Table of contents

Chapter 1: Water Concept

Kinds of water
Definition of water and properties
Resources of water such as
Surfs water and properties
Rain water and properties
Ground water and properties
Sea water and properties

Chapter 2: Water Usage

Uses of water
Drinking water and properties
Industrial water in power plant

Chapter 3: Water Properties: Physical, Chemical

Chemistry of water
Color
PH
Turbidity
Acidity
Alkanlity
Hardness
Chloride and chlorine

Chapter 4: Water Impurities and Toxic Materials

Impurities in water
Suspended solid
Gases
Total dissolved solids
Organic compound
Toxic compound.

Chapter 5: Impurities Impacts on Thermal Power and

Technical Solution

Effect of impurities in the thermal power stations such as:

- Corrosion
- Pollution
- Physical corrosion
- Deposit in tube boiler

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Chapter 6: Water Treatment Methods
Kinds of water treatment
Filtration precipitation coagulation
Kinds of filtration
Factor’s effecting on filtration process
Distillation
Boiling point simple distillation
Faction distillation
Distillation of water as treatment method
Reverse osmosis
Kinds of membranes uses in Ro system
 Cellulose acetate membrane
 Zealot
 Kinds of zealot natrolit nalcine
 Method of regeneration of zealot

Softeners
 Kinds of softeners
 Regeneration of softener
 Water out let properties after softener
 Problems in softener
Chapter 7: Water Analysis Methods
Analyses of water as ASME methods
Sampling of water
 kinds of sample
 method of sample
 sampling of water boiler at different temperature
Testing of water sample as ASTEM method
 PH conductivity
 Hardness
 Acidity
 Alkalinity
 Chloride and chlorine
 Sulfate
 Phosphate

Refernces

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 Chapter 1
Water Concept
: Concept
1. Kinds of water
2. Definition of water and properties
3. Resources of water such as
4. Surfs water and properties
5. Rain water and properties
6. Ground water and properties
7. Sea water and properties

1. What is Water

The origin of all water supply is moisture that has evaporated from land masses and
Oceans and subsequently precipitated from the atmosphere (See Figure 1). It may
descend from the clouds in the form of rain, snow, sleet, or hail to form rivers, lakes,
ponds, and streams. Pure water is colorless, odorless, and tasteless. The chemical formula
H2O signifies that it is made up of two parts hydrogen and one part oxygen. To some
degree, water can dissolve every substance on the earth and in the atmosphere. Because
of this, water will contain impurities, which are the source of potential trouble in
industrial water systems.

In many ways, water is a miracle liquid. It is essential for all living things (on this
planet at least), and it is often referred to as a universal solvent because many
substances dissolve in it. These unique properties of water result from the ways in
which individual H2O molecules interact with each other. Water covers 71% of Earth's
surface. The United Nations Environment Programme estimates there are 330 million
m3 of it available on Earth, and it exists in many forms. It appears mostly in the oceans
(saltwater) and polar ice caps, but it is also present as clouds, rain water, rivers,
freshwater aquifers, lakes, and sea ice. Water in these bodies perpetually moves
through a cycle of evaporation, precipitation, and runoff to the sea. Clean water is
essential to human life. In many parts of the world, it is in short supply. Significant
quantities are believed to exist on the moons Europa and Enceladus.

Chemical and physical properties of water

Water is the chemical substance with the chemical formula H2O; meaning that one
molecule of water is composed of two hydrogen atoms and one oxygen atom. Water is a
colorless, tasteless, and odorless liquid at ambient temperature and pressure. It is a very

4
important solvent, dissolving many other chemical substances, such as salts, sugars,
acids, alkalis, some gases and many organic molecules, to name a few of them.

Water is unusual in that it is a liquid under normal conditions, when relationships

between other analogous hydrides of oxygen's column in the periodic table suggest it
should be a gas, as is hydrogen sulphide. If the periodic table is examined, it will be noted
that the elements surrounding oxygen are nitrogen, fluorine, phosphorus, sulphur and
chlorine. All of these elements combine with hydrogen to produce gases at normal
temperature and pressure. The reason that oxygen forms a liquid is that it is more
electronegative; oxygen pulls on electrons much more strongly than hydrogen, leaving a
net positive charge on the hydrogen side of the molecule, and a net negative charge on
the oxygen side. The electrical attraction 'pulls' separate molecules closer together and
raises the boiling point. This attraction is known as hydrogen bonding.

Water has been referred to as the universal solvent, and the only real pure substance
found naturally on Earth in all three states of matter. It is in dynamic equilibrium between
the liquid and vapor states at standard temperature and pressure. Ionically, water can be
described as as a hydrogen ion (H+) that is bonded to a hydroxide ion (OH-).

2. Water Sources

a. The two principal sources of water supplies are groundwater (well) and surface
water (lakes and rivers). Groundwater comes from sources such as wells, springs,
and underground streams. Surface water comes primarily from rivers, lakes, and
streams.
b. Groundwater is usually free of suspended matter but contains high concentrations
of dissolved minerals. As rain and run-off water pass through the soil, suspended
particles are filtered out and minerals in the ground dissolve into the water.
Groundwater is relatively free of dissolved oxygen (O2) and high in carbon
dioxide (CO2). The high content of CO2 in groundwater is the result of decay of
organic matter in the surface soil.
c. Surface water, on the other hand, is known to be higher in suspended matter than
groundwater. The dissolved oxygen content in surface water is high due to
turbulence and its contact to the air. Surface water is the collection of rain and

5
 runoff that forms lakes, streams, and rivers. As the water flows across the land
surface, minerals are dissolved. The force of the flowing water will also carry
along fine particles and organic matter in suspension. Geographical location
usually determine the types and quantities of dissolved minerals in the water
supply.
d. Seawater

Figure 1. Hydrologic Cycle.

Water Cycle:

Evaporation:
As water is heated by the sun, it's surface molecules become sufficiently energized to
break free of the attractive force binding them together, and then evaporate and rise as
invisible vapour in the atmosphere.

Transpiration:
Water vapour is also emitted from plant leaves by a process called transpiration. Every
day an actively growing plant transpires 5 to 10 times as much water as it can hold at
once.

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Condensation:
As water vapour rises, it cools and eventually condenses,usually on tiny particles of dust
in the air. When it condenses it becomes a liquid again or turns directly into a solid (ice,
hail or snow). These water particles then collect and form clouds.

Precipitation:
Precipitation in the form of rain, snow and hail comes from clouds. Clouds move around
the world, propelled by air currents. For instance, when they rise over mountain ranges,
they cool, becoming so saturated with water that water begins to fall as rain, snow or hail,
depending on the temperature of the surrounding air.

Runoff:
Excessive rain or snowmelt can produce overland flow to creeks and ditches. Runoff is
visible flow of water in rivers, creeks and lakes as the water stored in the basin drains out.

Percolation:
Some of the precipitation and snow melt moves downwards, percolates or infiltrates
through cracks, joints and pores in soil and rocks until it reaches the water table where it
becomes groundwater.

Groundwater:
Subterranean water is held in cracks and pore spaces. Depending on the geology, the
groundwater can flow to support streams. It can also be tapped by wells. Some
groundwater is very old and may have been there for thousands of years.

Properties of groundwater

The geological nature of the soil determines the chemical composition of the
groundwater. Water is constantly in contact with the ground in which it stagnates or
circulates, so equilibrium develops between the composition of the soil and that of the
water: i.e. water that circulates in a sandy or granitic substratum is acidic and has a few
minerals. Water that circulates in limestone contains bicarbonates alkalinity. The
following table compares the characteristics of surface water and groundwater based on
the major analysis parameters.

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Some of the most typical characteristics of groundwater are weak turbidity, a constant
temperature and chemical composition and almost overall absence of oxygen. Circulating
groundwater can have extreme variation in the composition with the appearance of
pollutants and various contaminants. Furthermore, groundwater is often very pure
microbiologically.

Groundwater is in constant motion, although the rate at which it moves is generally

slower than it would move in a stream because it must pass through the intricate
passageways between free spaces in the rock. First groundwater moves downward due to
the pull of gravity. But it can also move upwards because it will flow from higher-
pressure areas to lower pressure areas.

The rate of groundwater flow is controlled by two properties of the rock: porosity and
permeability. Porosity is the percentage of the volume of the rock that is open space (pore
space). This determines the amount of water that a rock can contain. In sediments or
sedimentary rocks the porosity depends on grain size, grain shapes, the degree of sorting,
and the degree of cementation. Permeability is a measure of the degree to which the pore
spaces are interconnected, and the size of the interconnections. Low porosity usually
results in low permeability, but high porosity does not necessarily imply high

8
permeability. It is possible to have a highly porous rock with little or no interconnections
between pores. A good example of a rock with high porosity and low permeability is a
vesicular volcanic rock, where the bubbles that once contained gas give the rock a high
porosity, but since these holes are not connected to one another the rock has low
permeability.

Properties of Seawater

Salinity
Various salt constituents in 1m3 of seawater having (t, S) = (20, 35). Taken from
Neumann and Pierson, Principles of Physical Oceanography, 1966, Prentice-Hall.

Now, based on the equation of state (EOS-1980) for seawater, the density of seawater
3
having this (t,S) value should be 1024.8 kg/m . So the mass of salts divided by the mass
of the water is:
(35.956/1024.8) = 35.1, which should be 35.

Salinity used to be based on chlorinity (Cl) since it was found that many of the above salt
constituents had a constant ratio with Cl in seawater under a variety of values and
locations (based on the Challenger Expedition samples). After later finding out that this
was not universally true, a different, more accurate salinity scale was developed based on
the electrical conductance of seawater compared to a ―standard‖ solution of KCl at 15o C.
Salinity used to be reported as parts per thousand or grams per kg of seawater, but now
has no formal units under the new salinity scale.

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Temperature
Temperature is measured in an absolute scale (degrees Kelvin,K) from absolute zero, a
temperature of zero molecular motion. Other benchmarks have been picked somewhat
arbitrarily based on properties of various substances, which are readily available and have
some rather stable properties. The temperature scale used on oceanography is the Celcius
scale (degrees C) such that:
T = t + 273.15, where T is inoK and t is in o C.
Temperature scales have changed over the years (in 1948, 1968 and most recently in
1990) as various benchmark values have been changed. For the oceanographic
temperature range (-2 to 35oC), temperature is now based on electrical resistance
measurements of a pure platinum wire relative to the resistance at the triple point of
water, which is a temperature value at which solid, liquid and vapor phases are in
equilibrium at a standard atmosphere.
Some representative profiles of temperature and salinity vs. depth are given below. The
region of rapid temperature change with depth due to seasonal heating is called the
―seasonal thermocline‖. It lies above a permanent thermocline, which divides the upper
and deep parts of the ocean.

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 Temperature distribution in Ocean During the four seasons.

Pressure
Pressure is force/unit area acting on a surface. It has several units, with conventional units
different in meteorology and oceanography. The Standard International (SI) units are
based on the MKS (meter-kilogram-second) and is the Pascal.
Pressure at the bottom of the atmosphere is 1.013 bar or 1013 mbar. Meteorologists
commonly use millibars as pressure units and oceanographers use decibars because the
additional pressure under a layer of water that is 1 meter high is approximately 1 dbar.

11
We generally use gauge pressure, or the departure of pressure from atmospheric values at
sea level. Just to make things more complicated, pressure is often quoted in terms of cm
or inches of mercury in a manometer, where a standard atmosphere (1013 mbar) will
raise a column of mercury a height 76 cm. Pressure measuring instruments can generally
be calibrated by adding fixed masses that depress a fluid column a known amount, given
that one can independently measure or determine the local acceleration of gravity.

Density

Various different ways are used to describe the density of seawater and its relation to the
basic field variables of temperature, salinity and pressure. Usually density is
plotted/examined at fixed pressures. The internationally used equation of state of
seawater was suggested by Millero and accepted in 1980. The density of air at
atmospheric pressure is approximately 1.2 kg/m3, nearly a thousand times less than
seawater.

Rain water and properties

Rain plays a role in the hydrologic cycle in which moisture from the oceans evaporates,
condenses into clouds, precipitates back to earth, and eventually returns to the ocean via
streams and rivers to repeat the cycle again. There is also a small amount of water vapor
that respires from plants and evaporates to join other water molecules in condensing into
clouds.

The amount of rainfall is measured using a rain gauge. It is expressed as the depth of
water that collects on a flat surface, and is routinely measured with an accurary up to
0.1 mm or 0.01 in. It is sometimes expressed in liters per square meter (1 liter/m² = 1
mm).

Falling raindrops are often depicted in cartoons or anime as "teardrop-shaped" — round

at the bottom and narrowing towards the top — but this is incorrect. Only drops of water
dripping from some sources are tear-shaped at the moment of formation. Small raindrops
are nearly spherical. Larger ones become increasingly flattened on the bottom, like
hamburger buns; very large ones are shaped like parachutes. On average, raindrops are 1
to 2 mm in diameter. The biggest raindrops on Earth were recorded over Brazil and the
Marshall Islands in 2004 — some of them were as large as 10 mm. The large size is
explained by condensation on large smoke particles or by collisions between drops in
small regions with particularly high content of liquid water.

