1.

Introduction
1.1 Introduction
The source of any water supply determines the kinds and amounts of its impurities.
Groundwater obtained from deep wells usually contains high concentrations of
dissolved minerals. This water is usually clear and colorless due to its filtration
through rock and sand. It also may contain various types of pollution, including
detergents and industrial wastes. It is now known that such forms of pollution may
travel quite some distance in water. Shallow wells provide water with varying
amounts of mineral impurities. There is also the danger that water from such sources
may become contaminated with human and animal wastes.
Surface waters contain many impurities, silt, sand and clay, which give them a
muddy or cloudy appearance. If run-off to them passes over agricultural land, it may
also absorb chemical wastes and toxic refuse from animals.
Where water flows sluggishly through swampland, it may acquire objectionable taste,
odor and plant color. During periods of flooding, these swamps may discharge their
decayed vegetation, color and microorganisms into moving streams and rivers.
Deep wells and large lakes alone provide water that is more or less consistent from
season to season. Smaller bodies of water, shallow wells and springs often reflect
seasonal-even daily variations in their mineral content.
To understand why water from different sources varies in quality, it is necessary to
know something about basic water chemistry.
When suspended in the atmosphere, water vapor approximates distilled water. It is
free from impurities and remains thus as long as it stays aloft. When water vapor
condenses sufficiently to fall to earth, it comes into contact with gases in the
surrounding air-carbon dioxide, nitrogen and oxygen. Atmospheric dust may also
contain minute particles of silica, oxides of iron and other materials together with
dust, pollen and some microorganisms.
In falling, moisture absorbs amounts of the atmospheric gases because these are
partially soluble in water. The colder the water, the more of the surrounding gaseous
content it dissolves.
If we chemically diagram the action of water as it dissolves some of the carbon
dioxide in the air, it would look this way:
H2O + C2 --> H2CO3
Water dissolves and collects Carbon Dioxide to produce Carbonic Acid
Normally when such water reaches the earth, it is slightly acid, corrosive and
relatively soft (though not as soft as man can make it through his skill in the
treatment of water). After water reaches the ground, it may pick up additional
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amounts of carbon dioxide from decaying vegetable matter. Equipped with this
booster action it acquires even greater potential for dissolving minerals and other
impurities on or below the surface. Water at the surface is slightly acid. If, however, it
has the opportunity to seep into the soil and pass through a limestone stratum, the
acid condition due to the carbon dioxide will be neutralized. At the same time, the
water will get a large amount of mineral content. Chemically this can be
diagrammed:
H2CO3 + CaCO3 --> Ca(HC03)2
Carbonic Acid reacts with Insoluble Calcium Carbonate to produce Soluble Calcium
Bicarbonate
Limestone, a common rock formation, contains varying portions of both calcium and
magnesium carbonates. These are the unseen hardness minerals which plague so
many supplies. The basic reaction shown in the above diagram holds true for both
minerals. Iron and manganese are found in water supplies less frequently. But again,
their basic chemical reaction in water is quite similar. Because it is a solvent, water
also picks up the soluble chlorides, sulfates and nitrates of calcium and magnesium.
Similarly, it absorbs the carbonate, bicarbonate, chloride, sulfate and nitrate
compounds of sodium as well as quantities of silica. Close scrutiny of a water supply
after exposure to many common gases and minerals will give a good idea of the
active solvent that water can be.

1.2

Objective

We check the water quality twice but the objectives at each point is
different
1. Before entering the treatment plant to know the extent of impurities to
decide the degree of treatment.

2. After the treatment is done water quality is again checked to so check

how far the treated water satisfying the water quality standards before
supplying it to the community.

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2. pH (Potential of Hydrogen ion )

2.1 Definition

A figure expressing the acidity or alkalinity of a solution on a

logarithmic scale on which 7 is neutral, lower values are more acid and higher
values more alkaline. The pH is equal to log10 c, where c is the hydrogen ion
concentration in moles per litre.

2.2 Acidity

The term acid was probably derived from the

Latin acidus, meaning sour to the taste, and referred specifically to vinegar
(Jensen 1980). By the end of the 17th century, a number of physical and
chemical properties was used to characterize acids, e.g. solubility in water
and the ability to dissolve other substances. Robert Boyle added to that list
the abilities to precipitate sulfur from sulfide solutions and to turn blue plant
dyes red. In 1744, Rouelle introduced the term bases for a class of
substances that reacts with acids to form salts (Finston and Rychtman
1982).

2.3 Measurement of pH value (by pH meter)

A pH meter is an electronic device used for measuring

the pH (acidity or alkalinity) of a liquid (though special probes are
sometimes used to measure the pH of semi-solid substances). A typical
pH meter consists of a special measuring probe (a glass electrode)
connected to an electronic meter that measures and displays the pH
reading.
For very precise work the pH meter should be calibrated before each
measurement. For normal use calibration should be performed at the
beginning of each day. The reason for this is that the glass electrode does
not give a reproducible e.m.f. over longer periods of time. Calibration
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should be performed with at least two standard buffer solutions that span
the range of pH values to be measured. For general purposes buffers at
pH 4.01 and pH 10.00 are acceptable. The pH meter has one control
(calibrate) to set the meter reading equal to the value of the first standard
buffer and a second control which is used to adjust the meter reading to
the value of the second buffer. A third control allows the temperature to be
set. Standard buffer sachets, which can be obtained from a variety of
suppliers, usually state how the buffer value changes with temperature.
For more precise measurements, a three buffer solution calibration is
preferred. As pH 7 is essentially, a "zero point" calibration (akin to zeroing
or taring a scale or balance), calibrating at pH 7 first, calibrating at the pH
closest to the point of interest (e.g. either 4 or 10) second and checking
the third point will provide a more linear accuracy to what is essentially a
non-linear problem. Some meters will allow a three point calibration and
that is the preferred scheme for the most accurate work. Higher quality
meters will have a provision to account for temperature coefficient
correction, and high-end pH probes have temperature probes built in. The
calibration process correlates the voltage produced by the probe
(approximately 0.06 volts per pH unit) with the pH scale. After each single
measurement, the probe is rinsed with distilled water or deionized water to
remove any traces of the solution being measured, blotted with a scientific
wipe to absorb any remaining water which could dilute the sample and
thus alter the reading, and then quickly immersed in another solution.

