy-800. 89. 70. 72 Quality. 60. 36. 79. 34. 65 Cation Exchangers. 102. 45 Alkalinity. 29. 99 Corrosion Products. 71. 29. 11. 12 Boiler. 106 Chemical Oxygen Demand. 59. 76. 127. 103. 57. 66. 43. 46. 1 12 Total. 121 All Volat45. 28. 31.6. 44 Biological Monitoring. 65 Strong Base. 105. 87 High Pressure. 70. 50.37. 12. 70 Drum. 75. 47. 1 I. 101. 69 Bromine Biocides. /1. 2. 83. 56. 53. 69. 134 Filming. 131 Fertiliser. 44 Calciam Salts. 62. ll. 123. 75 Low Pressure. 130 Economiser. 58. 36. 73 Brass. 75 Once-Through.8$. 11. 47 Fission Products. 105 Explosion. 98. 40. 107 Injection. 121:1 Drinking Water Guidelines. 50. 27. 105. 102. 49 Hardness of Water. 15 Hardness. 74 Weak Acid. 107 Fluoride. 70. 79. 42. 132 Paper. 83 Ferrous Sulphate. 60. 43. 57. 113. 79. 113. 58 Ion Exchange Beds. 121 Conductivity Specific.50. 72. 40. 127 Deuterium. 67. 74. 48. 102 Carry Over Coefficients. 100. Jl4 Graphite. 49 Condensate Polishing. 61 . 98. 24. 90 Conditioning. 80. 135 Steel.84. 2. 100 Condenser. 122. 8. 65 Anion Exchangers. 47. 70. 49 Corrosion.61. 32. /15 Inter Granular. 41. 61. 58. 76 Crevice. 71. Effluents. 71. 102. 49: 50. 80. 132 Hot Conditioning. 95. 70 [{P. 102 Hydrazine. 80 Ammonia. 125 Hydrogen. 101. -4. 20 Dissolved Oxygen. 66. 2q Pitting. 105 Amines. 100-104 Inconel-600. I I Heat Exchangers. 134. 99. 100. 37 Deposition/DepositFormation. ll. 97. 51. 134 Anion Exchange. 75. i. 75. 52 Heaters. 115. ile Treatment. 132. 82. 59. 42. 132. 48. 2. 104 Geothermal Water Quality. 23 Deoxygenation. 96. 97. 44 Chloride. 45. 69. 53 Cooling Water. 3. 78. 72. 61. 93. 81. 51 MagneSium. 36. 62 Barnacles. 96. 26. 75. 12 Biological Oxygen Demand. 20. 70. 42 Chromate. 42. 62 Weak Base. 43. 66. 61. 60.70 Heavy Water. 101 Ion Exchange. 106 Coagulants. 29. 52. 48 Chlorine Demand. 4. 66 Deaerator. 2. 103 Hydrogen Sulphide. 123 Dissolved Solids. 10.130. 113. 3.80. 69 Cyclohexyl Amine. 115 Stress Corrosion Cracking. 3.

115 Steam. 70. 103 Make up Water Quality. 70 Surface Active Agents. 77. 121 Steam-Hydrogen Ratio. 94. 121 Super heated.108 Monel-400. 54 Molybdinum. 31. 94. 24. 76. 6. 51. 30. 16 Ruthenium. 60-62 Osmotic Shock. 106 Viscosity of Water. 62. 10. 4. 52-54 Pukarius Stability Index. 66. 96 Reactor Water Quality. 95 FOSSIL.138 Anion. 48 Man-Rem Problem. 91. 106 Nuclear Reactors. 79. 64.38. 3. 21. 25. 106 . 116 Uranium. 93. 102-104 Morpholine. 78 Phosphate Treatment. 128. 1 PHWR. 77 Hide Out. 2. 35. 63 Counter Current. 59 Capacity. 132 Wet AIr Oridation 134. 61. 80. 13. 14. 87. 7. 47 Zinc. 32. 32. 70. 121 Organics In Water. 79. 1. JOO. 69. 24 Phosphate. 81. 102 Addition. 28. 1. 20 Water. 65. 54 HEDP. 130. 93 Mixed Ferrites.8. ConductIvity. 2. 90 Saturated. 94. 59 Gel. 63 Type-ll. 36. 36. 60. 45. 13. 78 Coordinated. 125 Computer Control/ed. 124. 51. 105. 4. 54 AMP. 20. 101 RBMK. 120 Explosion. 60. 96.54 Zircoloy. 2 Generator. 102 Zirconium. 125. 135 n Zero Solids Treatment. 101 Phosphenates. 102. 95. 89. 106 Mussels. 53. 94. 15 Water Conservation. 106 Uranium Dioxide. 61 pH. 99 101 Reverse Osmosis. 53. 76. 62. 20. 132 Molybdate. 53 Point of Zero Charge.4. 65 Ionic Product. 123 Copper. 50 Polyphosphate. 98. 52 Lithium Hydroxide. 120. 5. 72. 100 Change With Temperature. 94. 122 Face. 83 Zeta Potential.94 VVER. 38. 117. 61. 63 Co Current. 82. 50. 62. 132 River Water Quality. 123 pH. 64 Ion Exchangers. 61. 70 Turbine. 26. 87. 101 Research. 86. 63. 93. 115. 87. 10.29. 123 Sp. 66. 51 Surface Tension of Water. 102 Sob1bility. 82 Silica. 70.56. 29. 17.26. 24 Water Chemistry EqUIlibria. 9. 87. 10. 93 BWR. 53.60 Macroporous. 59 Type-I. 121 Silica. 3. 63. 59 Cross Linking. 7. 125 Quality. 94. J08 Super Heater. 61. 49-52. 123 Sodium Absorption Ratio. 39 Thermophysical Properties. 106 On-Line Analysers. 104 Cation. 127. 43.idents. 124. 98-100. 120 Automated. 83. 49. 44 Polyelectrolytes. 20 Thermal Power Stations. 33. 100 RegeneratIOn. 76 Radiolysis of Water. 102. 93. 94. 2. 127. 90. 125 Quality Specific'ations. 62. 103 Formation. 125 Chloride. JOO. 93 Water Chemistry. 93 Power. 23. 69. 86. 95 Material Compatibility. 67. 31. 130 Sea Water Cooling. 28. 65 Three Resin Bed. 102. 102-104 PWR. 51 Langlier Index. 69. 65. 122. 104 Mixed. 9. 13. 96 Moderator. 91 Reheat. 108 Ryzoar Stability Index. 19-22 Water Chemistry. 52. 81. 52 Scale. 4. 66 Stratified. 62. 9 Stainless Steel.53. 43 Nuclear Acc. 61. 103 Magnetite. 130 Congruent.

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