Generally, rain has a pH slightly under 6. This is because atmospheric carbon dioxide
dissolves in the droplet to form minute quantities of carbonic acid, which then partially
dissociates, lowering the pH. In some desert areas, airborne dust contains enough calcium
carbonate to counter the natural acidity of precipitation, and rainfall can be neutral or
even alkaline. Rain below pH 5.6 is considered acid rain.

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 Chapter 3
Water Properties: Physical, Chemical

1. Chemistry of water
2. Color
3. PH
4. Turbidity
5. Acidity
6. Alkanlity
7. Hardness
8. Chloride and chlorine

In its pure state, water is one of the most aggressive solvents known. Called the
―universal solvent,‖ water, to a certain degree, will dissolve virtually everything to which
it is exposed. Pure water has a very high energy state and, like everything else in nature,
seems to achieve energy equilibrium with its surroundings. It will dissolve the quantity of
material available until the solution reaches saturation, the point at which no higher level
of solids can be dissolved. Contaminants found in water include atmospheric gases,
minerals, organic materials (some naturallyoccurring, others man-made) plus any
materials used to transport or store water.

Water evaporates from surface supplies and transpires from vegetation directly
into the atmosphere. The evaporated water then condenses in the cooler air on nuclei such
as dust particles and eventually returns to the earth’s surface as rain, snow, sleet, or other
precipitation. It dissolves gases such as carbon dioxide, oxygen, and natural and
industrial emissions such as nitric and sulfuric oxides, as well as carbon monoxide.
Typical rain water has a pH of 5 to 6.

The result of contact with higher levels of these dissolved gases is usually a
mildly acidic condition – what is today called ―acid‖ rain – that may have a pH as low as
4.0. As the precipitation nears the ground, it picks up many additional contaminants -
airborne particulates, spores, bacteria, and emissions from countless other sources.
Most precipitation falls into the ocean, and some evaporates before reaching the earth’s
surface. The precipitation that reaches land replenishes groundwater aquifers and
surface water supplies. The water that percolates down through the porous upper crust of
the earth is substantially ―filtered‖ by that process. Most of the particulate matter is
removed, much of the organic contamination is consumed by bacterial activity in the soil,
and a relatively clean, mildly acidic solution results. This acidic condition allows the
water to dissolve many minerals, especially limestone, which contributes calcium. Other
geologic formations contribute minerals, such as magnesium, iron, sulfates and chlorides.
The addition of these minerals usually raises groundwater pH to a range of 7 to 8.5.

This mineral-bearing water is stored in natural underground formations called

aquifers. These are the source of the well water used by homes, industries and

17
municipalities. Surface waters such as rivers, lakes and reservoirs typically contain less
mineral contamination because that water did not pass through the earth’s soils. Surface
waters will, however, hold higher levels of organics and undissolved particles because the
water has contacted vegetation and caused runoff to pick up surface debris.

Turbidity consists of suspended material in water, causing a cloudy appearance. This

cloudy appearance is caused by the scattering and absorption of light by these particles.
The suspended matter may be inorganic or organic. Generally the small size of the
particles prevents rapid settling of the material and the water must be treated to reduce its
turbidity. Correlation of turbidity with the concentration of particles present is difficult
since the light-scattering properties vary among materials and are not necessarily
proportional to their concentration.

Turbidity can be measured by different optical systems. Such measurements simply show
the relative resistance to light transmittance, not an absolute level of contamination. A
candle turbidimeter is a very basic visual method used to measure highly turbid water.
Its results are expressed in Jackson Turbidity Units (JTU). A nephelometer is more
useful in lowturbidity water, with results expressed in Nephelometric Turbidity Units
(NTU) or Formazin Turbidity Units (FTU). JTU and NTU are not equivalent. Suspended
matter can also be expressed quantitatively in parts per million (ppm) by weight or
milligrams per liter (mg/L). This is accomplished by gravimetric analysis, typically
filtering the sample through a 0.45-micron membrane disc, then drying and weighing
the residue.

The Silt Density Index (SDI) provides a relative value of suspended matter. The
measured values reflect the rate at which a 0.45-micron filter will plug with particulate
material in the source water. The SDI test is commonly used to correlate the level of
suspended solids in feedwater that tends to foul reverse osmosis systems.

Taste sense is moderately accurate and able to detect concentrations from a few tenths to
several hundred ppm. However, taste often cannot identify particular contaminants. A
bad taste may be an indication of harmful contamination in drinking water, but certainly
cannot be relied on to detect all harmful contaminants.

Color is contributed primarily by organic material, although some metal ions may also
tint water. While not typically a health concern, color does indicate a certain level of
impurities, and can be an aesthetic concern. ―True color‖ refers to the color of a sample
with its turbidity removed. Turbidity contributes to ―apparent‖ color. Color can be
measured by visual comparison of samples with calibrated glass ampules or known
concentrations of colored solutions. Color can also be measured using a
spectrophotometer.

Odor The human nose is the most sensitive odor-detecting device available. It can detect
odors in low concentrations down to parts per billion (ppb). Smell is useful because it
provides an early indication of contamination which could be hazardous or at least reduce
the aesthetic quality of the water.

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Further Analysis should focus on identification and quantification of specific
contaminants responsible for the water quality. Such contaminants can be divided into
two groups: dissolved contaminants and particulate matter. Dissolved contaminants are
mostly ionic atoms or a group of atoms carrying an electric charge. They are usually
associated with water quality and health concerns. Particulate matter – typically silt, sand,
virus, bacteria or color-causing particles – is not dissolved in water. Particulate matter is
usually responsible for aesthetic characteristics such as color, or parameters such as
turbidity, which affects water processes.

General Quantitative Identification

Following are the major quantitative analyses which define water quality.

pH

The relative acidic or basic level of a solution is measured by pH. The pH is a measure of
hydrogen ion concentration in water, specifically the negative logarithm (log) of the
hydrogen ion concentration. The measurement of pH lies on a scale of 0 to 14, with a
pH of 7.0 being neutral (i.e., neither acidic nor basic), and bearing equal numbers of
hydroxyl (OH-) and hydrogen (H+) ions. A pH of less than 7.0 is acidic; a pH of more
than 7.0 is basic. Since pH is expressed in log form, a pH of 6.0 is 10 times more acidic
than a pH of 7.0, and a pH of 5.0 is 100 times more acidic than a pH of 7.0. The pH has
an effect on many phases of water treatment such as coagulation, chlorination and water
softening. It also affects the scaling-potential of water sources. The pH level can be
determined by various means such as color indicators, pH paper or pH meters. A pH
meter is the most common and accurate means used to measure pH.

Total Solids

Total Solids (TS) is the sum of Total Dissolved Solids (TDS) and Total Suspended Solids
(TSS). In water analysis these quantities are determined gravimetrically by drying a
sample and weighing the residue. In the field, TDS is commonly measured by a
conductivity meter which is correlative to a specific salt solution; however, this
measurement is only an approximation most often based on a multiplication factor of
0.66 of the electrical conductivity.

Conductivity/Resistivity

Ions conduct electricity. Because pure water contains few ions, it has a high resistance to
electrical current. The measurement of water’s electrical conductivity, or resistivity, can
provide an assessment of total ionic concentration. Conductivity is described in
microSiemens/cm (μS) and is measured by a conductivity meter and cell. Resistivity is
described in megohm-cm, is the inverse of conductivity and is measured by a resistivity
meter and cell.

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 Chapter 4
Water Impurities and Toxic Materials
1. Impurities in water
2. Suspended solid
3. Gases
4. Total dissolved solids
5. Organic compound
6. Toxic compound

Impurities Found in Water

a. Suspended Solids

(1) Turbidity is finely divided suspended particles that give the water an unsightly
appearance. It can be caused by clay, silt, organic matter (dead plants and
animals), inorganic matter, or microscopic organisms. It can cause sludge to
form inside an industrial system which can lead to reduction of heat transfer and
water flow restriction. Turbidity can also interfere with the proper operation of
water treatment equipment. You can remove turbidity from water by
sedimentation, coagulation, or filtration.

(2) Another form of suspended solids found in some systems are Microbiological
organisms. They are divided into three separate categories:
(a) Deposit Producing Organisms – Slime forming microbes that deposit
in heat exchangers and cause fouling.
(b) Corrosion Causing Organisms – Microbes that produce corrosive
waste products that readily attack metals in cooling systems.
(c) Decay Causing Organisms – Organisms that convert the cellulose in
wood structures to food and feed on the lignin/tannis, thus, causing the
structure to weaken (also known as delignification). Cooling water
systems are mostly affected by the problems associated with the
presence of microbiological organisms.
b. Dissolved Gases

(1) Most dissolved gases show up in the form of oxygen and carbon
dioxide. These gases are absorbed in water as the rain falls, the stream
flows, and the water seeps through the earth’s surface. Water also
absorbs gases when it flows over decayed plants and animals.
(2) The extent of damages in a closed water system depends on the
amount of makeup water added to the system. With the addition of
makeup water come dissolved gases that continue the corrosion
process on unprotected metal.
(3) Dissolved gases in the makeup water for steam heating systems is
more damaging than for chilled and hot water systems. When makeup

20
 water enters a steam boiler, the gases vaporize and travel with the
steam. As the steam condenses, oxygen escapes and attacks the upper
surface of the condensate lines. Carbon dioxide combines with
condensed steam to form carbonic acid which lowers the pH and
corrodes the bottom section of the pipe.
(4) The majority of dissolved gases can be removed by mechanical means
(deaeration and aeration). Chemicals are added to a system for
complete removal or to mitigate the effects of the gases.
c. Dissolved Minerals

(1) Dissolved minerals are in water as a result of the water contact with
other substances (i.e., soil, rocks). The amount of minerals dissolved in
the water depends on the length of time the water is in contact with the
minerals. These minerals show up in the form of deposits on the
surface of the industrial system when the water is not treated. As stated
earlier, groundwater is more apt to have high mineral content than
surface water, so this discussion will focus primarily on the effects of
untreated groundwater. Minerals such as calcium, magnesium, and
silica are of major concern when considering makeup water for an
industrial system. These minerals become more insoluble as the
temperature of the water increases, thus leading to deposition in the
system.
(2) Minerals combined with other ions:

(a) Calcium – When combined with bicarbonate, forms calcium

bicarbonate. When heat is applied, carbon dioxide is released and
calcium carbonate precipitates to form scale. When combined with
sulfate, calcium sulfate is formed to produce a hard scale.
(b) Magnesium – When combined with bicarbonate, forms
magnesium bicarbonate. When heat is applied, carbon dioxide is
released and magnesium carbonate precipitates to form scale.
(c) Silica – Scale depositing.
(d) Iron – Contributes to resin fouling.

3. Specific Impurities

Sulfate Sulfate (SO42-) is very common. When present at lower levels, sulfate salts create
problems only for critical manufacturing processes. At higher levels, they are associated
with a bitter taste and laxative effect. Many divalent metal-sulfate salts are virtually
insoluble and precipitate at low concentrations.

Chloride
Chloride (Cl-) salts are common water contaminants. The critical level of chloride
depends on the intended use of the water. At high levels, chloride causes a salty or
brackish taste and can interfere with certain water treatment methods. Chlorides also
corrode the metals of water supply systems, including some stainless steels.

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Nitrate - Nitrite
Although nitrate (NO3-) and nitrite (NO2-) salts may occur naturally, their presence in a
water supply usually indicates man-made pollution. The most common sources of
nitrate/nitrite contamination are animal wastes, primary or secondary sewage, industrial
chemicals and fertilizers. Even low nitrate levels are toxic to humans, especially infants,
and contribute to the loss of young livestock on farms with nitrate-contaminated water
supplies.

Chlorine, because of its bactericidal qualities, is important in the treatment of most

municipal water supplies. It is usually monitored as free chlorine (Cl2) in concentrations
of 0.1 to 2.0 ppm. In solution, chlorine gas dissolves and reacts with water to form the
hypochlorite anion (ClO-) and hypochlorous acid (HClO). The relative concentration of
each ion is dependent upon pH. At a neutral pH of 7, essentially all chlorine exists as the
hypochlorite anion which is the stronger oxidizing form. Below a pH of 7, hypochlorous
acid is dominant, and has better disinfectant properties than the anion counterpart.
Although chlorine’s microbial action is generally required, chlorine and the compounds it
forms may cause a disagreeable taste and odor. Chlorine also forms small amounts of
trihalogenated methane compounds (THM’s), which are a recognized health hazard
concern as carcinogenic materials. The organic materials with which the chlorine reacts
are known as THM precursors.

Chloramines
In some cases, chlorine is also present as chloramine (i.e., monochloramine, NH2Cl) as a
result of free chlorine reacting with ammonia compounds. The ammonia is added to a
water supply to ―stabilize‖ the free chlorine. Chloramines are not as effective a microbial
deterrent as chlorine, but provide longer-lasting residuals.

Chlorine Dioxide
This material is often produced on-site primarily by large municipalities via the reaction
between chlorine or sodium hypochlorite and sodium chlorite. A more costly source of
chlorine dioxide is available as a stabilized sodium chlorite solution. Chlorine dioxide has
been used for taste and odor control and as an efficient biocide. Chlorine dioxide can
maintain a residual for extended periods of time in a distribution system and does not
form trihalomethanes (THM’s) or chloramines if the stabilized sodium chlorite form is
used. The possible toxicity of the chlorate and chlorite ions (reaction byproducts) may be
a concern for potable water applications.