2.4 water Quality standards with respect to pH of water

Permissible = 6.5 to 8.5

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2.5 Treatment
Soda ash/sodium hydroxide injection
This treatment method is used if water is acidic (low pH). Soda ash (sodium
carbonate) and sodium hydroxide raise the pH of water to near neutral when injected
into a water system. Unlike neutralizing filters, they do not cause hardness problems
in treated water.
Injection systems are a point-of-entry system. A corrosion-resistant chemical feed
pump injects soda ash or sodium hydroxide solution into the water to raise the pH.
The solution should be fed directly into the well to protect the well casing and pump
from corrosion.
If the water needs to be disinfected as well as neutralized, dual treatment is possible
within the injection system by adding a chlorine solution (sodium hypochlorite) along
with the neutralizing chemical.
Injection systems can treat water with a pH as low as 4.

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3. Alkalinity
3.1 Definition
Alkalinity is the name given to the quantitative capacity of an aqueous
solution to neutralize an acid. Measuring alkalinity is important in determining a stream's
ability to neutralize acidic pollution from rainfall or wastewater.

3.2 Introduction
Alkalinity is a measure of the capacity of water or any solution to
neutralize or buffer acids. This measure of acid-neutralizing capacity is important in
figuring out how buffered the water is against sudden changes in pH.
Alkalinity should not be confused with pH. pH is a measure of the hydrogen ion (H+)
concentration, and the pH scale shows the intensity of the acidic or basic character
of a solution at a given temperature. The reason alkalinity is sometime confused with
pH is because the term alkaline is used to describe pH conditions greater than 7
(basic).
The most important compounds in water that determine alkalinity include the
carbonate (CO32-) and bicarbonate (HCO3-) ions. Carbonate ions are able to react
with and neutralize 2 hydrogen ions (H+) and the bicarbonate ions are able to
neutralize H+ or hydroxide ions (OH-) present in water. The ability to resist changes
in pH by neutralizing acids or bases is called buffering.
Alkalinity is important to aquatic organisms because it protects them against rapid
changes in pH. Alkalinity is especially important in areas where acid rain is a
problem.

Important Compounds for Alkalinity

H+

Hydrogen ion (acid)

OH-

Hydroxide ion (base)

H2CO3

Carbonic acid

HCO3-

Bicarbonate ion

CO32-

Carbonate ion

CaCO3

Calcium carbonate (calcite)

CaMg(CO3)2 Dolomite lime

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3.3 Sources
One source of alkalinity is calcium carbonate (CaCO3), which is dissolved in water
flowing through geology that has limestone and/or marble. Limestone is a
sedimentary rock formed by the compaction of fossilized coral, shells and bones.
Limestone is composed of the minerals calcium carbonate (CaCO3) and/or dolomite
(CaMg(CO3)2), along with small amounts of other minerals. Limestone is converted
to marble from the heat and pressure of metamorphic events.
Alkalinity can increase the pH (make water more basic), when the alkalinity comes
from a mineral source such as calcium carbonate (CaCO3). When CaCO3 dissolves
in water, the carbonate (CO32-) can react with water to form bicarbonate (HCO3-),
which produces hydroxide (OH-):
CaCO3 (s) Ca2+ + CO32CO32- + H2O HCO3- +OHThe hydroxide ion (OH-) is a strong base. An increase in OH- concentration will
cause the pH to increase.
In addition to rocks and soils, the alkalinity of streams can be influenced by:

salts,
plant activity, and
waste water.

Wastewater can have higher alkalinity because it typically has higher concentrations
of nutrients and ions, some with acid buffering properties, such as silicates and
phosphates.
Storm water runoff leading to streams can carry lime (either calcite or dolomite),
which is applied to lawns and agricultural fields. Clay soils naturally have an acidic
pH(~pH 4-6), and ammonia-based fertilizers produce acid as they are decomposed:
(NH4)2SO4 + 4 O2 2 HNO3 + H2SO4 + 2 H2O
Lime is often added to increase soil pH and buffer soil and fertilizer acids.
In watersheds where calcium carbonate isnt available, carbonic acid is an important
source for carbonate and bicarbonate. Carbon dioxide and water are converted to
carbonic acid through the following reaction:
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CO2 + H2O H2CO3 (carbonic acid)

Carbonic acid provides bicarbonate and carbonate for buffering, just like CaCO 3:
H2CO3 HCO3- + H+
HCO3- CO32- + H+

While conversion of carbon dioxide to carbonic acid produces ions capable of

buffering pH, it also causes a decrease in pH (increase in H+) that CaCO3 doesnt.
Notice in the reaction that as carbonic acid (H2CO3) reacts to form carbonate (CO32-),
2 hydrogen ions H+) are released into the water.

