MUST DO TOPICS

UNIT-3
• Water

• Physical, chemical and biological characteristics

• EDTA method

• Caustic embrittlement

• Priming and Foaming

• Carbonate and Phosphate conditioning

• Calgon conditioning

• All external treatment (Lime soda process, Zeolite process and Ion-exchange process)

• Disinfection and Disinfectant

• Reverse Osmosis

• Electrodialysis
The Physical parameters include color, taste, odor, temperature, turbidity, solids, and electrical
conductivity. On the other hand, Chemical parameters can include pH, acidity, alkalinity,
chlorine, hardness, dissolved oxygen, and biological oxygen demand. Biological parameters
include bacteria, algae and viruses.

1) EDTA or its sodium salt forms stable complex ion with Ca2+ or Mg2+( hardness producing
ions ) in water. The titration is carried out in presence of indicator such as Eriochrome Black T (
EBT ) .

2) In a hard water sample ,the total hardness can be determined by titrating Ca2+ and Mg +
present in an aliquot of the sample with Na EDTA solution ,using NH4Cl , NH40H buffer
solution of pH = 10 and the metal indicator EBT

3)At pH 10 ,EBT indicator forms wine red coloured unstable complex with Ca2+ or Mg2+ ions
in hard water .

4)When EDTA is added from burette to this wine red complex ,there is formation of more stable
Ca-EDTA but colourless complex . Near the end point , when all Ca ions get complexed with
EDTA ,indicator EBT ions set free giving blue colour to the solution .

Caustic embrittlement is the phenomenon during which the boiler material becomes brittle due
to the accumulation of caustic substances. This type of boiler corrosion is caused by the use of
highly alkaline water in the high pressure boiler.

Caustic embrittlement can be prevented through several measures such as, Managing the
temperature and potential. Managing the Hardness and stress level- residual or load. Avoiding
the use of alkalis. Utilizing material that does not crack when used in a caustic environment.

Foaming: Boiler water carry-over is the contamination of the steam with boiler-water solids.
Bubbles or froth actually build up on the surface of the boiler water and pass out with the steam.
This is called foaming and it is caused by high concentration of any solids in the boiler water. It
is generally believed, however, that specific substances such as alkalis, oils, fats, greases, certain
types of organic matter and suspended solids are particularly conducive to foaming. In theory
suspended solids collect in the surface film surrounding a steam bubble and make it tougher. The
steam bubble therefore resists breaking and builds up foam. It is believed that the finer the
suspended particles the greater their collection in the bubble.

Priming: is the carry over of varying amounts of droplets of water in the steam (foam and mist),
which lowers the energy efficiency of the steam and leads to the deposit of salt crystals on the
super heaters and in the turbines. Priming may be caused by improper construction of boiler,
excessive ratings, or sudden fluctuations in steam demand. Priming is sometimes aggravated by
impurities in the boiler-water.

Some mechanical entrainment of minute drops of boiler water in the steam always occurs. When
this boiler water carryover is excessive, steam-carried solids produce turbine blade deposits. The
accumulations have a composition similar to that of the dissolved solids in the boiler water.
Priming is common cause of high levels of boiler water carryover. These conditions often lead to
super heater tube failures as well. Priming is related to the viscosity of the water and its tendency
to foam. These properties are governed by alkalinity, the presence of certain organic substances
and by total salinity or TDS. The degree of priming also depends on the design of the boiler and
its steaming rate.

Carbonate conditioning is used in Iow pressure boilers. In this method, sodium carbonate
solution is added to convert the calcium ions to soft and loose sludge. Soft CaC03 is formed
which is removed by blow down operation. Scale formation can be avoided by adding sodium
carbonate to boiler water.

CaS04+Na2C03+ CaC03+Na2S04

ADVANTAGES

• The scale forming salt like CaS04 is converted into CaC03 which can be removed easily.

• effective.

• good tolerability

LIMITATIONS:

• Only applicable to low pressure boilers.

• effectiveness is influenced by pH value.

• gastrointestinal complaint.

• in some circumstances influence on vascular calcification.

• Excess of can cause caustic embrittlement.

Why phosphate conditioning is preferred over carbonate conditioning?

Phosphate conditioning is used for both acidic and alkaline water in high pressure boilers and
carbonate conditioning is used for low pressure boilers. It is useful for softening acidic, neutral
and alkaline water. So phosphate conditioning is preferred over carbonate conditioning.