Silica
Every water supply contains at least some silica (SiO2). Silica occurs naturally at levels
ranging from a few ppm to more than 200 ppm. It is one of the most prevalent elements
in the world. Among the problems created by silica are scaling or ―glassing‖ in boilers,
stills, and cooling water systems, or deposits on turbine blades. Silica scale is difficult to
remove. Silica chemistry is complex. An unusual characteristic of silica is its solubility.
Unlike many scaling salts, silica is more soluble at higher pH ranges. Silica is usually
encountered in two forms: ionic and colloidal (reactive and nonreactive based on the
typical analytical techniques). Silica can be present in natural waters in a combination of

22
three forms: reactive (ionic), nonreactive (colloidal) and particulate. Ionic Silica
(reactive) Ionic or reactive silica exists in an SiO2 complex. It is not a strongly-charged
ion and therefore is not easily removed by ion exchange. However, when concentrated to
levels above 100 ppm, ionic silica may polymerize to form a colloid. – Colloidal Silica
(nonreactive) At concentrations over 100 ppm, silica may form colloids of 20,000
molecular weight and larger, still too small to be effectively removed by a particle filter.
Colloidal silica is easily removed with ultrafiltration, or can be reduced by chemical
treatment (lime softening). Colloidal silica can lower the efficiency of filtration systems
(such as reverse osmosis). Any silica can affect yields in semiconductor
manufacturing and is a major concern in high-pressure boiler systems.

Aluminum Aluminum (Al3+) may be present as a result of the addition of aluminum

sulfate [Al2(SO4)3] known as alum, a commonly used flocculant. Aluminum can cause
scaling in cooling and boiler systems, is a problem for dialysis patients, and may have
some effects on general human health. Aluminum is least soluble at the neutral pH
common to many natural water sources.

Sodium
The sodium ion (Na+) is introduced naturally due to the dissolution of salts such as
sodium chloride (NaCl), sodium carbonate (Na2CO3), sodium nitrate (NaNO3) and
sodium sulfate (Na2SO4). It is also added during water softening or discharge from
industrial brine processes. By itself the sodium ion is rarely a problem, but when its salts
are the source of chlorides (Cl-) or hydroxides (OH-), it can cause corrosion of boilers,
and at high concentrations (such as seawater) it will corrode stainless steels.

Potassium
Potassium is an essential element most often found with chloride (KCl) and has similar
effects but is less common than sodium chloride. It is used in some industrial processes.
The presence of KCl is |typically a problem when only ultrapure water quality is
required.

Phosphate Most phosphates (PO43-) commonly enter surface water supplies through
runoff of fertilizers and detergents in which ―phosphates‖ are common ingredients.
Phosphates also enter the hydrologic cycle
through the breakdown of organic debris. Phosphates are used in many antiscalant
formulations. At the levels found in most water supplies phosphates do not cause a
problem unless ultrapure water is required. Phosphates may foster algae blooms in
surface waters or open storage tanks.

Dissolved Gases

Hydrogen Sulfide The infamous ―rotten egg‖ odor, hydrogen sulfide (H2S) can
contribute to corrosion. It is found primarily in well water supplies or other anaerobic
sources. H2S can be readily oxidized by chlorine or ozone to eliminate sulfur.

23
Radon is a water-soluble gas produced by the decay of radium and its isotopes. It is the
heaviest gas known and occurs naturally in groundwater from contact with granite
formations, phosphate and uranium deposits. Prolonged exposure may cause human
health problems including cancer.

Heavy Metals

Heavy metals such as lead, arsenic, cadmium, selenium and chromium – when present
above certain levels – can have harmful effects on human health. In addition, minute
concentrations may interfere with the manufacture and effectiveness of pharmaceutical
products, as well as laboratory and industrial processes of a sensitive nature.

Dissolved Organic Compounds

Dissolved organic materials occur in water both as the product of material decomposition
and as pollution from synthetic compounds such as pesticides.

Naturally-Occurring Tannins, humic acid and fulvic acids are common natural
contaminants. They cause color in the water and detract from the aesthetics of water but,
unless they react with certain halogens, they
have no known health consequences in normal concentrations. In the presence of free
halogen compounds (principally chlorine or bromine), they form chlorinated
hydrocarbons and trihalomethanes (THM’s), which are suspected carcinogens.
Maximum allowable limits of THM’s in municipal systems have been imposed by the
United States Environmental Protection Agency (EPA).

Synthetic Organic Compounds (SOC’s)

A wide variety of synthetic compounds which are potential health hazards are present in
water systems due to the use of industrial and agricultural chemicals. These compounds
are not readily biodegradable
and leach from soil or are carried by runoff into water sources. Many are suspected
carcinogens and are regulated by the EPA.

Volatile Organic Compounds (VOC)

Due to relatively low molecular weight, many synthetic organic compounds such as
carbon tetrachloride, chloroform and methylene chloride will easily volatilize. Volatility
is the tendency of a compound to pass into the vapor state. Most are introduced into the
water supply in their liquid phase. If ingested they may be absorbed into the bloodstream.
Many are suspected carcinogens.

Radioactive Constituents Water in itself is not radioactive but may contain

radionuclides. They are introduced either as naturally-occurring isotopes (very rare) or
refined nuclear products from industrial or medical processes, radioactive fallout or
nuclear power plants.

24
 Chapter 5
Impurities Impacts on Thermal Power and Technical
Solution

1. Effect of impurities in the thermal power stations such as:

2. Corrosion
3. Pollution
4. Physical corrosion
5. Deposit in tube boiler

4. Purpose for Water Treatment

a. Water treatment programs are designed to protect the equipment in the system.
The metallurgy of a system is critical when planning or designing a water
treatment program, making sure that the end result is adequate protection of the
metals.
b. A good water treatment program will help conserve energy by minimizing energy
used to raise or lower water temperature. It will also reduce water consumption
and lessen the chemical usage.
c. Equipment reliability also depends on the quality of the industrial water treatment
program. Corrosion and scale buildup can cause premature equipment failure
during peak operation. Scale deposition on a boiler tube can lead to tube rupture
and ultimately boiler explosion.
d. Reduced labor cost is another end product of an effective water treatment
program. It takes less man-hours to perform scheduled maintenance on systems
that are free of scale deposits, microbiological growth, and corrosion by-products.

Boiler

A boiler is a closed vessel in which water or other fluid is heated under pressure. The hot
fluid is then circulated out of the boiler for use in various process or heating applications.

25
Diagram of a fire-tube boiler

Construction of boilers is mainly limited to copper, steel and cast iron. In live steam toys,
brass is often used.

Sources of heat for the boiler can be combustion of fuels such as wood, coal, oil, or
natural gas. Electric boilers use resistance or immersion type heating elements. Nuclear
fission is also used as a heat source for generating steam. Heat recovery steam generators,
use the heat rejected from other processes such as gas turbines.

Boilers can also be classified into:-

 Fire-tube boilers. Here the heat source is inside the tubes and the water to be
heated is outside.
 Water-tube boilers. Here the heat source is outside the tubes and the water to be
heated is inside.
 A primitive, inefficient type where there are no tubes and the fire heats one side of
the water container.

The goal is to make the heat flow as completely as possible from the heat source to the
water. For example, steam locomotives have fire-tube boilers, where the fire is inside the

26
tube and the water on the outside. These usually take the form of a set of straight tubes
passing through the boiler through which hot combustion gases flow.

Diagram of a water-tube boiler.

In water-tube boilers the water flows through a large number of narrow tubes around the
fire. The tubes frequently have a large number of bends and sometimes fins to maximize
the surface area. This type of boiler is generally preferred in high pressure applications
since the high pressure water/steam is contained within narrow pipes which can contain
the pressure with a thinner wall.

In a cast iron sectional boiler, sometimes called a "pork chop boiler" the water is
contained inside cast iron sections. These sections are mechanically assembled on site to
create the finished boiler.

27
 Diagram of a Cornish Boiler

There are other types of boilers, largely of historical interest. For example, the Cornish
boiler developed around 1812 by Richard Trevithick for generating steam for steam
engines. This was both stronger and more efficient than the simple boilers which
preceded it. It was a cylindrical water tank around 27 feet long and 7 feet in diameter, and
had a coal furnace placed in a single cylindrical tube about three feet wide which passed
centrally along the long axis of the tank. The fire was tended from one end and the hot
gases from it travelled along the tube and out of the other end, to be circulated back along
flues running along the outside of the boiler before being expelled via the chimney. This
was later improved upon in the Lancashire boiler which had a pair of furnaces in separate
tubes side-by-side. This was an important improvement since each furnace could be
stoked at different times, allowing one to be cleaned while the other was operating. These
designs are really primitive fire tube boilers, and led on to the Scotch boiler which
remains a popular fire tube design.

28
A superheated boiler on a steam locomotive.

Most boilers heat water until it boils, and then the steam is used at saturation temperature
(i.e., saturated steam). Superheated steam boilers boil the water and then further heat the
steam in a superheater. This provides steam at much higher temperature, and can
decrease the overall thermal efficiency of the steam plant due to the fact that the higher
steam temperature requires a higher flue gas exhaust temperature. However, there are
advantages to superheated steam. For example, useful heat can be extracted from the
steam without causing condensation, which could damage piping and turbine blades.

Superheated steam presents unique safety concerns, however, if there is a leak in the
steam piping, steam at such high pressure/temperature can cause serious, instantaneous
harm to anyone entering its flow. Since the escaping steam will initially be completely
superheated vapor, it is not easy to see the leak, although the intense heat and sound from
such a leak clearly indicates its presence.

29
Steam generation power plant.

Supercritical steam generators are frequently used for the production of electric power.
They operate at "supercritical pressure". In contrast to a "subcritical boiler", a
supercritical steam generator operates at such a high pressure (over 3200 PSI, 220 Bar)
that actual boiling ceases to occur, the boiler has no water - steam separation. There is no
generation of steam bubbles within the water, because the pressure is above the "critical
pressure" at which steam bubbles can form. It passes below the critical point as it does
work in the high pressure turbine and enters the generator's condenser. This is more
efficient resulting in slightly less fuel use and therefore less greenhouse gas production.
The term "boiler" should not be used for a supercritical pressure steam generator, as no
"boiling" actually occurrs in this device.

IMPURITIES FOUND IN A STEAM SYSTEM

The concentration of impurities in water is measured and expressed as parts per million
(ppm). Parts per million is a measure of proportion by weight such as one pound in a
million pounds. A majority of the scale forming impurities and dissolved gases can be
removed from boiler feedwater with pretreatment. In the event pretreatment is not
available, chemical treatment is required to control these impurities that may be in the
boiler water. Oxygen and carbon dioxide can be detrimental to a steam system. These

30
gases are most destructive in the condensate lines causing localized pitting and
channeling of the pipes. Calcium, magnesium, and silica are minerals that can precipitate
out of the water to form scale on the heating surfaces. Dissolved iron can precipitate and
form sludge deposits in the boiler.

BOILER WATER PRETREATMENT

1. Dissolved Gas Removal

a. Aeration is a process used to remove carbon dioxide from the boiler

feedwater (see Figure 2). The water is distributed at the top of the
tank and free-falls to a collection basin at the bottom. The forced-
draft degasifier blows an air stream countercurrent to the water flow.
The undesirable gas escapes through the vent on the top of the
aerator. A disadvantage to this process is that the water is saturated
with oxygen after aeration.
b. Deaeration is a mechanical process used to remove noncondensible
gases (oxygen and carbon dioxide) in the boiler feedwater (see
Figure 3). The deaeration process involves heating the makeup water
and the condensate return in a pressurized vessel to drive off the
noncondensible gases. Trays or spray heads are used to break the
water into small droplets. Steam is used to heat these droplets to the
boiling point. As the water temperature increases, the gases are
liberated and released to the atmosphere through the deaerator vent.
Deaeration is especially necessary if there is an aerator in the system
that saturates the water with oxygen.

31
Figure 2. Degasifier Blows Air Through the Packing Countercurrent to the Downward
Flow of Water to Remove gases with heating ( can be used for CO2 removal )

32
Figure 3. Spray Type Deaerator.

2. Dissolved Minerals Removal

a.Precipitation Softening (Lime Soda)

(1) Hot lime softening (figure 4) is accomplished in a pressure

vessel at temperatures between 220oF to 240oF. The source of
heat is live or exhaust steam. Hydrated lime is added to the
water and reacts with calcium and magnesium to form calcium
carbonate sludge. The insolubility of magnesium hydroxide
increases at this high temperature resulting in a greater
reduction of hardness minerals. Hot lime units operating at
high temperatures will drive off any CO2 and O2, thus reducing
the additional chemical needed to control CO2 and O2. This
process uses anthracite (coal) filters to remove any floc that
carryover with the processed water.

33
Figure 4. Hot Lime Softener. Steam mixes with raw water and chemical in the upper
zone. Water flows to the bottom, rises through the sludge blanket, and
discharges to the anthracite filters.