Typical Alkalinity Ranges

(mg/L CaCO3)
Rainwater

< 10

Typical surface water

20 - 200

Surface water in regions with alkaline soils 100 - 500

Groundwater

50 - 1000

Seawater

100 - 500

3.4 Measurement of alkalinity

1. Clean the burette and fill almost to the top with N/50 sulfuric acid. Then
run some acid to waste until the "zero" mark is reached. This should leave
the stopcock and tip of the burette full of the solution.
2. Measure out 100 mL of the water to be tested and pour into a clean white
porcelain evaporating dish. Stir the sample.
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3. With a dropping bottle, add 5 drops of phenolphthalein indicator to the

sample and stir. When phenolphthalein alkalinity is present, the solution
becomes pink. No color indicates the phenolphthalein alkalinity is zero and
that the test is complete. No color also indicates that free carbon dioxide is
present, and the same sample may be used to test for carbon dioxide.
4. If pink color results after the indicator is added, slowly and carefully add
N/50 sulfuric acid from the burette to the contents of the dish until the
coloration disappears. While adding the acid, the solution should be gently
stirred with the stirring rod.
5. Record the volume of sulfuric acid used to reach the endpoint.
6. Calculate the phenolphthalein alkalinity, in ppm, as follows:
P. alk. = (mL of acid) (10 ppm/mL)
For example, if 2.4 mL of acid were used, the phenolphthalein alkalinity would be:
P. alk. = (2.4) (10) = 24 ppm CaCO3

3.5 Water quality standard with respect to alkalinity

Desirable= <200 mg/lit as caco3
Permissible=< 600mg/lit as caco3

3.6 Treatment

Alkalinity is of little sanitary significance, although extremely high levels of alkalinity

in water can be problematic. It has been reported that a carbonate concentration of
350 ppm is unhealthy. In addition, free caustic (hydroxide) alkalinity may impart a
bitter taste to the water and can even cause a burning sensation at high
concentrations. However, in most water treatment plants, operators are more
concerned with ensuring that there is enough alkalinity in the water to promote
coagulation and prevent corrosion than they are with removing alkalinity from water.
Alkalinity is essential for proper coagulation. When alum is added to raw water, the
alum reacts with the alkalinity present to form floc. As a rule of thumb, coagulation
usually requires an alkalinity equal to half of the amount of alum used. So, if your
plant treats raw water with 25 ppm of alum, then a minimum of 12.5 ppm of alkalinity
must be present in the water for floc to form. If insufficient alkalinity is present in the
water during coagulation, then dense floc with not form and soluble alum will be left
in the water.
Since coagulation uses up alkalinity in the water, treated water often tends to be
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corrosive (acidic). The operator must make sure that an adequate amount of
alkalinity is present in the treated water as well as in the raw water to prevent
corrosion of pipes in the distribution system. We will discuss the math used to
determine the appropriate alkalinity of treated water in the alkalinity lab.
Water treatment may require the addition of artificial alkalinity to enhance
coagulation or to prevent corrosion. If the source water does not contain an
adequate amount of natural alkalinity, treatment will usually include the addition of
lime or soda ash to artificially increase the amount of alkalinity in the water.

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4. Hardness
4.1 Definition
Calcium and magnesium dissolved in water are the two most common minerals
that make water "hard." The hardness of water is referred to by three types of
measurements: grains per gallon, milligrams per liter (mg/L), or parts per million (ppm).

4.2 Introduction
Hard drinking water is generally not harmful to one's health, but can pose serious
problems in industrial settings, where water hardness is monitored to avoid costly
breakdowns in boilers, cooling towers, and other equipment that handles water. In
domestic settings, hard water is often indicated by a lack of suds formation
when soap is agitated in water, and by the formation of limescale in kettles and water
heaters. Wherever water hardness is a concern, water softening is commonly used
to reduce hard water's adverse effects
.

4.3 Sources

Water's hardness is determined by the concentration of multivalent cations in the water.

Multivalent cations are cations (positively charged metal complexes) with a charge greater than
1+. Usually, the cations have the charge of 2+. Common cations found in hard water include
Ca2+ and Mg2+. These ions enter a water supply by leaching from minerals within an aquifer.
Common calcium-containing minerals are calcite and gypsum. A common magnesium mineral
is dolomite (which also contains calcium). Rainwater and distilled water are soft, because they
contain few ions.
The following equilibrium reaction describes the dissolving and formation of calcium carbonate :
CaCO3 (s) + CO2 (aq) + H2O (l) Ca2+ (aq) + 2HCO3 (aq)
The reaction can go in either direction. Rain containing dissolved carbon dioxide can react
with calcium carbonate and carry calcium ions away with it. The calcium carbonate may be
re-deposited as calcite as the carbon dioxide is lost to atmosphere, sometimes
forming stalactites and stalagmites.
Calcium and magnesium ions can sometimes be removed by water softeners

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4.4 Types of hardness

Temporary hardness
Temporary hardness is a type of water hardness caused by the presence
of dissolved bicarbonate minerals (calcium bicarbonate and magnesium
bicarbonate). When dissolved these minerals yield calcium and
magnesium cations (Ca2+, Mg2+) and carbonate and bicarbonate anions (CO32-,
HCO3-). The presence of the metal cations makes the water hard. However, unlike
the permanent hardness caused by sulfate and chloride compounds, this
"temporary" hardness can be reduced either by boiling the water, or by the addition
of lime (calcium hydroxide) through the softening process of lime softening.[4] Boiling
promotes the formation of carbonate from the bicarbonate and precipitates calcium
carbonate out of solution, leaving water that is softer upon cooling.

