Water treatment
• Water is the most common solvent used in many applications such as in industries and
and household usage.
• The quality of water is a critical measure that if not well mantained may result in
serious damage of properties and loss of life.
• There are standard conditions that water treetments use to define the quality of water.
• The table below shows some of the key parameterds.
• One of the critical parameters in water treatment is water harness.
Water Hardness
What is water hardness?
• Hard water is any sample of water that is high in dissolved minerals, largely
calcium and magnesium salts. Whereas soft water contains low concntration of
dissolved minerals.
• The presence of ions such as Fe+ 2, Zn+2, and Al+3 may also result in water hardness
however, the presence of high amounts of Ca+ 2 and Mg+ 2 ions in water usually leads to
water hardness.
calcium/magnesium hardness
• This is the most common type of hardness in natural waters. The hardness caused by
these materials is known as total hardness.
• The part of the total hardness corresponding to carbonate and bicarbonate ions in the
water is defined as carbonate hardness.
• These ions also determine water alkalinity.
Waters are classified according to hardness grades as follows.
(mg/L) CaCO3 Degree of Hardness
0-75 Soft
75-150 Middle
150-300 Hard
300 and over Very hard
Effects of hard water
• It causes damage of water appliances such water taps, sinks, shower
heads, kettles.
• These appliances get coated by solid carbonate scales that changes
their shiny appearance.
• Large accumulation water hardness scales and sludges may lead to
inefficient of water boilers. (Containers used in industries to boil
water)
because it will take longer to boil water
• Hard water reacts with soap to produces sticky precitates of calcium & Mg soaps.
These are insoluble formations called scums.
• This results in less lather formation and cleaning quality of soap is decreased and a
lot of it is wasted
The major source of hard water.
Major net chemicl chemical recations leading to water hardness
The carbonic acid formed creates an acidic environmment that promote the dissolving of
solid of basic solid calciumcarbonate and magnesium carbonate respectively
Through this chemical recations the concentration of both Ca2+ and Mg2+ is incerseaed .
Type of Water hardness
Temprary water hardness + Permanent water hardness = Total water hardness.
Water softening methods
• The method for softening hard water is based on the type of hardnes present in
watter, whether is temporary or permanent hardnes.
Softening methods of temporary water hradness
1. By boiling water
2. By chemical reaction with slaked lime Ca (OH)2
Softening temporary water hardness by boiling
this is just a
reverse of
reactions
leading to
water hardness
so it involves
continous heating may solve
heating and this problem
filtering of
the solid pr
ecipitates
this heatings and filterings explain how we can practically get rid of water
hardness
• Boling can be a costly method as it require more energy to boil a large smple of
water.
Softening temporary hard water by lime method (Clark's process)
• Lime is a solution of calcium hydrxide Ca(OH)2 and if it is addedd to a sample of
hard water the following reactions are taking place.
carbon dioxide forms an acid
when reacted with water and
it is this acid that promotes the
dissolving of mg and ca carbonates
leading to hardness
remember co2 is formed only
during heating
• In ths reactions water is being softened by removing both Ca2+ and Mg2+ as solid
precipitates of carcium carbonate and magnesium hdroxide respectively.
take note that mg ions are removed
as magnesium hydroxide
mh(hc03)
• The solid precipitates are filtered off.
• This method is more eeffective than boling.
Methods for softening permanent water hardnes
• Permanent water hardness is mainly caused by the presence of CaCl2 , CaSO4 ,
MgCl and MgSO4.
• Permanent water hardnes cannot be softened by boiling or Lime alone.
• The following methods are used:
1. Lime -Soda method
2. Zeolite method
3. Ion exchange method
The Lime-Soda Method
• This method involves the use of a combination of two chemical reagents: Lime,
Ca(OH)2 and Soda Na2 CO3 .
• The lime-soda process can be carried out both at room temperature as well as at
higher temperatures. The process carried out at room temperature is called cold lime –
soda process and that carried out at 94°-100°C is called hot lime-soda process.
• The Lime- Soda method removes temporary hardness, permanent hardness,
dissolved iron and aluminium salts, dissolved CO2.
• The reactions involved are as follows:
1. Removal of temporary calcium and magnesium hardness using Lime
Ca (HCO3)2 + Ca (OH)2 → 2CaCO3 + 2H2O
Mg (HCO3)2 + 2Ca (OH)2 → 2CaCO3 + Mg (OH)2 + 2H2O
2.. Removal of permanent magnesium hardness MgCl2 and MgSO4
MgCl2 (aq) + Ca (OH)2 (aq) → Mg (OH)2 (s) + CaCl2 (s)
mg is dealt with using
caoh MgSO4 (aq) + Ca (OH)2 (aq) → Mg (OH)2 (s) + CaSO4 (s)
4. Removal of permanent hardness of CaCl2 and CaSO4 originally present in a
hard water and that produced from the removal of MgCl2 and MgSO4 using
soda (Na2CO3).