(2) Cold lime softening involves precipitation of the hardness

impurities and discharge it in the form of a sludge. Hydrated
lime is added to the water and reacts with calcium and
magnesium to form calcium carbonate sludge. The scale
depositing minerals are not completely removed with the
hydrated lime alone. Additional reduction of these minerals is
attained by supplementing the lime with soda ash and sodium
aluminate. Silica reduction is also attained because it
precipitates with magnesium hydroxide.
b. Ion Exchanger

34
 (1) Sodium zeolite softening was one of the first industrial
applications of ion exchange. The primary purpose of sodium
zeolite softening is to remove the scale forming ions of calcium
and magnesium. This ion exchanger consists of an exchange
medium (zeolite resins) that has the ability to exchange sodium
ions for hardness ions (calcium and magnesium) upon contact
(see Figure 5). In operation, the water passes through a layer of
zeolite material which releases the sodium ions and retains the
hardness ions. Over a period of time the resins become
saturated with hardness ions and the exchange process comes
to a halt. When this occurs the softener needs to be
regenerated. To regenerate the softener, a strong concentration
of sodium solution is used to wash away the hardness ions, and
restore the sodium ions on the zeolite resins. One disadvantage
of sodium zeolite softening is that hardness is removed without
alkalinity reduction. However, the advantages are a safe
regenerate (salt), cost savings, and nonhazardous discharges.

Figure 5. Typical Ion Exchange Unit Showing Service Flow Valve Nest for Resin
Regeneration (Backwashing, Injection of Regenerant, and Rinsing)

35
 (2) A hydrogen zeolite softener (figure 6) uses acid instead of salt
to regenerate the resins. The hydrogen ions are exchanged for
calcium, magnesium, and sodium ions. This type of softening
is often used for water that is high in hardness and high in
bicarbonate alkalinity. The following disadvantages are
associated with the hydrogen zeolite softener:

(a) The acid used in the regeneration process makes the

effluent water more corrosive (lower pH on effluent).
(b) The hazards that exist in handling the acid.
(c) The additional expense incurred for initial installation,
chemicals, and corrosion resistant materials. An aerator is
often installed to dispel the carbon dioxide picked up in the
softening process.

Figure 6. Hydrogen-Cation Unit Destroys Bicarbonate and Carbonate Alkalinity.

Degasifier reduces CO2. Caustic soda raises pH to desired level. (Courtesy
of Power: McGraw-Hill Publications).

(3) A split-stream dealkalizer (see Figure 7) is used in areas where

the water must be softened and dealkalized before it can be put
to use in an industrial system. Sodium zeolite/hydrogen zeolite
split-stream softening divides the flow of water through a
parallel arrangement of a sodium zeolite exchanger and a
hydrogen zeolite exchanger. Water passes through the two
units and the effluents are blended to produce water of a
desired alkalinity. Decarbonation for CO2 removal is necessary

36
 for the blended product. Regeneration is accomplished for
these units in the same manner as previously stated.

Figure 7. Split-Stream Dealkalizer Blends Water from Hydrogen and Sodium

Units. Degasifier reduces CO2. (Courtesy of Power: McGraw-Hill
Publications)

INTERNAL WATER TREATMENT

Although the boiler feedwater has completed the process of pretreatment, it may
still require additional treatment once it enters the boiler. Internal treatment is an essential
element to the overall industrial water treatment program. Internal treatment
complements external treatment by removing any impurities in the boiler that escape
during pretreatment. Internal treatment is accomplished by using a variety of chemicals
that will either eliminate the problem causing impurities or condition the impurities to
prevent damage to the system.

1. Boiler Water Treatment Guidelines

a. The two main considerations for treatment are the boiler operating pressure
and the amount of hardness in the boiler feedwater.
b. Better control of treatment program is required as the pressure in the boiler
increases. Since the boiler is much more critical at high pressures, less
hardness and dissolved solids can be tolerated.

37
c. Boiler water treatment is to prevent scale, corrosion, and carryover (priming
and foaming). The scale is primarily due to the presence of calcium and
magnesium hardness in the water. Silica is also a contributing factor.
Corrosion is due to the presence of carbon dioxide and oxygen; and carryover
is the result of high water level and high solids in the boiler water, or sudden
load swings.
d. External treatment is usually the first line of defense against scale deposits in
the boiler. If external treatment is not available, scale can be controlled within
the boiler with internal treatment. Controlling silica in the boiler is only
accomplished with blowdown. The higher the operating pressure, the greater
the need of external treatment.
e. Low pressure boiler corrosion due to oxygen is primarily controlled with
oxygen scavengers. High pressure systems may require external oxygen
removal equipment (deaerating heaters) which should remove the majority of
oxygen. An oxygen scavenger is also used to eliminate any remaining oxygen
that enters the boiler.
f. Antifoam chemicals are used to control foaming and carryover in steam
boilers.
g. The types of scale control treatment within the boiler can be described as
sludge conditioning and solubilizing type of treatment. Sludge conditioning
allows the hardness to precipitate, the sludge is then treated to prevent baking-
on to the heat transfer surface (see figure 8). The solubilizing type of
treatment maintains the hardness in a soluble condition. Sludge conditioning
becomes more favorable when the hardness in the makeup water is high.

38
Figure 8. Precipitated Minerals. Sludge is formed at the bottom of the boiler as minerals
precipitate.

2. Chemicals
a. Orthophosphate – Prevents calcium carbonate and calcium
sulfate scales. Combines with calcium to form calcium
phosphate which breaks down to form a fluid like sludge.
b. Sodium Lignosulfonate – Ensures sludge is in a fluid state with
the proper characteristic for removal by blowdown.
c. Sodium Hydroxide – Prevents magnesium phosphate scale
formation and corrosion. Controls the alkalinity and maintains
the desired pH (usually 10.5 to 11.5).
d. Sodium Sulfite – Prevents oxygen corrosion on the steam side;
oxygen scavenger.
e. Morpholine – Neutralizes the acid condition to prevent
carbonic acid corrosion in the condensate return system. Short
run.
f. Cyclohexylamine – Neutralizes the acid condition to prevent
carbonic acid corrosion in the condensate return system. Long
run.

39
 g. Octadecylamine – A protective barrier is deposited on the pipe
surface to prevent corrosion in the condensate return system.
Filming amine.
3. Blowdown
a. Sometimes it may be necessary to remove a portion of the boiler water by
blowdown to control the concentration of total solids. The objective is to maintain
a balance between treatment and blowdown so that the treatment chemical
residuals remain within the prescribed ranges and the solids are kept within a safe
operating limit.
b. Small low pressure boilers are equipped with a manual bottom blowdown, while
larger high pressure boilers may have a continuous blowdown line located in the
steam drum and a bottom blowdown on the mud drum. In either case, it is best to
use short duration blowdown and give the boiler time to fully recover before any
subsequent blowdown. See Table 1 for boiler operating ranges and limits.
4. Oxygen Removal Process
a. A major contributor to corrosion that occurs in any industrial water system is
oxygen, dissolved or free. The most common method for removing dissolved
oxygen in a high pressure system is mechanical deaeration. To assure complete
oxygen removal, sodium sulfite is added to the feedwater to maintain a residual in
the boiler water. In low pressure systems, sodium sulfite alone will suffice for
scavenging oxygen.
b. Deaeration is a mechanical process used to remove dissolved oxygen and
dissolved carbon dioxide in the boiler feedwater (see Figure 9). The deaeration
process involves heating the makeup water and the condensate return in a
pressurized vessel to drive off the noncondensible gases. Trays or spray heads
(located in the deaerator) are used to break the water into small droplets. See
Table 2 for pressure/temperature corresponding chart. Steam is used to heat these
droplets to the boiling point. As the water temperature increases, the gases are
liberated and released to the atmosphere through the vent. Deaeration is especially
necessary if pretreatment includes aeration.

Table 1. Limits on boiler water conditions for an effective treatment program

40
Figure 9. Spray Type Deaerator with Feedwater Storage Tank. (Courtesy of Puckorius &
Associates).

c. Adjusting the deaerator vent valve to eliminate the maximum amount of

condensible gases while venting the least amount of steam will optimize the
deaerator operation. The optimum vent valve opening is established by following
the procedures below:
(1) Stop feeding sodium sulfite.
(2) Wait for the boiler to use an equivalent of ten times the deaerator
storage capacity.
(3) Open the vent valve fully.
(4) Measure the oxygen content in the feedwater.
(5) Close vent valve one full turn and repeat dissolved 02 test.
(6) Continue step 5 until the 02 content increases.
(7) At this point open the vent valve ¼ turn and measure 02 content.
(8) Use the smallest vent opening which gives minimum 02 in the
feedwater.
(9) Resume sodium sulfite feed.
Once the final adjustment is made on the vent valve, a noticeable change in

41
energy consumption can be expected.

d. Sodium sulfite is used to scavenge oxygen in most boilers. However, sodium

sulfite can decompose at 500oF to produce an acidic gas; therefore, hydrazine is
usually the oxygen scavenger of choice if the water temperature exceeds 500oF.

Corrosion Control

Water in a closed recirculating system is completely confined within the system. The
most serious problems closed recirculating water systems encounter are corrosion and
corrosion product fouling. Corrosion is an electrochemical process by which metals
return to their native state. For example, mild steel reverts to iron oxide. When corrosion
occurs, the corrosion products accumulate in the system and form deposits throughout the
heat exchangers, piping, etc. The corrosion process contributes to the destruction of
costly equipment, decreases the efficiency/capacity, and causes considerable downtime
and costly production losses. Chemicals are introduced into the system to control the
corrosion process.

A number of characteristics can influence the amount and rate of corrosion that will
occur. The most important ones are:
1. Oxygen content
2. Water velocity
3. Temperature
4. Microbial growths

Type of corrosion

The three basic types of corrosion attack that occur are:

1. General attack – a term that describes the uniform distribution of corrosion over an
entire metal surface. The large amount of iron oxide produced through general attack
contributes to the severe fouling problem.

2. Localized or Pitting Attack – Occurs when isolated metal areas are corroded. Pitting is
the most serious type of corrosion because all the corrosive action is concentrated in a
very small area. Pitting attack can cause metal to perforate in a very short time, causing
pinhole leaks in the piping.

3. Galvanic Attack – Occurs when two different metals are in physical contact. In such
a case, the more active metal corrodes rapidly. Common examples in a water system are
steel and brass, aluminum and steel, zinc and steel, and zinc and brass. In each case, the
first metal of the pair will corrode. A simple example of galvanic corrosion between two
dissimilar metals is a steel pipe screwed into a bronze valve or copper tubes joined to a
ild steel tubesheet in a heat exchanger. Another example of galvanic corrosion in action
is depicted. Positive ions flow through the electrolyte from the anode to the cathode. At
the same time, electrons flow through the metallic path from the anode to the cathode.

42
Corrosion Inhibitors

One approach for preventing or minimizing corrosion in the system is to form a

protective film by using chemical inhibitors. These inhibitors are fed into the cooling
water and transported to the metal surfaces. Several chemicals have been developed that
will protect mild steel with a film so thin that it will not affect heat transfer. These
chemicals are called corrosion inhibitors. Some work at the cathodes, some at the anodes.
Corrosion inhibitors reduce or stop corrosion by interfering with the corrosion process. In
practice, they usually affect either the corrosion cell anode or cathode. The most logical
corrosion preventive approach is to disrupt the cell. A corrosion cell consists of an
electrolyte, an anode, a cathode, and a metallic path. One method involves imposing a
nonconducting barrier (the film) between the metal and the electrolyte. This barrier can
be a thin, adherent layer of scale on the metal surface, insulating it from the electrolyte,
or it can be the product of the reaction between a corrosion inhibitor and the metal.

Anodic corrosion inhibitors, called passivators, interfere with the anodic reaction. If
insufficient anodic inhibitor is present, the entire corrosion will concentrate at the
unprotected area, which can cause severe pitting. Cathodic inhibitors, on the other hand,
interfere with the cathodic reaction and reduce the corrosion rate in direct proportion to
the reduction of the unprotected cathodic area. They are often referred to as blocking
agents.

43
 Chapter 6
Water Treatment Methods

Kinds of water treatment

Filtration precipitation coagulation
Kinds of filtration
Factor’s effecting on filtration process
Distillation
Boiling point simple distillation
Faction distillation
Distillation of water as treatment method
Reverse osmosis
 Kinds of membranes uses in Ro system
 Cellulose acetate membrane
 Zealot
 Kinds of zealot natrolit nalcine
 Method of regeneration of zealot

Softeners
 Kinds of softeners
 Regeneration of softener
 Water out let properties after softener
 Problems in softener

Methods of Water Treatment

Water treatment can be defined as any procedure or method used to alter the composition
or ―behavior‖ of a water supply. Water supplies are classified as either surface water or
groundwater. This classification often determines the condition and therefore the
treatment of the water. In general the treatment usually can be classified as follows:

Screen Prefiltration
A coarse screen, usually 50 to 100 mesh (305 to 140 microns), at the intake point of a
surface water supply, removes large particulate matter to protect downstream equipment
from clogging, fouling, or physical damage.