Permanent hardness
Permanent hardness is hardness (mineral content) that cannot be removed
by boiling. When this is the case, it is usually caused by the presence of calcium
sulfate and/or magnesium in the water, which do not precipitate out as
the temperature increases. Ions causing permanent hardness of water can be
removed using a water softener, or ion exchange column.
Total Permanent Hardness = Calcium Hardness + Magnesium Hardness
The calcium and magnesium hardness is the concentration of calcium and
magnesium ions expressed as equivalent of calcium carbonate.
Total permanent water hardness expressed as equivalent of CaCO3 can be
calculated with the following formula: Total Permanent Hardness (CaCO3) =
2.5(Ca2+)

4.5 Effects of hard water

With hard water, soap solutions form a white precipitate (soap scum) instead of
producing lather, because the 2+ ions destroy the surfactant properties of the soap
by forming a solid precipitate (the soap scum). A major component of such scum
is calcium stearate, which arises from sodium stearate, the main component of soap:
2 C17H35COO- (aq) + Ca2+ (aq) (C17H35COO)2Ca (s)
Hardness can thus be defined as the soap-consuming capacity of a water
sample, or the capacity of precipitation of soap as a characteristic property of
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water that prevents the lathering of soap. Synthetic detergents do not form such
scums.

A portion of the ancient Roman Eifel aqueduct in Germany. In service for about
180 years, a deposit of scale up to 20cm thick built up within it.
Hard water also forms deposits that clog plumbing. These deposits, called
"scale", are composed mainly of calcium carbonate (CaCO3),magnesium
hydroxide (Mg(OH)2), and calcium sulfate (CaSO4).[2] Calcium and magnesium
carbonates tend to be deposited as off-white solids on the inside surfaces of
pipes and heat exchangers. This precipitation (formation of an insoluble solid) is
principally caused by thermal decomposition of bicarbonate ions but also
happens in cases where the carbonate ion is at saturation concentration. The
resulting build-up of scale restricts the flow of water in pipes. In boilers, the
deposits impair the flow of heat into water, reducing the heating efficiency and
allowing the metal boiler components to overheat. In a pressurized system, this
overheating can lead to failure of the boiler.The damage caused by calcium
carbonate deposits varies on the crystalline form, for
example, calcite or aragonite.[7]
The presence of ions in an electrolyte, in this case, hard water, can also lead
to galvanic corrosion, in which one metal will preferentially corrode when in
contact with another type of metal, when both are in contact with an electrolyte.
The softening of hard water by ion exchange does not increase its corrosivity per
se. Similarly, where lead plumbing is in use, softened water does not
substantially increase plumbo-solvency.
In swimming pools, hard water is manifested by a turbid, or cloudy (milky),
appearance to the water. Calcium and magnesium hydroxides are both soluble in
water. The solubility of the hydroxides of the alkaline-earth metals to which
calcium and magnesium belong (group 2 of the periodic table) increases moving
down the column. Aqueous solutions of these metal hydroxides absorb carbon
dioxide from the air, forming the insoluble carbonates, giving rise to the turbidity.
This often results from the pH being excessively high (pH > 7.6). Hence, a
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common solution to the problem is, while maintaining the chlorine concentration
at the proper level, to lower the pH by the addition of hydrochloric acid, the
optimum value being in the range of 7.2 to 7.6

4.6 Measurement of hardness

1. Take 50ml of water sample in conical flask.

2. Add 1ml of buffer solution (Aluminum Hydroxide n Ammonium Chloride) of
hardness1.
3. Add 3 drops of ferrochrome black tea to the flask and shake well.
4. Place the flask below the burette containing EDTA (Ethylene diamine tetraacitic acid) solution of 0.02 normality.
5. Note the initial reading of the burette and open the tape of the burette to allow
the solution to flow in the flask.
6. Note The Final Reading when the color of the water in the flask turn bluish.
7. The total harness (temporary + permanent hardness) is found by using the
following formula.

4.7 Water quality standard with respect to hardness

Desirable = 300 mg/lit
Permissible = 600 mg/lit

4.8 Treatment

The most common means for removing water hardness rely on ion-exchange
polymers or reverse osmosis. Other approaches include precipitation methods and
sequestration by the addition of chelating agents. Devices which
use magnetism or electrolysis as a water softening technique claim to inhibit scale
buildup without actually removing hardness ions from the water. Such devices have
been marketed to consumers since the early 20th century, but are fraudulent.

Ion-exchange resin devices

Conventional water-softening appliances intended for household use depend on
an ion-exchange resin in which "hardness ions" - mainly Ca2+ and Mg2+ - are
exchanged for sodium ions. As described by NSF/ANSI Standard 44 ion exchange

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devices reduce the hardness by replacing magnesium and calcium (Mg2+ and Ca2+)
with sodium or potassium ions (Na+ and K+)."

Ion exchange resins, in the form of beads, are a functional component of domestic
water softening units.
Types of ion exchange materials
Ion exchange resins are organic polymers containing anionic functional groups to
which the dications (Ca++) bind more strongly than monocations (Na+). Inorganic
materials called zeolites also exhibit ion-exchange properties. These minerals are
widely used in laundry detergents. Resins are also available to remove carbonate,
bi-carbonate and sulphate ions which are absorbed and hydroxide ions released
from the resin.
Regeneration of ion exchange resins
When all the available Na+ ions have been replaced with calcium or magnesium
ions, the resin must be re-charged by eluting the Ca2+ and Mg2+ ions using a solution
of sodium chloride or sodium hydroxide depending on the type of resin used.[6] For
anionic resins, regeneration typically uses a solution of sodium hydroxide (lye) or
potassium hydroxide. The waste waters eluted from the ion exchange column
containing the unwanted calcium and magnesium salts are typically discharged to
the sewage system.

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5.0 Chlorides

5.1 Definition
Chloride, in the form of the Cl ion, is one of the major inorganic anions, or negative
ions, in saltwater and freshwater. It originates from the dissociation of salts, such as
sodium chloride or calcium chloride, in water.