Phosphate conditioning

A common additive is Na3P04, though other phosphates such as NaH2P04, NazHP04 and
NazP207 are also used depending on the acidity of the water. Phosphate is added to the water at
25-50 mg/L to precipitate the calcium as the insoluble
Scale formation can be avoided by adding sodium phosphate to boiler water phosphate reacts
with Ca and Mg salts and formed easily removable sludge

3CaC12(boiled water) +2Na3POÅ

3CaS04+2Na3P04 Ca3(P04)2+3Na2S04

calcium cannot be precipitated below a pH=9.5 hence the selection of phosphate has to be based
on the pH of the boiler feed water

If water is

• Acidic then trisodium phosphate is used

• Alkaline then sodium dihydrogen phosphate is used

• Neutral then disodium hydrogen phosphate is used.

Calgon conditioning:

• It is a complex salt which is used to soften hard water.

• The chemical name of Calgon is hexametaphosphate.

• The chemical formula of Calgon is (NAPO3)6.

Process:

In this process, when Calgon is added to hard water, it causes the magnesium and calcium ions
present in hard water to displace sodium ions from the anion complex of Calgon.

It means a complex anion is formed when Calgon ionizes.

The chemical reaction is as follows:

It results in the elimination of magnesium and calcium ions from hard water with Calgon.
When water is softened then sodium ions are released in the water.
Lime Soda process
Zeolite Softening process is the process of removing permanent as well as temporary hardness of
the water. Zeolite Softening occurs when magnesium (Mg) and calcium (Ca) zeolites (insoluble)
in water get precipitated. In this zeolite softening process, zeolite works as a catalyst which helps
in exchanging ions from Ca2+ or Mg2+ with sodium ions.
Certain complex inorganic salts possess the property of exchanging calcium and magnesium ions
present in hard water for Na2+ ions. An important salt of this type is sodium aluminium
orthosilicate or sodium zeolite (Na2Al2Si2O8.xH2O), commonly known as permutit (artificially
synthesized zeolite). This sodium zeolite salt belongs to a family of complex salts known as
zeolites.
Zeolite Softening Process of Water
When hard water containing magnesium and calcium ions passes through a zeolite bed of
sodium, then sodium (Na2+) ions get displaced or replaced by the ions of Mg2+ and Ca2+ and
when the replacement is complete i.e. all the sodium ions get replaced by Mg2+ and Ca2+ ions
then the zeolite get inactivated. This zeolite then gets regenerated by passing brine solution
through the inactive zeolite bed. This process of softening water is mainly used in laundry.
Reactions involved;
Ca2+ + Na2Al2Si2O8.xH2O → CaAl2Si2O8.xH2O + 2Na+
Mg2+ + Na2Al2Si2O8.xH2O → MgAl2Si2O8.xH2O + 2Na+
Ion-exchange process or Deionization or Demineralization Process - Recently ion-exchange
resins have been used to remove all minerals from water. It is a process by which ions held on a
porous, essentially insoluble solid are exchanged for ions in solution that is brought in contact
with it.
Ion-exchange Resin – An ion-exchange resin is a crosslinked organic polymer network having
some ionisable group. It may be of two types depending upon the nature of the ionizable group.
(i) Cation Exchange Resin or Cation Exchanger - Such resins have - SO3H, -- COOH or -OH
(phenolic) group as the ionizable group. Since these resins exchange the cationic portion of
minerals by their hydrogen atom, they are known as cation exchangers.
(ii) Anion Exchange Resin or Anion Exchanger – These resins have -NH2, -NHCH3, -N(CH3)2
or -OH group. They exchange the anionic portion of the minerals and they are known as anion
exchanger.
Uses of Ion-exchange Resin – Water treatment by ion-exchange resin includes softening
deionization and de-alkalization of water. Therefore, hard water can be converted into soft water
by making use of ion-exchange resins.