Clarification is generally a multistep process to reduce turbidity and remove suspended

matter. First, the addition of chemical coagulants or pH-adjustment chemicals react to
form floc. The floc settles by gravity in settling tanks or is removed as the water
percolates through a gravity filter. The clarification process effectively removes particles
larger than 25 microns. Clarification steps may also be taken to reduce naturally-
occurring iron, and to remove colors, taste, and odor by adding strong oxidizing agents
such as chlorine. Where gravity filters are used, activated carbon slurries are sometimes

44
added to aid in color and odor removal. Clarification can remove a high percentage of
suspended solids at a relatively low cost per gallon. However, most clarification
processes will not remove all types of suspended or colloidal contamination and remove
few dissolved solids. The clarification process is not 100% efficient; therefore, water
treated through clarification may still contain some suspended materials.
METHODS OF WATER PURIFICATION
Lime-Soda Ash Treatment the addition of lime (CaO) and soda ash (Na2CO3) reduces
the level of calcium and magnesium and is referred to as ―lime softening.‖ The purpose
of lime softening is to precipitate calcium and magnesium hydroxides (hardness) and to
help clarify the water. The process is inexpensive but only marginally effective, usually
producing water of 50 to 120 ppm (3 to 7 gpg) hardness. A shortcoming of this process is
the high pH of the treated water, usually in the 8.5 to 10.0 range. Unless the pH is
buffered to approximately 7.5 to 8.0, the condition of the water is usually unacceptable
for general process use.

Disinfection is one of the most important steps in municipal water treatment. Usually
chlorine gas is fed into the supply after the water has been clarified and/or softened. The
chlorine kills bacteria. In order to maintain the ―kill potential‖ an excess of chlorine is fed
into the supply to maintain a residual. The chlorine level at outlying distribution points is
usually monitored at a target level of about 0.2 to 0.5 ppm. However, if the water supply
is heavily contaminated with organics, the chlorine may react to form chloramines and
certain chlorinated hydrocarbons (THM’s), many of which are considered carcinogenic.
In other cases the chlorine can dissipate and no residual level is maintained at the point-
of-use, allowing microbial growth to occur. To prevent this problem, some municipalities
add ammonia or other nitrogen compounds to create chloramines. The NH2Cl compounds
formed have a much longer half-life, allowing a measurable chlorine residual to be
maintained to extreme points-of-use. The residual chloramines may pose their own
problems.

pH Adjustment
Municipal waters may be pH-adjusted to approximately 7.5 to 8.0 to prevent corrosion of
water pipes and fixtures, particularly to prevent dissolution of lead into a potable water
supply. In the case of excessive alkalinity, the pH may be reduced by the addition of acid.
The alkalinity will convert to CO2.

Specific water treatment processes

Filtration and its Kinds

Sand Filters
Sand is one filtration medium used to remove turbidity. Sand filters can economically
process large volumes, but have two limitations. The finer sand medium is located on top
of coarser support media, which causes the filter to plug quickly and requires frequent
backwashing. Also, the coarseness of sand media allows smaller suspended solids to
pass, so secondary filters with tighter media are often required.

45
Neutralizing Filters

Neutralizing filters usually consist of a calcium carbonate, calcite medium (crushed

marble) to neutralize the acidity in low pH water.

Oxidizing Filters use a medium treated with oxides of manganese as a source of oxygen
to oxidize a number of contaminants including iron, manganese and hydrogen sulfide.
The oxidized contaminants form a precipitate that is captured by the particle filtration
capacity of the medium.

Activated carbon (AC) is similar to ion exchange resin in density and porosity. It
adsorbs many dissolved organics and eliminates chlorine or other halogens in water. It
does not remove salts. AC filters are one of the only low-cost methods available to
remove low-molecular weight (<100 MW) organics and chlorine. AC filters may become
a breeding site for bacteria and pyrogenic materials. The carbon must be sanitized or
changed periodically to avoid bacterial growth, and when all adsorption sites are used it
must be reactivated by a controlled heat process. This is not easily reactivated in the field.
The suspended solids accumulated in the bed from most water sources require frequent
backwashing of the filter unless installed after reverse osmosis or ultrafiltration.

Dual- or Multi-Media Filters Progressively finer layers of filter media trap increasingly
smaller particles. The arrangement of the media (coarse and less dense on top of finer
higher density placed deeper in the bed) enables the filter to run for longer periods of
time before backwashing is necessary. Dual-media filters remove suspended solids to as
low as 10-20 microns in size, but no dissolved solids. The top layer is a typically coarse
anthracite followed by fine sand.

Pre-Coat Filters
Pre-coat filters use a filter aid medium, usually a diatomaceous earth (DE) slurry which is
put on a coarser support medium and used to remove very small particulate matter. DE
filters can remove particles down to 5 microns and below, including some removal of
protozoa and even bacteria. The medium must be changed frequently and presents a
waste disposal problem. Pre-coat filters are most practical for limited volume applications
and are common for swimming pools, beverage plants, and certain industrial applications.

Cartridge filters were once considered only as a point-of-use water treatment method for
removal of larger particles. However, breakthroughs in filter design, such as the
controlled use of blown microfiber filters (as opposed to wrapped fabric or yarn-wound
filters), have tremendously broadened cartridge filter utilization. Cartridge filters fall into
two categories: depth filters or surface filters.

Depth Cartridge Filters

In a depth cartridge filter the water flows through the thick wall of the filter where the
particles are trapped throughout the complex openings in the medium. The filter may be

46
constructed of cotton, cellulose and synthetic yarns, chopped fibers bound by adhesives,
or ―blown‖ microfibers of polymers such as polypropylene. The most important factor in
determining the effectiveness of depth filters is the design of the porosity throughout the
thick wall. The best depth filters for many applications have lower density on the outside
and progressively higher density toward the inside wall. The effect of this ―graded
density‖ (Figure 9) is to trap coarser particles toward the outside of the wall and the finer
particles toward the inner wall. Graded-density filters have a higher dirt-holding capacity
and longer effective filter life than depth filters with constant density construction.
Disposal of spent cartridges is an environmental concern; however, some cartridges have
the advantage of being easily incinerated. Depth cartridge filters (Figure 10) are usually
disposable and cost-effective, and are available in the particle-removal size range of 0.5
to 100 microns. Generally, they are not an absolute method of filtration since a small
amount of particles within the micron range may pass into the filtrate. However, there
are an increasing number of depth filters in the marketplace that feature near-absolute
retention ratings.

Surface Filtration – Pleated Cartridge Filters

Pleated cartridge filters typically act as surface filters. Flat sheet media, either membranes
or nonwoven fabric materials, trap particles on the surface. The media are pleated to
increase usable surface area. Pleated filters are usually not cost-effective for water
filtration, where particles greater than one micron quickly plug them. However, pleated
membrane filters serve well as submicron particle or bacteria filters in the 0.1- to 1.0-
micron range and are often used to polish water after depth filters and other treatment
steps in critical applications. Pleated filters are usually disposable by incineration, since
they are constructed with polymeric materials, including the membrane. Newer cartridges
also perform in the ultrafiltration range: 0.005- to 0.15-micron.

Ultrafiltration (UF) Cartridge Filters

UF membrane cartridges perform much finer filtration than depth filters but are more
expensive and require replacement as the filter becomes ―blinded,‖ i.e., covered with an
impervious thin coating of solids. Typically the smaller the pore the more quickly this
blinding occurs. To avoid blinding of the pores, point-of-use ultrafiltration cartridges are
built in a spiral-wound configuration to allow crossflow mode operation to help keep the
surface clean by rinsing away the solids. Point-of-use ultrafiltration cartridges are used to
remove colloids, pyrogens and other macromolecular compounds from ultrapure water.

Softeners

Ion Exchange Systems An ion exchange system consists of a tank containing small
beads of synthetic resin (Figure 13). The beads are treated to selectively adsorb either
cations or anions and release (exchange) ―counter-ions‖ based on the relative activity
compared to the resin. This process of ion exchange will continue until all available
exchange sites are filled, at which point the resin is exhausted and must be regenerated by
suitable chemicals. Ion exchange systems are used in several ways.

Water Softening

47
The ion exchange water softener is one of the most common tools of water treatment. Its
function is to remove scaleforming calcium and magnesium ions from hard water. In
many cases soluble iron (ferrous) can also be removed with softeners. A standard water
softener has four major components: a resin tank, resin, a brine tank to hold sodium
chloride, and a valve or controller. The softener resin tank contains the treated ion
exchange resin – small beads of polystyrene. The resin bead exchange sites adsorb
sodium ions and displace multivalent cations during regeneration with 6-10% solution
of NaCl. The resin has a greater affinity for multivalent ions such as calcium and
magnesium than it does for sodium. Thus, when hard water is passed through the resin
tank in service, calcium and magnesium ions adhere to the resin, releasing the sodium
ions until equilibrium is reached. When most of the sodium ions have been replaced by
hardness ions, the resin is exhausted and must be regenerated. Regeneration is achieved
by passing a concentrated NaCl solution through the resin tanks, replacing the hardness
ions with sodium ions. The resin’s affinity for the hardness ions is overcome by the
concentrated NaCl solution. The regeneration process can be repeated indefinitely
without damaging the resin. Water softening is a simple, well-documented ion exchange
process. It solves a very common form of water contamination: hardness. Regeneration
with sodium chloride is a simple, inexpensive process and can be automatic, with no
strong chemicals required. The limitations of water softening become apparent when
highquality water is required. Softening merely exchanges the hardness ions for normally
less-troublesome sodium ions which are still unsuitable for many uses.

Deionization (DI)
Ion exchange deionizers use synthetic resins similar to those in water softeners. Typically
used on water that has been prefiltered, DI uses a two-stage process to remove virtually
all ionic material in water. Two types of synthetic resins are used: one to exchange
positively-charged ions (cations) for H+ and another to exchange negatively-charged
ions (anions) for OH, Cation deionization resins (hydrogen cycle) release hydrogen
(H+) in exchange for cations such as calcium, magnesium and sodium. Anion
deionization resins (hydroxide cycle) exchange hydroxide (OH-) ions for anions such as
chloride, sulfate and bicarbonate. The displaced H+ and OH- combine to form H2O.
Resins have limited capacities and must be regenerated upon exhaustion. This occurs
when equilibrium between the adsorbed ions is reached. Cation resins are regenerated by
treatment with acid which replenishes the adsorption sites with H+ ions. Anion resins are
regenerated with a base which replenishes the resin with (OH-) ions. Regeneration can
take place off-site with exhausted resin exchanged with deionizers (Figure 16) brought in
by a service company. Regeneration can also be accomplished on-site by installing
regenerable-design deionizer equipment and by proper use of the necessary chemicals.

Two-Bed and Mixed-Bed Deionizers

The two basic configurations of deionizers are two-bed and mixed-bed. Two-bed
deionizers have separate tanks of cation and anion resins. In mixed-bed deionizers
(Figure 18) the two resins are blended together in a single tank or vessel. Generally
mixed-bed systems will produce higher-quality water, but with a lower total capacity than
two-bed systems. Deionization can produce extremely high-quality water in terms of
dissolved ions or minerals, up to the maximum purity of 18.3 megohms/cm resistance.

48
However, it generally cannot remove organics, and can become a breeding ground for
bacteria actually diminishing water quality if organic and microbial contamination are
critical. Failure to regenerate the resin at the proper time may result in salts remaining in
the water or even worse, being increased in concentration. Even partially-exhausted resin
beds can increase levels of some contaminants due to varying selectivity for ions, and
may add particulates and resin fines to the deionized water.

Distillation Methods

Distillation is the collection of condensed steam produced by boiling water. Most

contaminants do not vaporize and, therefore, do not pass to the condensate (also called
distillate). With a properly-designed still, removal of both organic and inorganic
contaminants, including biological impurities such as pyrogens, is attained. Since
distillation involves a phase change, when properly carried out by a correctly designed
and operated still, it removes all impurities down to the range of 10 parts per trillion
(ppt), producing water of extremely high purity. Close control over boiling temperature
and boiling rate, as well as the separation of steam from potential carryover, is required
for the purest water. Distillation is comparatively energy-intensive. However, the
development of multiple-effect distillation has dramatically reduced the energy
consumption required versus single-effect units. Higher temperature steam is used
repeatedly, losing some heat in each stage (effect) but substantially reducing overall
energy use. Today the most significant use of stills is in laboratories and the
biotechnology and pharmaceutical industries because of their critical concern for
biological contamination. Distillation is the most accepted technology for a consistent
supply of pyrogen-free water without the use of chemical additives. Careful temperature
monitoring is required to ensure purity and avoid recontamination of the purified water.