NaCl(s) ----> Na+(aq) + Cl(aq)

CaCl2(s) ----> Ca2+(aq) + 2 Cl(aq)

5.2 Introduction

These salts, and their resulting chloride ions, originate from natural
minerals, saltwater intrusion into estuaries, and industrial pollution.
There are many possible sources of manmade salts that may contribute to
elevated chloride readings. Sodium chloride and calcium chloride, used to
salt roads, contribute to elevated chloride levels in streams. Chlorinated
drinking water and sodium-chloride water softeners often increase chloride
levels in wastewater of a community.
In drinking water, the salty taste produced by chloride depends upon the
concentration of the chloride ion. Water containing 250 mg/L of chloride
may have a detectable salty taste if the chloride came from sodium
chloride. The recommended maximum level of chloride in U.S. drinking
water is 250 mg/L.

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5.3 Sources of chlorides in water

Some sources of Chloride Ions

River streambeds with salt-containing minerals
Runoff from salted roads
Mixing of seawater with freshwater
The Use of Water softeners
Irrigation water returned to streams
Chlorinated drinking water

Salinity is the total of all non-carbonate salts dissolved in water, usually

expressed in parts per thousand (1 ppt = 1000 mg/L). Unlike chloride (Cl)
concentration, salinity is a measure of thetotal salt concentration,
comprised mostly of Na+ and Cl ions. Even though there are smaller
quantities of other ions in seawater (e.g., K+, Mg2+, or SO42), sodium and
chloride ions represent about 91% of all seawater ions. Salinity is an
important measurement in seawater or in estuaries where freshwater from
rivers and streams mixes with salty ocean water. The salinity level in
seawater is fairly constant, at about 35 ppt (35,000 mg/L), while brackish
estuaries may have salinity levels between 1 and 10 ppt. Since most
anions in seawater or brackish water are chloride ions, salinity can be
determined from chloride concentration. The following formula is used:
salinity (ppt) = 0.0018066 5 Cl (mg/L)

A Chloride Ion-Selective Electrode can be used to determine the chloride

concentration, which is converted to a salinity value using the above
formula.
Salinity can also be measured in freshwater. Compared to seawater or
brackish water, freshwater has much lower levels of salt ions such as
Na+ and Cl; in fact, these ions are often lower in concentration than hardwater ions such calcium (Ca2+) and bicarbonate (HCO3). Because salinity
readings in freshwater will be significantly lower than in seawater or
brackish water, readings are often expressed in mg/L instead of ppt (1 ppt
= 1000 mg/L).
Salinity is also of interest in bodies of water where seawater mixes with
freshwater, since aquatic organisms have varying abilities to survive and
thrive at different salinity levels. Saltwater organisms survive in salinity

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levels up to 40 ppt, yet many freshwater organisms cannot live in salinity

levels above 1 ppt.

5.4 Measurement of chlorides

Mohr method of determination of chlorides by titration with silver nitrate is one of the
oldest titration methods still in use - it was researched and published by Karl
Friedrich Mohr in 1856.
The idea behind is very simple - chlorides are titrated with the silver nitrate solution
in the presence of chromate anions. End point is signalled by the appearance of the
red silver chromate.
Intense yellow color of chromate may make detection of first signs of formation of red
silver chromate precipitation difficult. As some excess of silver must be added before
precipitate starts to form, if concentration of titrant is below 0.1M, we may expect
singificant positive error. To correct for this error we can determine a blank, titrating a
solution of the indicator potassium chromate with standard silver nitrate solution. To
make result more realistic we can add small amount of chloride free calcium
carbonate to the solution to imitate the white silver precipitate.
Solution during titration should be close to neutral. In low pH silver chromate
solubility grows due to the protonation of chromate anions, in high pH silver starts to
react with hydroxide anions, precipitating in form of AgOH and Ag2O. Both processes
interfere with the determination accuracy.
Exactly the same approach can be used for determination of bromides. Other halides
and pseudohalides, like I- and SCN-, behave very similarly in the solution, but their
precipitate tends to adsorb chromate anions making end point detection difficult.

Reaction taking place during titration is

Ag+ + Cl- AgCl(s)
Assuming 0.1M titrant concentration and 50 mL burette, aliquot taken for titration
should contain about 0.12-0.16 g chloride anion (3.5-4.5 millimoles).

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Before titration small amount of sodium or potassium chromate is added to the

solution, making its slightly yellow in color. During titration, as long as chlorides are
present, concentration of Ag+ is too low for silver chromate formation. Near
equivalence point concentration of silver cations rapidly grows, allowing precipitation
of intensively red silver chromate which signalls end point.

Pipette aliquot of chlorides solution into 250mL Erlenmeyer flask.

Dilute with distilled water to about 100 mL.

Add 1 mL of 5% potassium chromate solution.

Titrate with silver nitrate solution till the first color change.