CaCl2 + Na2CO3 → CaCO3 (s) + 2NaCl
CaSO4 + Na2CO3 → CaCO3(s) + Na2SO4
The drawbacks associtaed with Lime-soda process
• The chemical reactions involved in the lime-soda process are quite slow.
• Moreover, the precipitates formed [particularly of CaCO3 and Mg(OH)2] are fine and
have a tendency to form super-saturated solutions. This results in after deposition of
these precipitates later in the pipes and boiler tubes leading to their clogging and
corrosion.
having moore solutes than expexteed under specific conditions
• These drawbacks of the process can be overcome by
o thorough mixing of chemicals and water.
o allowing proper time for the completion of reactions.
o the use of accelerators such as active charcoal and
to remove silica and some oil present
o the use of coagulants such as alum or NaAlO2
A typical recation vessel for Lime-soda softening method
reactions
Softening permanet hard water by Zeolite method
• Zeolites are naturally occuring hydrated sodium aluminium silicate, Na2O. Al2 O3. x
SiO2 yH2 O where x = 2 to 10 and y = 2 to 6.
• The synthetic form of zeolite is known as permutit. Synthetic zeolite is represented
by Na2Ze.
• The sodium ions which are loosely held in Na2 Ze are replaced by Ca2+ and Mg2+ ions
present in the water.
• Natural zeolites are non-porous. simply means it has higher
• Synthetic zeolites are porous and gelly structure. They are prepared by heating allowance
natural
compared to
together china clay, feldspar and soda ash.
• These synthetic zeolites have higher exchange capacity per unit weight than natural
zeolites.
The Zeolite process
• In this process, the hard water is passed through a bed of sodium zeolite (Na2 Ze).
• The hardness causing ions (Ca2+, Mg2+ ) in hard water is replaced by loosely held sodium
ions in zeolite bed.
• The outgoing soft water contains only sodium ions.
The major reactions are as follow.
Na2Ze + Ca (HCO3)2 → CaZe + 2NaHCO3
Na2Ze + Mg (HCO3)2 → MgZe + 2NaHCO3
Na2Ze + CaCl2 → CaZe + 2NaCl
both hardness can be removed
Na2Ze + MgCl2 → MgZe + 2NaCl
Na2Ze + CaSO4 → CaZe + Na2SO4
Na2Ze + MgSO4 → MgZe + Na2SO4
Regeneration of the exhausted regeneration bed
• After the softening process, the zeolite is completely converted into calcium and
magnesium zeolites, and it gets exhausted.
• At this stage the hard water supply is stopped, and the inlet for NaCl solution is
opened. The exhausted bed is regenerated by treating with a concentrated 10% brine
(NaCl) solution.
CaZe + 2NaCl → Na2Ze + CaCl2
MgZe + 2NaCl → Na2Ze + MgCl2
Exhausted Regenerated
Zeolite Zeolite
Advantages of the Zeolite process
• This process removes hardness up to 10ppm.
• Operational cost is less.
• The equipment used is compact No sludge formation.
• The plant can be connected to water supply line as it avoids double pumping.
Requires less time for softening.
• Maintenance and operation is easy.
Limitations of the Zeolite process
• The process exchanges only Ca2+ and Mg2+ ions with Na+ ions. It does not remove
the acidic ions like HCO3-, CO32-. Water containing such ions is not much suitable for
boilers as it may cause corrosion of boilers.
• Turbid water, if used clogs the pores of the Zeolite bed, making it inactive.
• Highly acidic or alkaline water will destroy the Zeolite bed.
• Coloured ions (Fe2+ and Mn2+) if present in water should be removed first and then
the water is sent to the bed, as these ions convert sodium Zeolite into their respective
Zeolites (FeZe, MnZe) which are difficult to be regenerated.
• High capital cost
Ion exchanger method of Softening permanent water hardnes
• In this method ion exchange resins are used as softening material.
• In this process cations like Ca2+, Mg2+ and anions like Cl-, SO4 2- which are
responsible for hardness are removed respectively by cation exchange resins and
anion exchange resins.
• Ion exchange resins are insoluble, cross linked, long chain organic polymers with a
micro porous structure. moore allowance to small particles such as ions
• The functional groups attached to the chains are responsible for the ion exchanging
properties.
remember hardness is caused by dissoved minerals in water
Cation exchange resins (RH+)
• Resin containing acidic functional groups (-COOH, -HSO3) can exchange their H+
ions with cations of hard water.
• The proton (H+) of those functional groups can exchanged with cations from water.
• For example calcium cation Ca2+ can be removed from water by this reaction
2RH ++ CaCl2 → R2Ca + 2HCl
Anion exchange resins (ROH-)
Resins containing basic functional groups (-NH2, -OH) can exchange their OH- ions with the
anions of hard water.