49
Figure 10. Distillation Process

Reverse osmosis

Reverse osmosis, invented in 1959, is the newest major method of water purification and
one of the types of crossflow membrane filtration. It is a process which removes both
dissolved organics and salts using a mechanism different from ion exchange or activated
carbon. The pressurized feedwater flows across a membrane, with a portion of the feed
permeating the membrane. The balance of the feed sweeps parallel to the surface of the
membrane to exit the system without being filtered. The filtered stream is the permeate‖
because it has permeated the membrane. The second stream is the ―concentrate‖ because
it carries off the concentrated contaminants rejected by the membrane. Because the feed
and concentrate flow parallel to the membrane instead of perpendicular to it, the process
is called ―crossflow filtration‖ (or, erroneously, ―tangential flow‖). Depending on the size
of the pores engineered into the membrane, crossflow filters are effective in the classes of
separation known as reverse osmosis, nanofiltration, ultrafiltration and the more recent
microfiltration. Crossflow membrane filtration allows continuous removal of
contaminants which in ―normal flow‖ filtration would ―blind‖ (cover up) or plug the

50
membrane pores very rapidly. Thus the crossflow mode of operation is essential to these
processes

Figure 11. Reverse osmosis

Reverse osmosis (RO) was the first crossflow membrane separation process to be widely
commercialized. RO removes most organic compounds and up to 99% of all ions. A
selection of RO membranes is available to address varying water conditions and
requirements. RO can meet most water standards with a single-pass system and the
highest standards with a double-pass system. This process achieves rejections of 99.9+%
of viruses, bacteria and pyrogens. Pressure in the range of 50 to 1000 psig (3.4 to 69 bar)
is the driving force of the RO purification process. It is much more energy-efficient
compared to phase change processes (distillation) and more efficient than the strong
chemicals required for ion exchange regeneration. F WATER PURIFICATION

Nanofiltration (NF) equipment removes organic compounds in the 250 to 1000

molecular weight range, also rejecting some salts (typically divalent), and passing more
water at lower driving pressures than RO. NF economically softens water without the
pollution of regenerated systems and provides unique
fractionation capabilities such as organics desalting.

51
Figure 12. Nanofiltration.

Ultrafiltration (UF) is similar to RO and NF, but is defined as a crossflow process that
does not reject ions. UF rejects solutes above 1000 daltons (molecular weight). Because
of the larger pore size in the membrane, UF requires a much lower differential operating
pressure: 10 to 100 psig (0.7 to 6.9 bar). UF removes larger organics, colloids, bacteria,
and pyrogens while allowing most ions and small organics such as sucrose to permeate
the porous structure.

Figure 12. Ultrafiltration process.

Microfiltration (MF) membranes are absolute filters typically rated in the 0.1- to 3.0-
micron range. Available in polymer, metal and ceramic membrane discs or pleated
cartridge filters, MF is now also available in crossflow configurations. Operating

52
differential pressures of 5 to 25 psig (0.3 to 1.7 bar) are typical. Crossflow MF
substantially reduces the frequency of filter media replacement required compared to
normal flow MF because of the continuous self-cleaning feature. Crossflow MF systems
typically have a higher capital cost than MF cartridge filter systems; however, operating
costs are substantially lower.
OF WATER PURIFICATION

Figure 13. Ultrafiltration process.

Membrane Configurations
Crossflow membranes are manufactured into various configurations – tubular, hollow-
fiber, flat-sheet or spiral-wound. Due to relative efficiency and economy, spiral-wound
membrane elements (called sepralators) are by far the most popular for crossflow water
purification.

Sepralators (Spiral-Wound Membrane Elements) Sepralators have gained the greatest

acceptance in the market. They are the most rugged, leak-free and pressure-resistant
configuration. The spiral design allows for optimum membrane surface area and fluid
dynamics to produce a high permeate flow for the size of equipment required. Sepralators
are available with RO, NF, UF, and MF membranes. Sepralators are quite easy to
maintain with a routine cleaning program. A major advantage is enhanced ―self-cleaning‖
due to turbulent flow at the membrane surface. This feature dramatically reduces fouling,
thereby enhancing performance and membrane life. Spiral-wound designs also offer the
greatest selection of membrane material, allowing users to ―tailor‖ a system design to suit
their purification requirements.

53
Figure 14. Spiral-Wound Membrane Element.

Hollow Fine-Fiber Elements

Hollow fine-fiber elements consist of hollow fibers each roughly the size of a human
hair. Thousands of fibers are closely bundled in each housing. The pressurized feed flows
slowly over the outside of the fibers and pure water permeates to the center. Then the
water is collected out of potted tube sheet. In the early 1970’s hollow fine-fiber water
purification systems gained popularity because of their high productivity resulting from
very high membrane surface areas. The major disadvantage of this element is the amount
of prefiltration required to keep the tightlypacked membrane surface free of severe
fouling due to the laminar flow in the element.

Figure 15. Hollow Fine-Fiber Permeator

54
Hollow Fat-Fiber Elements are only used in UF and MF due to burst-strength
limitations. The pressurized feed flow is on the inside of the fiber and water permeates to
the outside of the fiber. The fibers are potted at each end in a housing. Their self-
supporting nature limits maximum feed flows. 70 psid (4.8 bar) is the pressure limit
through elements constructed with these small fibers.

Figure 15. Hollow Fat-Fiber Element.

Disinfection – Control of Microbes

Control of microorganism populations is essential in maintaining the performance of any
water system. An example is in ultrapure water systems in which bacterial fouling is a
leading cause of contamination, and carefully monitored bacterial control is a necessity.
Biological control of a water system is accomplished by maintaining a continuous biocide
residual throughout the system, or by sanitizing the system on a regular basis. A
continuous biocide residual is preferable because it keeps bacterial growth in check and
prevents ―biofilms.‖ However, in some high-purity water systems this is not possible, so
regular sanitizations are needed. In either case, one of the most effective control measures
is to keep the system running continuously, since bacteria reproduce more quickly during
shutdown. If this is not possible, a 15- to 30-minute flush every four hours is helpful.
Two important considerations when using a biocide are concentration and contact time.
The higher the concentration, the shorter the contact time needed for effective
disinfection. Other factors which affect biocide activity are pH, temperature, water
hardness, establishment of a biofilm and general cleanliness of equipment. In many cases,
the system needs to be cleaned before it is disinfected. Cleaning helps to remove bacterial
film and dirt that can mask bacteria and viruses in the equipment. The film would allow
only the surface bacteria to be killed, and the bacteria would quickly re-establish
themselves.

55
 Chapter 7
Water Analysis Methods

1. Analyses of water as ASME methods

2. Sampling of water
 kinds of sample
 method of sample
 sampling of water boiler at different temperature
3. Testing of water sample as ASTEM method
 PH conductivity
 Hardness
 Acidity
 Alkalinity
 Chloride and chlorine
 Sulfate
 Phosphate

INTRODUCTION FOR WATER ANALYSIS

WATER SAMPLING AND TESTING OF WATER SYSTEMS

WATER SAMPLING AND TESTING

Water sampling and testing procedures provide information that can be used for the
following purposes: to ensure the protection of the water system equipment; to prevent
unexpected system failure; to provide information used to control water quality; and to
verify that water treatment chemicals are maintained at the proper concentration within
the system or, if not, to allow for adjustment of their concentration. Adequate chemical
treatment of water systems requires that specific levels of specific chemicals be
maintained in the water to provide the system with protection from corrosion and
deposits. This requirement applies to both cooling and boiler water systems. The purpose
of a sampling and analysis program for industrial water is to ensure and verify that the
required levels of treatment chemicals are being maintained and that the water quality
parameters are within the specified control ranges. The sampling and analysis program
incorporates two levels of testing: in-plant routine testing used for operational purposes,
and periodic independent (third-party) QA testing used for verification and oversight.
When an analytical test indicates that the concentration of a given chemical is not within
the limits required, the testing process must be evaluated to determine that the sampling
and testing were performed properly and that the test result is valid. As part of an
adequate QA/QC program, test methods, including the chemical reagents, must be
checked on a routine basis. A properly applied industrial water treatment program
incorporates procedures that ensure that representative samples, which are samples that

56
are representative of actual water system conditions, have been collected and analyzed.
Safety considerations must be a priority when sampling any industrial water system
(particularly boilers) and when conducting laboratory tests.

In-Plant Testing. In-plant testing is used by water system operators to monitor and
ensure both the proper operation of system equipment and the proper quality of the water
in the equipment. Routine, appropriate, in-plant operational testing of the system waters
is an essential component of a water treatment program. Routine testing of specific
operational parameters and water quality criteria allows the operator to verify the
adequacy of the water treatment program and to make necessary adjustments to avoid and
prevent operational problems. When an analytical test indicates that the concentration of
a given chemical is not within the limits required, the testing process must be evaluated to
determine that the sampling and testing were performed properly and that the test result is
valid. If testing data for the water quality analyses are inconsistent with that expected for
the treatment method being used, the reasons must be determined. This determination can
involve reanalysis and checking of the test reagents, as well as checking the accuracy of
the in-plant testing results through independent QA analysis. Military installations are
required to obtain water testing chemicals and equipment from commercial sources. Test
procedures will be furnished with the test kits.

Independent QA Analysis. To verify the accuracy of the in-plant testing, as well as to

provide supplemental or additional analyses, independent (third-party) QA analytical
services are incorporated as part of the plant’s QA program. These services can be more
complete than routine in-plant testing and can provide a more detailed analysis of the
system conditions. Independent QA analysis is a useful tool for plant managers and
operators to verify that their systems are being maintained properly, and is an especially
important tool for government managers at sites where plant operations have been
contracted out (outsourced).

Boiler Water Sampling Procedures

ROUTINE BOILER WATER SAMPLING AND TESTING

57
Boiler water is very hot and under pressure. Caution should be exercised and appropriate
safety procedures followed when collecting samples. If the boiler water is not cooled as it
is sampled, part of the water will flash off as steam during the sampling process and the
remaining sample will not be truly representative of the boiler water. The sample could
contain a lower level of oxygen or carbon dioxide than the actual levels in the boiler
water. Values of other sample constituents would be higher because less water would be
present in the test sample due to the release of the steam.

Boiler Water Sampling Cooler

A commercially available boiler water sample cooler can be used when collecting a
boiler water sample. If one is not available, then a 4.6- to 6.1-meter long (15- to 20-foot)
coil of copper or stainless steel tubing (60 millimeters [0.25 inch]) may be used to cool
the sample. The coil can be immersed in a permanent cooling jacket as shown in Figure
below or it may be immersed in a bucket of cold water, if this does not interfere with
operation of the system or create a hazard. The flow of the boiler water sample through
the coil must be slow enough so that the cooled boiler water sample is no more than just
o
warm to the hand (approximately 38 °C [100 F]).

Boiler or Condensate Water Sample Cooling Coil

The cooling water to the jacket cooling coil is turned on before taking the boiler water
sample and turned off after the sample has been collected. The coil with boiler water is
flushed with several times its volume before collecting the sample to be tested. The
cooled end of the boiler water sample coil is then extended to the bottom of the sample
bottle and at least 1 volume of the bottle is allowed to overflow the container during the
collection process. The sample collection bottle can be plastic or glass. Glass bottles are
not used if the boiler is silica limited or if high silica is suspected.

Sampling Locations

Typical locations for water sampling points in a steam boiler system are shown in the
following Figure Each sampling point has a separate cooling coil. Two or more sampling
points are not connected by a single manifold to the same cooling coil because it is
almost impossible to determine if one of the valves has a leak that might contaminate the
sample being taken. Guidelines for sample collection are provided below.

• The makeup water sample does not have to be cooled. The sample location typically
will be the output of an ion exchange unit or some other water-softening unit.
• The boiler feedwater sample is a combination of makeup and condensate return. An
appropriate location for sample collection is from the discharge of the boiler feed pump.
This will be a hot sample, so a cooling coil is used. Alternatively, sample collection for
feedwater can be from the low-pressure deaerator outlet.

58
• The boiler water is very hot. Collect this sample from the continuous blowdown line
between the boiler and the regulating valve if possible. You may collect it from a gauge-
glass connection, if necessary. Use of a cooling coil is recommended.
• The steam condensate is hot. For small systems, collect this sample from a line that
enters the deaerating heater if possible. For medium and large systems, you may need to
collect condensate samples at two or more locations in the system to obtain sufficient
data for calculation of the proper treatment level. When attempting to find a leak, you
may need to collect condensate samples from various locations in the system. Use of a
cooling coil is recommended.
• Steam is collected regularly for systems with high-quality steam requirements like those
with turbines and those meeting steam quality requirements. Otherwise, steam samples
are rarely collected. Refer to the ASME Performance Test Code (ASME PTC 19.11,
Steam and Water Sampling, Conditioning and Analysis in the Power Cycle, for sampling
procedures.

59
 Table 2. Water Sampling Frequency and Testing Requirements for Boiler Water
Systems

Total Hydroxyl Copper

Source of pH Alkalinity* Alkalinity Calcium Ortho-
TDS and Sulfite
Sample Hardness phosphate
(M) (Causticity) Iron
Makeup water -- 1/W -- 1/W 1/W -- -- --
Feedwater,
small boilers
-- 1/W -- 1/W 1/W -- -- --
(< 245 kW [25
hp])
Feedwater,
medium
boilers (245– -- 2/W -- 2/W 2/W -- -- --
1470 kW [25-
150 hp])
Feedwater,
large boilers
-- 1/D -- 1/D 1/D -- -- --
(> 1470 kW
[150 hp])
Boiler water,
1/W -- 1/W -- 1/W -- 1/W 1/W
small boilers
Boiler water,
medium 2/W -- 2/W -- 2/W -- 2/W 2/W
boilers
Boiler water,
1/D -- 1/D -- 1/D -- 1/D 1/D
large boilers
Condensate
As
return (small 1/W -- -- 1/W 1/Q -- --
needed
boilers)
Condensate
return As
2/W -- -- 2/W 1/Q -- --
(medium needed
boilers)
Condensate
As
return (large 1/D -- -- 1/D 1/Q -- --
needed
boilers)

NOTES: W = Week (for example, 1/W = once per week). Q = Quarter (for example, 1/Q - once per 3
months). * = Feedwater alkalinity only for boilers that use dealkalizers.