5.5 Water quality standard with respect to chlorides

Desirable = 250 mg/lit
Permissible = 1000 mg/lit

5.6 Treatment (Reverse Osmosis)

RO is based on the principle of osmosis. In osmosis, a membrane separates two

solutions containing different amounts of dissolved chemicals. The membrane allows
some compounds like water to pass through it, but does not allow larger compounds
through (i.e., a semipermeable membrane). Pressure differences cause pure water
to pass through the membrane from the dilute to the more concentrated solution.
The pressure is called osmotic pressure and this process is osmosis. The natural
tendency is for water to move through the membrane from the dilute to the
concentrated solution until chemicals reach equal concentrations on both sides of
the membrane. Figure 1 shows the natural osmotic process.
In reverse osmosis, pressure is applied to the concentrated side of the membrane
(the contaminated side). This forces the osmotic process into reverse so that, with
adequate applied pressure, pure water is forced from the concentrated
(contaminated) side to the dilute (treated) side. Treated water is collected in a
storage container. The rejected contaminants on the concentrated side of the
membrane are washed away as wastewater. Figure 2 shows the reverse osmosis
process.
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The amount of treated water that an RO membrane typically used in the home can
produce, per day, is in the range of 10 to 35 gallons per day. The amount of treated
water produced depends on several factors, including membrane type and condition,
operating conditions (such as flow control and pressure) and feed water quality (i.e.,
contaminant concentration, temperature, and pH).
Two measures of performance of an RO membrane are recovery rate and rejection
rate. Recovery rate refers to the fact that only part of the water that flows into an RO
system comes out as treated water. Part of the water fed into the system is used as
wastewater to wash away the rejected contaminants. The recovery rate is therefore
a measure of efficiency calculated as:
% Recovery = (Volume of treated water produced / Total volume of feed water) x 100
The use of large quantities of water to produce little treated water may be avoided by
properly designed RO systems. Most household RO systems are designed with a 20
percent - 30 percent recovery rate.
This means that a system with 100 gallons/day of untreated water fed to it and a 20
percent recovery rate would yield 20 gallons/day of treated water and dispose of 80
gallons/day in the waste stream. Proper adjustment of the flow regulator on the side
of the waste stream is important. If the flow of wastewater is slow, more time is
available for water to pass through the membrane, so the recovery rate is higher.
However, RO membranes are readily fouled if concentrated contaminants are not
washed away soon enough. Conversely, if the waste flow rate is too fast, the
recovery rate is low and excessive water flows down the drain.
Closely related to flow rate, water pressure is another key factor in RO systems. The
incoming feed line pressure must be adequate to overcome the osmotic pressure
and any back pressure generated from the storage tank down-line from the
membrane. Auxiliary pumps can be added to increase incoming water pressure as
necessary. Generally, the higher the pressure difference across the membrane the
better the rejection of contaminants and recovery rate. Also, some RO systems have
shut off valves to stop flow whenever storage tank pressure is too high for efficient
recovery or if the storage tank is full.

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Temperature and pH of the feed water are also factors in performance. There is a 1
to 2 percent decrease in treated water produced for every degree below the standard
77F. Well water at 45F (a typical temperature for Nebraska groundwater) would
produce about half the amount of treated water that would be produced at 77F.
Also, slightly acidic feed water may prolong the life of the membrane and help
decrease scale buildup in the system.
The rejection rate is the percentage of contaminant that is not allowed to move
through the membrane. A rejection rate is calculated for each contaminant
separately, as well as for Total Dissolved Solids (TDS). For contaminants that cause
health concerns, the rejection rate needs to be high enough to reduce the
contaminant to a safe level. The quality of the incoming water, or feed water, is
crucial here. For example, if the water supply contains nitrate at 40 mg/L, an RO
membrane with 85 percent rejection would reject 40 x 0.85 = 34 mg/L nitrate, leaving
6 mg/L in the treated water.
However, if the water supply contains 80 mg/L nitrate, an 85 percent rejection rate
would reduce the nitrate concentration to 12 mg/L in the treated water. This nitrate
level, even after RO treatment, is above the maximum contaminant level (MCL) of 10
mg/L nitrate set by the EPA.
Equipment
Treatment systems can be classified as either Point-of-Use (POU) or Point-of-Entry
(POE). POU devices treat water at the point it is used, such as the faucet. Most RO
systems are POU systems placed under the sink or on the countertop. A separate
faucet is generally installed at the sink to allow the option of using treated water only
for drinking and cooking. Water treated by RO can be more corrosive than untreated
water so special plumbing, in addition to the faucet, is installed with RO systems.

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POE devices treat water as it

enters the household so all water
used within the house is treated.
POE reverse osmosis units are
more costly to purchase, install
and operate than POU systems.
Although the RO process is
simple, the complete system is
often complex. Typical RO
systems consist of a pretreatment

Figure 3. A schematic of a typical RO system.

filter, the RO membrane, flow

From Water Treatment Notes: Reverse

regulator, post-treatment filter,

Osmosis Treatment of Drinking

storage tank and dispensing

Water, Cornell Cooperative Extension, New

faucet as shown in Figure 3. AC or

York State College of Human Ecology.