Process – In this process first we passed hard water through cation exchange column, which
removes all the cations (like Ca+2, Mg+2 etc.) from it and equivalent amount of H+ ions are
released from this column to water.
Thus,
2RH+ + Ca+2 -> R2Ca+2 + 2H+
2RH+ + Mg+2 -> R2Mg+2 + 2H+
After this process, hard water is passed through anion exchange column, which removes all the
anions (like SO4-2, Cl- etc.) from it, and equivalent amount of OH- ions are released from this
column to water. Thus,
R'OH-2 +Cl-2 -> R'Cl-+ OH-
2R'OH- + SO2-4 -> R'2 SO2-4 + 2OH-
2R'OH- + CO2-3 -> R'2 CO2-3 + 2OH-
H+ and OH - ions get combined to produce water molecule
H+ + OH- + H2O
The water coming out from the exchanger is free from cations as well as anions. Ion-free water is
known as a deionized or demineralized water.
Reverse Osmosis, separation technique in which pressure applied to a solution forces the solvent
through semipermeable membrane from a region of low concentration to one of high
concentration, leaving behind the solutes. The membrane allows passage of small solution
components, such as fresh water, while preventing passage of larger molecules, like salts and
other impurities.
Reverse osmosis is an effective means of concentrating impurities, recovering contaminated
solvents, cleaning up polluted streams, and desalinizing seawater and is often used as an
alternative to distillation for water purification. Reverse osmosis can also be utilized in certain
instances to perform separations prior to a chemical assay.
Electrodialysis (ED) is used to transport salt ions from one solution through ion-exchange
membranes to another solution under the influence of an applied electric potential difference.
This is done in a configuration called an electrodialysis cell. The cell consists of a feed (dilute)
compartment and a concentrate (brine) compartment formed by an anion exchange membrane
and a cation exchange membrane placed between two electrodes. In almost all practical
electrodialysis processes, multiple electrodialysis cells are arranged into a configuration called an
electrodialysis stack, with alternating anion and cation-exchange membranes forming the
multiple electrodialysis cells. Electrodialysis processes are different from distillation techniques
and other membrane based processes (such as reverse osmosis (RO)) in that dissolved species are
moved away from the feed stream, whereas other processes move away the water from the
remaining substances. Because the quantity of dissolved species in the feed stream is far less
than that of the fluid, electrodialysis offers the practical advantage of much higher feed recovery
in many applications.
Anode and cathode reactions
Reactions take place at each electrode. At the cathode,
2e− + 2 H2O → H2 (g) + 2 OH−
while at the anode,
H2O → 2 H+ + ½ O2 (g) + 2e− or 2 Cl− → Cl2 (g) + 2e−
Small amounts of hydrogen gas are generated at the cathode and small amounts of either oxygen
or chlorine gas (depending on composition of the E stream and end ion-exchange membrane
arrangement) at the anode. These gases are typically subsequently dissipated as the E stream
effluent from each electrode compartment is combined to maintain a neutral pH and discharged
or re-circulated to a separate E tank. However, some (e.g.,) have proposed collection of hydrogen
gas for use in energy production.
MUST DO QUESTIONS
UNIT-3
•Briefly explain the temporary and permanent hardness of water.

•Explain the EDTA method to estimate the total hardness of water. (6)

OR

•Explain how the hardness of water is removed by EDTA method.

OR

Write principle of EDTA method of determination of hardness of water.

OR

•Describe the principle and theory of EDTA method of determination of hardness of water. (6.5)

•Explain the carbonate and phosphate conditioning methods for water softening. (3.5)

OR

Explain the following:-

(1)carbonate and Phosphate conditioning. (2)Lime soda process (6)

•A sample of ground water has 150 mg/l of Ca2+ and 60 mg/L of mg2+.Find the total hardness
expressed in milliequivalents per litre and mg/L in terms of CaCOg. (3)

•What is the principle of reverse osmosis. Name the membranes employe din it. Also, state the
advantages of this process. (4)

•A 50 ml of a sample of hard water consumes 32.5 ml of 0.01 M EDTA. What will be the
hardness of water. (2.5)

•Define the following:

(i) Calgon conditioning, (ii) Priming and foaming, (iii) Electrodialysis. (6)

OR

Explain the following terms:

•100 ml of H20 sample when titrated against N/50 H2S04. Using phenophthalein as an indicator,
gave the end point with 10 ml of acid. Another 100 ml of the sample also required 10 ml of the
acid to obtain methyl orange end point. What type of alkalinity is present in the sample and what
is its magnitude?

•50 mo of a sample of hard water was titrated against 0.01 EDTA if required 15 ml of EDTA for
titration. 50 ml of the same hard water after boiling and filtering etc. required 5 ml of EDTA for
titration. Calculate the total hardness of water.

•What is caustic embrittlement? Explain its causes and prevention.

•What are the methods of water softening of by external treatment.

•What are ion-exchange resins? How are they used for softening of water, explain with reactions
and diagram? How can they be regenerated after getting exhausted? (7)

•Calculate the lime (84% pure) and soda (92% pure) required for treatment of 50000 liters of
water containing Ca(HC03) = 40.5 ppm, Mg(HC03) =36.5 ppm, MgS04 = 30.0 ppm, CaS04 =
34 ppm, CaC12 = 27.75 ppm and NaCl = 10.0 ppm. (8)

•If 50 ml of sample of hard water consumed 15mI of 0.01M. What is the hardness of water? (5)

•1 g Of CaC08 was dissolved in dil. HCl and solution dilute to 1 litre. 50 ml of this solution
required 42 ml of EDTA solution while 50 ml of sample water required 15 ml of EDTA. On the
other hand when 50 ml of boiled water sample titrated against EDTA, consumed 9 ml of
solution. Calculate total permanent and temporary hardness of water in ppm. (6)