60
Typical Locations for Water Sampling in a Steam Boiler Water System

Frequency of Sampling and Testing. The recommended sampling and testing frequency
for steam boiler systems is summarized in Table 2.

Boiler Feedwater Sample. Boiler feedwater samples should be collected once per week
for small boilers (less than 245 kilowatts [25 horsepower]), at least 2 times per week for
medium boilers (245 to 1470 kilowatts [25 to 150 horsepower]), and daily for large
boilers (greater than 1470 kilowatts [150 horsepower]). The samples should be tested for
M alkalinity, conductivity, and calcium hardness.

Condensate Water Sample. Condensate water samples should be collected once per
week for small boilers (less than 245 kilowatts [25 horsepower]), at least 2 times a week
for medium boilers (245 to 1470 kilowatts [25 to 150 horsepower]), and daily for large
boilers (greater than 1470 kilowatts [150 horsepower]). The samples should be tested for
pH and conductivity. If the conductivity is greater than 35 micromhos, the sample should
be tested for calcium hardness. If applicable based on the metallurgy of the system, the
condensate samples should be tested for iron and copper on a quarterly basis.

Boiler Blowdown Water Sample. Boiler blowdown water samples should be collected
for small boilers (less than 245 kilowatts [25 horsepower]) once per week, for medium
boilers (245 to 1470 kilowatts [25 to 150 horsepower]) at least 2 times per week, and for

61
large boilers (greater than 1470 kilowatts [150 horsepower]) daily. The samples should
be tested for hydroxyl (OH) alkalinity (causticity), neutralized conductivity, scale
treatment chemicals (e.g., orthophosphate), and sulfite.

Boiler Water Quality Assurance (QA) Analysis

Appropriate boiler water sampling requirements are described below.

 Each operating boiler plant equipped with hot water or steam boilers and having one
or more boilers of 980 kilowatts (3.3 million BTU per hour or 100 horsepower) or
greater capacity may submit a boiler water sample for QA once per month to an
independent QA laboratory or to the contractor providing the service to the military.
These QA contractors are independent experts in the field of boiler and cooling water
treatment and interpretation of sample analysis data.
 Each operating boiler plant equipped with hot water or steam boilers of less than 980
kilowatts (100 horsepower) capacity submits a boiler water sample for QA once every
3 months to an independent QA laboratory or to the contractor providing the service
to the military.
 For all high-pressure (greater than 103 kilopascals [15 pounds per square inch
gauge]) boilers and for low-pressure boilers treated with caustic, phosphate, tannin,
and sodium sulfite, the boiler water sample size is a 1-liter plastic bottle, or as
required by the QA laboratory.
 For low-pressure boilers (less than 103 kilopascals [15 pounds per square inch
gauge]) treated only with caustic, the boiler water sample size is a 0.12-liter (4-ounce)
plastic bottle, although a 1-liter plastic bottle may be used.
 For hot water boilers, the boiler water sample size is a 1-liter plastic bottle, or as
required by the contract laboratory.
 Boiler water sample shipping containers and bottles used for submitting boiler water
check samples can be obtained by request to the contract laboratory. Shipping
containers for high-pressure boiler water samples are designed for shipping a 1-liter
plastic bottle. Shipping containers for water samples from low-pressure boilers
treated with caustic soda are designed for shipping a 0.12-liter plastic bottle. Pack the
bottle carefully so it will not leak during shipping. A completed information data
sheet must be enclosed in each sample shipping container shipped to the laboratory.

WATER TESTING

Routine and appropriate testing of the system water is an essential component of a water
treatment program. Water testing provides information that can be used: to ensure the
protection of the water system equipment; to prevent unexpected system failure; to
provide information used to control water quality; and to verify that water treatment
chemicals are maintained at the proper concentrations within the system or, if not, to

62
allow for adjustment of their concentrations. An adequate testing program requires proper
recordkeeping of the data that are used for assessing the effectiveness of the water
treatment program. If testing data for the water quality analyses are inconsistent with that
expected for the treatment method being used, determine the reasons. This determination
can involve reanalysis and checking of the test reagents. If the test results are correct, the
water quality and water treatment program must be re-evaluated and modified, if
necessary. Paragraph 6-6 describes interpretation of water test results.

1. Water Sample Testing Methods. Water tests are usually performed with test kits
obtained from commercial sources. Test kits can be used to test for: alkalinity-
phenolphthalein (P); alkalinity-methyl orange (M or total); alkalinity-hydroxyl
(OH) or ―causticity‖; conductivity; tannin; pH; hardness (total and calcium,
magnesium by difference); phosphate (ortho and total); sulfite; nitrite; chloride;
molybdate; phosphonate; chlorine or bromine (total and free); total iron; and total
copper.

2. Corrosion Testing. Corrosion test specimens or corrosion testing instruments can

be used to monitor the rate of corrosion. Corrosion test information can also be
used to evaluate how well equipment is being protected from corrosion by the
water treatment program. The degree of corrosion (if any) that is occurring in
large or critical heating and cooling systems should be determined at all military
installations. Consider the following information when developing a program of
corrosion testing:

3. Corrosion Test Results. Corrosion test results are usually determined as a rate of
corrosion penetration into the metal and reported in mils metal loss per year
(mpy). A mil is 2.5-thousandths of a centimeter (one-thousandth [0.001] of an
inch); thus, the corrosion rate of 10 mpy means that the thickness of a piece of
metal is reduced by 10 x 0.0025 = 0.025 centimeter per year (0.01 inch per year).
If the metal coupon being studied is 0.1588 centimeter (0.0625 inch) thick, this
means that it will be completely dissolved or corroded in just over 6 years.
Corrosion rates may also be expressed in millimeters per year (mmpy) corrosion.
The relationship between mpy and mmpy is: 1 mpy = 0.0254 mmpy; 1 mmpy =
39.4 mpy. Corrosion also may be given as a weight loss in milligrams per square
decimeter per day (mdd). For mild steel, the relationship is: 1 mdd = 0.2 mpy or 1
mpy = 5 mdd.

4. Testing Instruments. A variety of electronic instruments are available to monitor

and record corrosion rates. These instruments are installed and maintained by
individuals who have been adequately trained for these activities. The most
commonly used instrument of this type is a linear polarization corrosion
instrument that provides instantaneous corrosion measurement and is often used
for troubleshooting.

5. Heat Transfer Corrosion Test Equipment. Heat transfer corrosion test

equipment is used to determine the corrosion rate under heat transfer conditions.

63
 This type of equipment can more accurately determine corrosion in chillers.

INTERPRETATION OF RESULTS FROM WATER TESTS

Adequate chemical treatment of water systems requires that specific levels of specific
chemicals be maintained in the water to provide the system with protection from
corrosion and deposits. This requirement applies to both cooling and boiler water
systems. When an analytical test indicates that the concentration of a given chemical is
not within the required limits, the testing process must be evaluated to determine whether
sampling and testing were performed properly and the test result is valid. As part of an
adequate QA/QC program, test methods, including the chemical reagents, must be
checked on a routine basis. Consider these guidelines when evaluating test results:

Alkalinity Test Relationships

Sources of Alkalinity. The three basic sources of alkalinity in water result from the
- - -
bicarbonate ion (HCO3 ), the carbonate ion (CO3 ), and the hydroxyl ion (OH ). The
amount of each of these ions in water can be determined by titration with an acid to
specific pH levels (end points) using phenolphthalein (P alkalinity) or methyl orange (M
alkalinity) indicators to their particular titration end-points. The relationship between pH
and the various types of alkalinity is shown in the following Figure.

64
Acidity, Alkalinity, and pH Ranges

Relationship of P, M, and OH Alkalinities

Test procedures for determining P and M alkalinities are included in commercially

-
available test kits. The OH alkalinity can be determined by a specific test or it can be
-
estimated by knowing the P and M alkalinity values. The OH alkalinity is contributed by
-
the hydroxyl ions (OH ) in the water, and is also known as "caustic alkalinity" or
"causticity.‖ The relationship between the measured P and M alkalinity values and the
level of hydroxyl, carbonate, and bicarbonate forms of alkalinity are shown in Table 3
and described below.

65
Table 3. Alkalinity Relationship Based on P and M Tests

Situation Hydroxyl Level of Alkalinity Contributed by Bicarbonate

Carbonate
P=M M 0 0
P > ½M 2P – M 2 (M - P) 0
P = ½M 0 M 0
P < ½M 0 2P M - 2P
P=0 0 0 M

66
EXAMPLE :

If P = 86 ppm as CaCO3, and if M = 118 ppm as CaCO3

Then, situation 2 (from Table 3) exists (P > ½M) or P is greater than ½ of M);

Hydroxyl = 2P − M = (2 x 86) − 118 = 54 ppm as CaCO3 , Causticity = hydroxyl

−
alkalinity as CaCO3 ÷ 3 = 54 ÷ 3 = 18 ppm as OH

Carbonate = 2(M − P) = 2 X (118 - 86) = 64 ppm as CaCO3

Bicarbonate = 0 ppm as CaCO3

Check: Total = 54 + 64 + 0 = 118 ppm M alkalinity as CaCO3

Review of each situation in Table 3 provides this information, with situation:

1. The tests for P alkalinity and M alkalinity are equal. This means that all of
the alkalinity is due to hydroxyl ions. There is no carbonate or bicarbonate
present. (This is rare but occurs when a caustic solution is not exposed to
air.)

2. The P alkalinity is greater than one-half of the M alkalinity. This indicates

that there is hydroxyl and carbonate alkalinity, but no bicarbonate
alkalinity.

3. The P alkalinity is equal to one-half of the M alkalinity. This indicates that

all the alkalinity is due to carbonate. There is no bicarbonate alkalinity,
and the hydroxyl alkalinity is insignificant.

4. The P alkalinity is less than one-half of the M alkalinity. This indicates that
carbonates and bicarbonates are present.

5. The P alkalinity is zero. The M alkalinity is due to bicarbonates only. No

hydroxyl or carbonate alkalinity are present.

pH (Hydrogen Ion Concentration)

Meaning of pH. The pH (value) is a measure of the acidity or alkalinity of water. The
test specifically measures the concentration of hydrogen ions in the water. Neutral water
will have a pH of 7. Water with a value of less than pH 7 is considered acidic, while
water with a value greater than pH 7 is considered alkaline. Examples are shown below.

• Common pH values for materials on the acid side include: spinach with a pH of
approximately 5.5; orange juice and most soft drinks with a pH of approximately 3.5;

67
lemon juice with a pH of approximately 2.2; and 0.1 normality (N) sulfuric acid with a
pH of 1.2.
• Common pH values of materials on the alkaline side include: sodium bicarbonate with a
pH of approximately 8.4; milk of magnesia with a pH of approximately 10.5; household
ammonia with a pH of approximately 11.5; and 0.1 N sodium hydroxide with a pH of
13.0.

The pH scale is logarithmic. A pH of 4 is 10 times as acidic as a pH of 5 and 100 times

as acidic as a pH of 6. This is important to consider when adding a strong acid to a
system, because 0.1 N sulfuric acid will have more than 1 million times the acidity of
neutral water.

Relationship to Causticity. When the pH of water exceeds a value of 9.6 to 9.8, a

-
measurable concentration of hydroxyl ions (OH ) is present in the water. As the hydroxyl
alkalinity (causticity) increases, the pH of the solution also increases. The relationship
between causticity and pH is shown in Table 4.

68
Table 4. Relationship Between Causticity and pH

Hydroxyl Alkalinity (ppm)

pH as CaCO3 as OH
9.0 0.5 0.17
9.5 1.6 0.54
10.0 5 1.70
10.2 8 2.2.72
10.5 16 5.44
10.6 20 6.80
10.7 25 8.50
10.8 33 11.2
10.9 40 13.6
11.0 50 17.0
11.1 63 21.4
11.2 79 26.9
11.3 100 34.0
11.4 126 42.8
11.5 158 53.7
11.6 199 67.7
11.7 250 85.0
11.8 315 107
11.9 397 135
12.0 500 170

Conductivity and TDS

Each of these water quality parameters is a measure of the amount of soluble minerals
present in the water. Conductivity is measured with an electronic instrument based on the
flow of an electrical current through the water sample. The measurement of TDS requires

69
evaporation of a fixed amount of water to determine the weight of the remaining minerals
(i.e., the TDS in the water). The conductivity instrument may report the mineral content
as micromohs or as dissolved solids. In neutral or alkaline waters, there is no consistent
relationship between conductivity and TDS since each ion has its own specific
conductivity. The hydroxyl ion has the highest conductivity of all the common ions found
in boiler water. If alkaline boiler water is acidified to the phenolphthalein end-point with
an organic acid, such as gallic acid, which neutralizes causticity but does not contribute to
conductivity, the TDS is approximately equal to two-thirds of the neutralized
conductivity in micromhos. This is known as ―neutralized conductivity."