sediment filters before the RO membrane and AC filters after the RO membrane are
commonly used. Pre-filters help extend the life of the system by removing silt and
other large particles and/or chlorine that may be harmful to the RO membrane. If the
feed water is not chlorinated, AC filters should not be used for pre-filtration because
they can encourage microbial growth on the membrane surface. In this case, only a
sediment pre-filter is recommended. AC post-filters can also remove certain
pesticides and organic solvents that the RO membrane does not remove. The AC
treatment process is also improved since the RO membrane removes compounds
that may hinder adsorption by the carbon.
Membrane selection is an important aspect of RO treatment that can significantly
affect performance. RO membranes are generally made of thin film composite
(TFC), cellulose acetate (CA), or cellulose triacetate (CTA). TFC membranes have
better durability as well as generally higher rejection rates than CA/CTA membranes.
All are synthetic fibers.
TFC membranes are more costly, but have greater strength and durability than
cellulose-types. They have higher total dissolved solids rejection rates, are more
resistant to microbial attack, and are more tolerant of high pH. Cellulose type
membranes are less costly and can tolerate chlorine, which is commonly used for
disinfection of drinking water. TFC membranes deteriorate in chlorinated water. If the
feed water is chlorinated and a TFC membrane is used, an AC prefilter is needed to
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remove chlorine from the water. The membrane can be spiral wound (like a rolled-up
newspaper), or individual hollow fibers can be bundled together. This provides a very
large surface area for water treatment within a compact tube element.
The storage tank generally has a capacity of 2 to 5 gallons. It is pressurized to
provide adequate flow when the tap is open. Post-filters can be used for removing
any taste and odor compounds or residual organics not removed by the RO process.
If an AC filter is used for pre-filtration, post-filtration can be eliminated.
Monitoring gauges and lights are also becoming increasingly common. Shut-off
valves are important to stop water flow when the storage tank is full, so excess water
is not wasted. Since RO treatment uses significant amounts of water, consideration
must be given to the adequacy of the household septic system. The wastewater,
carrying rejected contaminants, typically is connected to a household drain and this
wastewater increases the load on the septic system.
As with any drinking water treatment system, regular maintenance is important to
extend the life of the system and to help ensure peak performance. Pre-filters and
post-filters require regular replacement. The length of time before prefilter
replacement depends upon water volume, quality and contaminant concentration.
Post-filter replacement also depends on contaminant concentration, as well as
membrane rejection percentages and AC removal efficiency. Manufacturers and
dealers can assist in determining replacement intervals.
Microorganisms (alive or dead) can clog RO membranes. This is called bio-fouling.
Disinfect RO systems regularly with products provided by the manufacturer. Clogged
RO membranes can decrease water flow in the system and cause poor
performance. If membrane fouling is detected early, it is possible to clean and
regenerate the membrane; the method depends on the type of membrane and
fouling. Completely clogged or torn membranes require replacement. However,
damaged RO membranes are not easily detected. Periodically test water to
determine if the membrane is intact and functioning properly. For relatively hard
water, pretreatment of the water by a softener can increase the life of the membrane.
Many systems are equipped with a monitor that indicates high total dissolved solids
content or inadequate TDS rejection, one indicator of improper functioning. Other
monitors measure the cumulative water treated since the membrane was last
replaced, another indicator of expected membrane life.
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6. Dissolved Oxygen (DO)

6.1 Definition
Dissolved oxygen refers to the level of free, non-compound oxygen present
in water or other liquids. It is an important parameter in assessing water quality because
of its influence on the organisms living within a body of water.

6.2 Introduction

Every animal living in the lake needs dissolved oxygen in order to breathe, or
respire. That is why scientists keep a close eye on the level of dissolved
oxygen in the lake using dissolved oxygen probes. These probes have
specialized receptors that record a measurement every time an oxygen
molecule passes through the membrane and comes in contact with the
receptor. The deep, hypolimnion layer, becomes anoxic during certain times
of the year meaning that the bacteria at the bottom of the lake use up all of
the oxygen. This can cause fish kills during the winter, when the lake is
covered with ice. The layer of ice blocks the transport of oxygen from the
atmosphere to the water. The epilimion, or top layer, can become
supersaturated. This means that the water in that layer can hold more oxygen
than usual. If you see a value of more than 100% for Dissolved Oxygen in
this dataset, it means that the water is supersaturated. The middle layer, or
metalimnion, is usually under-saturated, meaning that there is less oxygen
present than it is capable of having. The middle layer has less oxygen than
the top layer because it lacks the influence of wind; it pushes oxygen into the
water. Plants play a critical role in pumping oxygen back into the water
through photosynthesis.

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6.3 Sources
Oxygen dissolves into water from two sources: the atmosphere and from plants
in the water. The primary source of oxygen for a pond is from microscopic algae
(phytoplankton) or submerged plants. In the presence of sunlight, these produce oxygen
through photosynthesis and release this oxygen into the pond water.

6.4 Measurement of Dissolved Oxygen (DO)

Dissolved Oxygen Meter

A DO meter consists of a probe filled with potassium chloride and covered with a
semi-permeable membrane, a wire carrying electricity, and two electrodes. When
the probe is placed in the water, the potassium chloride attracts oxygen, just as
hemoglobin does in our blood, and pulls the oxygen out of the water and into the
probe. The semi-permeable membrane allows oxygen to pass into the probe but
does not allow water in.
The probe is connected to a wire through which DC electricity flows (the red dashes
in the drawing above.) There is a gold and a silver electrode on the wire, one on
either side of the probe. You can think of these electrodes as devices which
measure the amount of electricity passing through the wire at that point.
Where the probe joins the wire, oxygen mingles with the electricity. Oxygen is not
very ionized, meaning that it does not have a negative charge as electricity does, so
the oxygen dilutes the current at the electrode beyond the probe. The meter
measures the difference in current between the two electrodes and uses that
difference to determine the amount of oxygen in the water.
When using a DO meter, the meter must be properly cared for. The membrane must
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be kept wet and have potassium chloride solution within it at all times. The electrode
should also be maintained. The electrode assembly can be cleaned by dipping the
electrode tip into ammonium hydroxide.
The meter must also be calibrated before use to ensure that the reading is
accurate. The meter can be calibrated using water with a known concentration of
DO at at set temperature. This can be done by filling a biological oxygen demand
(BOD) bottle halfway full of distilled water. The water is shaken vigorously to
saturate the water with air. Then the probe is placed in the bottle and the reading is
adjusted to the known concentration of DO in the bottle. Alternatively, the meter can
be calibrated using the Winkler method, which involves adding chemicals to the
water and forming a precipitate.

Modified Winkler Dissolved Oxygen Determination

In the modified Winkler method, various chemicals are added to the water
sample. Then PAO or Sodium Thiosulfate is titrated into the sample.
The dissolved oxygen concentration can be calculated based on the amount of titrant
added to the sample. The formula used is:

BuretFinal is the reading of the buret after titration and BuretStart is the reading of the
buret at the beginning of titration. N is the normality of the solution used to titrate the
sample.
If a 200 mL sample and a 0.025 N titrant are used, then the formula can be simplified
to:
DO (mg/L) = Amount of Titrant Used (mL)
Example: The operator titrates a 200 mL dissolved oxygen sample. The buret
reading at the start of the titration was 0.0 mL. At the end of the titration the buret
read 7.4 mL. The concentration of the titrating solution was 0.025 N. What is the
D.O. concentration in mg/L?