Example:
(i) Cross-linked quaternary ammonium salts.
R-NR3OH ;
(ii) Urea-formaldehyde resin
R-NH2 R(OH)2
The major process involved in ion exchange.
• The hard water first passed through a cation exchange column which absorbs all the
cations like Ca22+, Mg2+, Na+, K+ etc., present in the hard water.
2RH ++ CaCl2 → R2Ca + 2HCl
2RH + + MgSO4 → R2Mg + H2SO4
RH+ + NaCl → RNa + HCl
• The cation free water is then passed through an anion exchange column, which
absorbs all the anions like Cl-, SO42- etc., present in the water.
2ROH- + 2HCl → 2RCl + 2H2O
2ROH- + H2SO4 → R2SO4 + 2H2O
• Thus, the water coming out from the anion exchange is free from both cations and
anions. This water is known as ion free water (or) deionised (or) demineralised water.
• Water used in lead- acid battery is deionised water.
Advantages
• The process can be used to soften highly acidic (or) alkaline water.
• It produces water of very low hardness (2ppm).
Disadvantages:
• The equipment is costly and more expensive chemicals are needed.
• If the water contains turbidity, the output is low due to clogging.
Osmosis
• Osmosis is when solvent molecule (water) pass through a semipermeable membrane
from a dilute solution to a concentrated solution. define this way in chemistry concept
• This process takes place because of high osmotic pressure on the side of the dilute
solution than on the concentrated solution.
• Osmosis will continue taking place until the osmotic pressure on both side of the
membrane is equal.
• Reverse osmosis takes when external pressure is applied on the side of high
concentration. This external pressure will force water molecules to move from a
concentrated solution to the dilute solution.
• As long the applied external pressure is greater than osmotic pressure reverse
osmosis will occur.
Application of Reverse Osmosis
• Reverse osmosis is used in water purification especially the desalination of sea water.
• Desalination process involves the removal of salt from sea water.
• The reverse osmosis cell consists of a chamber fitted with a semi.
permeable membrane, above which sea water / impure water is taken and a pressure of
15 to 40 kg/cm2 is applied on the sea water / impure water.
• The pure water is forced through the semi-permeable membrane which is made of
very thin films of cellulose acetate.
Advantages:
1. Reverse osmosis possesses a distinct advantage of removing ionic as well as non-ionic,
colloidal and high molecular weight organic matter.
2. It removes colloidal silica, which is not removed by demineralization.
3. The maintenance cost is almost entirely on the replacement of the semi permeable
membrane.
Electrodialysis
• Electrodialysis is a membrane-based process involving removal of ions through
semipermeable membranes using an applied electric field.
• This process is carried out in cell compartments placed between oppositely
electrically charged electrodes.
• Each cell has two sides of ion specific membranes. The cation exchange membrane
allows only cations to pass through while the anions exchange membrane allows only
anions to pass through.
• The direction of ion movement is determined by the charges of electrodes. Cations
move toward the cathode (-) while anions toward to the anode.
• More cells can be aligned in parallel with the space in-between for the tube that
receive the ions and become more concentrated.
• The diagram below is a representation of electrodialysis system of salty water with
two channels of diluted solutions and one channel becoming concentrated.
• The most common applications employing electrodialysis include water desalination,
and table salt production.
Topic related review Questions
1. How is the chemical composition of hard water different from that of soft water?
2. Using relevant reaction equations elaborate how water from natural resources is
turned into hard water.
3. How is the chemical composition of permanent hard water is different from
temporary hard water?
4. Explain briefly as to why permanent water hardness cannot be treated by boiling
method?
5. Using relevant reaction equations, describe how the Lime-Soda method removs
water hardness.
6. Explain why the Lime- Soda method is sometimes preferred over the Lime
method?
7. Give the general formula for the synthetic Zeolite complex.
8. What special properties does the Zeolite complex have that make it to be suitable
for hard water treatment?
9. Write down the general equations all reactions that take place when hard water
pass through the Zeolite bed.
10. What special properties do ion exchange resins have that make special fit for their
functions.
11. Using relevant reaction equations elaborate how cation and anion exchanger resins
are regenerated after several operations.
12. Both sludges and scales can be formed in hard water in boilers. State the major
difference between scale and sludge.
13. Elaborate using relevant equations how chemical scale formation occur in boilers.
boiling reactions
14. Describe briefly how the cleaning effectives of soaps can be affected by water
hardness.
15. State the similarity of Reverse Osmosis and Electrodialysis methods water
purification. force is applied in both cases for water to pass through a spm
16. Imagine you are employed as Design Engineer for new hard water treatment
plant. State all possible factors that you would put into consideration that will
make treatment to operate and maintained at optimum level.