WATER ANALYSIS METHODS

pH-ELECTROMETRIC METHOD TEST PROCEDURES

PH Meter, Beaker, 150 ml, Heavy Duty Plastic, Wash Bottle, 500 ml, Heavy Duty Plastic

REAGENTS:

Standard pH Buffer Solution, pH-4

Standard pH Buffer Solution, pH-7
Standard pH Buffer Solution, pH-10

METHOD:

Carefully follow the procedures provided with the pH meter. They should be similar to
the following:

1. Turn the meter from ―standby‖ to ―on‖ position.

2. Standardize instrument by immersing the electrode(s) in two different

Standard pH Buffer Solutions in the test beaker as follows:

a. Place electrode(s) in pH-7 Buffer Solution and adjust the meter to read
pH-7.

b. Place electrode(s) in the second pH Buffer Solution, either the pH-4

or pH-10, depending on the suspected range of the unknown
sample to be tested, and adjust the meter to the same pH.

70
 3. Remove electrode(s) and thoroughly wash with distilled or condensate
water.
4. Immerse the electrode(s) in the water sample and turn the meter to ―test‖
or ―pH‖ position and read meter.
5. Rinse the electrodes with distilled or condensate water and turn the
instrument to the ―standby‖ position. Do not turn off.

NOTES:

1. When not in use, keep the glass electrode soaking in a pH-4 Buffer
Solution.
2. When not in use, keep the plastic cap on the reference electrode. Some
reference electrodes must be kept full of electrolyte. Follow the
instrument instructions on this.

CONDUCTIVITY TEST PROCEDURES

APPARATUS: Conductivity Meter.

In general, there are two types of conductivity meters. One has an electrode that is put
into a cell containing the water to be tested. The other has a small cup mounted on the
meter into which the water to be tested is poured. Either type of meter may be
automatically temperature compensated, or the meter may require a temperature
correction. The meter may indicate TDS or conductivity as micromhos, but either
measurement represents the same characteristic of the water sample. Where the meter is
designed to give either measurement, it is important to always use the same measurement
to avoid an error.

Cylinder, Ungraduated, Footed Base, about 5 inches high x 1 ½-inch diameter

Thermometer.

REAGENTS:
Phenolphthalein Indicator Solution, 1 percent, Gallic Acid Powder

METHOD:

It is necessary to follow the instructions furnished with the conductivity meter that is
being used. The general procedure should be similar to the following steps:

1. The quantity of water sample should be as specified for the meter.

2. Add 3 drops of Phenolphtlaein Indicator. If the sample turns red, add
Gallic Acid Powder until the red color disappears. If the water does not
turn red when the Phenolphthalein Indicator is added, continue the test.
3. Follow the instructions for the meter to measure the conductivity, using
the appropriate method (that is, with or without the acid addition).

71
RESULTS:

Depending upon the type of meter used, the results are read as either conductivity in
micromhos or TDS in ppm. The relationship between these measurements when these
procedures are used is as follows:
TDS, ppm = 0.66 x Conductivity, micromhos
Conductivity, micromhos = 1.5 x TDS, ppm.

NOTES:
1. Periodically the meter should be calibrated against a standard solution.
Two standard potassium chloride solutions are available from the check-analysis
laboratory:

TOTAL HARDNESS TEST PROCEDURES

APPARATUS:
Burette 10 ml, Graduated Cylinder 50 ml, Plastic, Casserole, Porcelain, Heavy Duty, 200
ml Capacity, Stirring Rod, Plastic Spoon, Plastic, 0.1 gm Capacity Bottle, w/Dropper, 2
oz (for Hardness Buffer Solution).

REAGENTS:
Standard Hardness Titrating Solution, 1 ml = 1 mg CaCO3
Hardness Buffer Solution
Hardness Indicator Powder

METHOD:

1. Measure the amount of water to be tested in the graduated cylinder. The

amount should be based on the expected results of the test according to the
following: Hardness Expected, as CaCO3 Sample Size Factor Less than
100 ppm 50 ml 20 More than 100 ppm 20 ml 50
2. Pour the sample into the casserole.
3. Add 1 ml Hardness Buffer Solution and 1 spoon of Hardness Indicator
Powder to the sample. If the water turns blue, there is no hardness present,
and it is reported as zero. If the water turns purple or red, then the test
should be continued.
4. Squeeze the rubber bulb to force the Standard Hardness Titrating Solution
from the bottle to fill the burette just above the zero mark; then allow the
excess to drain back automatically into the bottle.
5. While stirring the sample constantly, add Standard Hardness Titrating
solution slowly from the burette to the casserole until the purple or red
color changes to blue. This is the end point. Read the burette to the

72
 nearest 0.1 ml.

RESULTS:

The total hardness (TH), ppm as CaCO3, is obtained as follows:

Total hardness, ppm = (ml solution) x (factor).

EXAMPLE:

6.5 ml of the Standard Hardness Titrating Solution were required to change the color of
a 50 ml sample of water from red or purple to blue.
Total hardness = 6.5 x 20 = 130 ppm as CaCO3

NOTE:

When testing water softener effluent, use a 200 ml sample and a factor of 5, or a 500 ml
sample and a factor of 2.

TOTAL ALKALINITY TEST PROCEDURES

APPARATUS:
Burette, 10 ml, Graduated Cylinder, 50 ml, Plastic Bottle, w/Dropper (for Mixed
Indicator) 2 oz, Casserole, Porcelain, Heavy Duty, 200 ml Capacity Stirring Rod, Plastic.

REAGENTS:
Standard Sulfuric Acid Solution, N/50
Mixed Indicator Solution.

METHOD:

1. Measure the amount of water to be tested in the graduated cylinder. The

amount should be based on the expected results of the tests according to
the following: M Alkalinity Expected, As CaCO3 Sample Size Factor Less
than 100 ppm 50 ml 20 More than 100 ppm 20 ml 50
2. Pour into the casserole.
3. Add 10 drops of Mixed Indicator Solution to the casserole and stir. If the
water changes to a light pink color, free mineral acid is present. There is
no mixed indicator alkalinity, and the ―M‖ reading is reported as ―zero.‖
If the water changes to a green or blue color, ―M‖ alkalinity is present and
the test should be continued.
4. Squeeze the rubber bulb to force the Standard Sulfuric Acid Solution to

73
 fill the burette to just above the zero mark; then allow the excess to drain
back automatically into the bottle.
5. While stirring the water constantly, add Standard Sulfuric Acid Solution
slowly from the burette to the casserole until the green or blue color
changes to light pink. This is the end point. Read the burette to the nearest
0.1 ml.

RESULTS:

The M alkalinity (ppm as CaCO3) is calculated as follows:

M alkalinity (ppm as CaCO3) = (ml acid) x (factor)

EXAMPLE:

5.9 ml of N/50 sulfuric acid were required to change the color of a 50 ml sample of water
from green to light pink: M alkalinity = 5.9 x 20 = 118 ppm as CaCO3

NOTES:

1. If the end point color is difficult to see, repeat the entire test using 15
drops of Mixed Indicator Solution.
2. Just before the end point is reached, the green or blue color fades to a
light blue color and then becomes light pink. The end point is the first
appearance of a permanent pink color.

CHLORIDE TEST PROCEDURES

APPARATUS:
Burette, 10 ml Automatic (for Mercuric Nitrate Solution)

Graduated Cylinder, 50 ml, Plastic

Casserole, Porcelain, Heavy Duty, 200 ml Capacity
Stirring Rod, Plastic
Bottle, w/Dropper, 2 oz (for Chloride Indicator Solution)

REAGENTS:

Standard Mercuric Nitrate Solution, 0.0141 N

Chloride Indicator Solution
Standard Sulfuric Acid Solution, N/50

METHOD:

74
 1. Measure the amount of water to be tested in the graduated cylinder. The
amount should be based on the expected results of the test according to the
following: Chloride Expected, as C1 Sample Size Factor Less than 20 ppm
100 ml 10 More than 20 ppm 50 ml 20
2. Pour into the casserole.
3. Add 1.0 ml of Chloride Indicator Solution to the water in the casserole and
stir for 10 seconds. The color of the water should be a green-blue color at
this point.
4. Add the standard Sulfuric Acid Solution a drop at a time until the water
turns from green-blue to yellow.
5. Squeeze the rubber bulb to force the Standard Mercuric Nitrate Solution
from the bottle to fill the burette just above the zero mark; then allow the
excess to drain back automatically into the bottle.
6. While stirring the sample constantly, add Standard Mercuric Nitrite Solution
slowly from the burette to the casserole until a definite purple color appears.
This is the end point. (The solution will turn from green-blue to blue a few
drops from the end point.) Read the burette to the nearest 0.1 ml.

RESULTS:

The Chloride, in ppm C1, is calculated as follows: Chloride, ppm C1 = (ml of

Mercuric Nitrate – 0.2) x factor.

EXAMPLE:

11.2 ml of 0.0141 N Mercuric Nitrate Solution were required to change the color of a 50
ml sample of water from a green-blue to purple. Chloride = (11.2 – 0.2) x 20 = 220 ppm)

SULFITE TEST PROCEDURES

APPARATUS:
Burette, 10 ml Automatic (for Potassium Iodide-Iodate Solution) (item 1001)
Graduated Cylinder, 50 ml, Plastic (item 1004)
Casserole, Porcelain, Heavy Duty, 200 ml Capacity (item 1003)
Stirring Rod, Plastic (item 1006)
Measuring Scoop, Plastic, 1 gm Capacity (item 1008)
Bottle, w/Dropper, 2 oz (for Phenolphthalein Indicator Solution) (item 1005)

REAGENTS:

Standard Potassium Iodide-Iodate Solution, 0.0125 N (item 2017)

Phenolphthalein Indicator Solution, 1 percent (item 2040)
Dual Purpose Sulfite Indicator Powder (item 2060) – CAUTION STRONG ACID

75
METHOD:

1. Measure the amount of water to be tested in the graduated cylinder. The

amount should be based on the expected results of the test according to the
following: Sulfite Expected, as SO3 Sample Size Factor Less than 100
ppm 50 ml 10 More than 100 to 500 ppm 10 ml 50.
2. Pour the sample into the casserole.
3. Add 5 drops of Phenolphthalein Indicator Solution to the casserole.
4. Add 2 or more ―scoopfuls‖ of Sulfuric Indicator Powder to the sample in
the casserole and stir slowly until the red color disappears.
5. Squeeze the rubber bulb to force the Standard Potassium Iodide-Iodate
Solution to fill the burette just above the zero mark; then allow the excess
to drain back automatically into the bottle.
6. While stirring the sample constantly, add Potassium Iodide-Iodate
Solution slowly from the burette to the casserole until a faint but
permanent blue color appears. This is the end point. Read the burette to
the nearest 0.1 ml.

RESULTS:

The sulfite level, in ppm SO3, is calculated as follows: Sulfite, ppm = (ml solution) x
(factor).

EXAMPLE:

2.3 ml of the Potassium Iodide – Iodate Solution were required to change the color of a
50 ml sample of water from colorless to faint blue. Sulfite = 2.3 x 10 = 23 ppm SO3

NOTES:

1. To ensure accurate results, water samples should be cooled with minimum

exposure to air.

2. The test should be done as quickly as possible to reduce the introduction of

oxygen.

3. Use a minimum of 2 scoopfuls of Sulfite Indicator Powder plus any

additional amount to neutralize all the alkalinity (elimination of red color) in
the water to be tested, as indicated in step 4 of the method.

4. The end point is the first appearance of a faint, permanent blue color and not
the deep blue color that develops if Potassium Iodide-Iodate is added past
the end point.

76
 5. To express sulfite levels as ppm sodium sulfite (Na2SO3), multiply ppm SO3
by 1.575.

EXAMPLE:

23 ppm SO3 is equal to 1.575 x 23 or 36 ppm as Na2SO3.

TOTAL PHOSPHATE TEST PROCEDURES

APPRATUS:
Comparator Slide Base, Taylor No. 9190, or equal, High Phosphate Comparator, Range
5 to 100 ppm, Taylor No. 9119, or equal
Phosphate Mixing Tube, Graduated at 5, 15, and 17.5 ml, with
Rubber Stopper, Taylor No. 4021, or equal

Test Tube, 5 ml (two required), Taylor No. 4023, or equal

Wash Bottle for Molybdate Reagent
Funnel, Plastic
Filter Paper, Whatman No. 5, 12.5 cm dia, or equal
Test Tube Cleaning Brush
Measuring Cup, Plastic, 0.1 gm Capacity
Beaker, Plastic, 150 ml Capacity
Erlenmeyer Flask, 250 ml, Glass
Hot Plate
Graduated Cylinder, 50 ml, Plastic
Sulfuric Acid Solution, 4 N – CAUTION STRONG ACID
Sodium Hydroxide Solution, 4 N - CAUTION STRONG CAUSTIC
Phosphate Indicator Powder
Molybdate Reagent Solution – CAUTION STRONG ACID.
Distilled Water.

77
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