6.5 Water quality standards with respect to dissolved oxygen

Desirable = 6mg/lit
Permissible = >4mg/lit
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6.6 Treatment (Aeration)

Aeration is the process of bringing water and air into close contact in order
to remove dissolved gases, such as carbon dioxide, and to oxidize dissolved metals
such as iron. It can also be used to remove volatile organic chemicals (VOC) in the
water. Aeration is often the first major process at the treatment plant. During
aeration, constituents are removed or modified before they can interfere with the
treatment processes.

TYPES OF AERATORS
Aerators fall into two general categories. They either introduce air into the water or water into
the air. The water-to-air method is designed to produce small drops of water that fall through
the air. The air-to-water method creates small bubbles of air that are injected into the water
stream. All aerators are designed to create a greater amount of contact between the air and
water to enhance the transfer of the gases.

WATER INTO AIR

Cascade Aerators
A cascade aerator consists of a series of steps that the water flows over. In all cascade
aerators, aeration is accomplished in the splash zones. The aeration action is similar to a
flowing stream. Splash areas are created by placing blocks across the incline. Cascade
aerators can be used to oxidize iron and to partially reduce dissolved gases. They are the
oldest and most common type of aerators.

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Cone Aerators
Cone aerators are used primarily to oxidize iron and manganese from the ferrous state to the
ferric state prior to filtration. The design of the aerator is similar to the cascade type, with the
water being pumped to the top of the cones and then being allowed to cascade down through
the aerator.

Slat and Coke Aerators

The slat and coke trays are similar to the cascade and cone types. They usually consist of
three-to-five stacked trays, which have spaced wooden slats in them. The trays are filled with
fist-sized pieces of coke, rock, ceramic balls, limestone, or other materials. The primary
purpose of the materials is to provide additional surface contact area between the air and
water.

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Draft Aerators
A draft aerator is similar to the others except that the air is induced by a blower. There are
two basic type of draft aerators. One has external blowers mounted at the bottom of the tower
to induce air from the bottom of the tower. Water is pumped to the top and allowed to
cascade down through the rising air. The other, an induced-draft aerator, has a top-mounted
blower forcing air from bottom vents up through the unit to the top. Both types are effective
in oxidizing iron and manganese before filtration.

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Spray Aerators
This type of aerator has one or more spray nozzles connected to a pipe manifold. Moving
through the pipe under pressure, the water leaves each nozzle in a fine spray and falls through
the surrounding air, creating a fountain affect. In general, spray aeration is successful in
oxidizing iron and manganese and is successful in increasing the dissolved oxygen of the
water.

AIR INTO WATER

These are not common types used in water treatment. The air is injected into the water
through a series of nozzles submerged in the water. It is more commonly used in wastewater
treatment for the aeration of activated sludge.

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Pressure Aerators
There are two basic types of pressure aerators. One uses a pressure vessel. The water to be
treated is sprayed into the high-pressure air, allowing the water to quickly pick up dissolved
oxygen.
A pressure aerator commonly used in pressure filtration is a porous stone installed in a
pipeline before filtration. The air is injected into the stone and allowed to stream into the
water as a fine bubble, causing the iron to be readily oxidized.
The higher the pressure, the more readily the transfer of the oxygen to the water.
The more oxygen that is available, the more readily the oxidation of the iron or manganese.

AIR STRIPPING
If operated properly, a process called air stripping can be quite effective in removing volatile
organic chemicals (VOCs) from water. The presence of VOCs, many of which are man-made
or formed during industrial processes, is increasingly becoming a problem for public water
suppliers. US EPA has set Maximum Contaminant Levels for many VOCs (see the Public
Water Supply Regulation chapter). A major concern is that VOCs may be carcinogens.
Example of VOCs are benzene from gasoline and trichloroethylene from dry cleaning
establishments.
Air stripping has been shown to be capable of removing up to 90 percent of the most highly
volatile VOCs. It can be accomplished by letting the water flow over cascade aerators or in
specially designed air-stripping towers. In these, water is allowed to flow down over a
support medium or packing contained in the tower, while air is being pumped into the bottom
of the tower.

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References
1. water.usgs.gov/edu/Introduction.html
2. IS 10500-2012, Water quality standards, Bureau of indian standards, New delhi
india.
3. World Health Organisation; Guidelines for Drinking-water Quality 2011, Fourth
Edition
4. Diersing, Nancy (2009). "Water Quality: Frequently Asked Questions." Florida
Brooks National Marine Sanctuary, Key West, FL.
5. Babbitt, Harold E. & Doland, James J. Water Supply Engineering (1949)
McGraw-Hill p.388
6. World Health Organization (2004). "Consensus of the Meeting: Nutrient minerals
in drinking-water and the potential health consequences of long-term consumption of
demineralized and remineralized and altered mineral content drinkingwaters." Rolling Revision of the WHO Guidelines for Drinking-Water Quality
(draft). From November 1113, 2003 meeting in Rome, Italy at the WHO European
Centre for Environment and Health
7. World Health Organization (2011). "WHO technical notes for emergencies." Water
Engineering Development Centre, Loughborough University, Leicestershire, UK.
8. Linsley, Ray K. & Franzini, Joseph B. Water-Resources Engineering, (1972)
McGraw-HillISBN 0-07-037959-9 pp.454-456
9. Peavy, H. S., Rowe, D. R. and Tchobanoglous, G., Environmental Engineering,
McGraw-Hil International Ed., 1985.

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