WATER

INTRODUCTION

HARDNESS OF WATER

ESTIMATION OF HARDNESS

SOFTENING OF WATER

BOD,COD Defination,significance&NPs
 What is Hardness?
•A measure of the soap or detergent
consuming power of water.
•Caused by divalent metallic cations that
react with soap to form precipitates, and
with some anions to form scale.
•Typically calcium and magnesium ions.
SOAP TEST:

2(C17H35COONa) + CaCl2 or MgSO4 → (C17H35 COO)2Ca +

FROM WATER
2NaCl or Na2SO4
SOAP
CURDY WHITE PPT.
=SCUM
Reaction with soap :

Divalent cations:
Soap is usually composed of Lauric acid

C-C-C-C-C-C-C-C-C

C-C-C-C-C-C-C-C-C

C-C-C-C-C-C-C-C-C
Ca This is insoluble
C-C-C-C-C-C-C-C-C
 HARDNESS OF WATER

Hardness is defined as “ It is the property of water by virtue of

which it resist to form a lather or foam, when it comes in contact
with soap.”
UNITS OF HARDNESS :

PARTS PER MILLION : 1ppm hardness means 1 part of CaCO3

equivalent hardness per million parts of water.

MILLIGRAMS/LITER : 1 mg./lit. hardness is 1 mg. Of CaCO3 equivalent

hardness per liter of water sample.

CLARKE’S DEGREE : 1 Clarke’s degree is 1 grain equivalent hardness

present in 1 gallon (10 lb) of water..

FRENCH DEGREE : 1 French degree hardness is 1 part of CaCO3

equivalent hardness per 1000000 parts of water.
Thus, conversion from one unit of
hardness to other units of hardness can be
done as follow:

1 mg / lit = 1 ppm
1 Deg. Cl. = 14.3 ppm
1 Deg. Fr. = 10 ppm
Origin of water "hardness"
 HARDNESS

TEMPORARY PERMANENT
CARBONET NON-CARBONET
HARDNESS HARDNESS

It can be removed by mere It can not be removed by

boiling. boiling.
Ca(HCO3)2 CaCO3 + H2O + CO2
Known as Non-Carbonate
Known as Carbonate Hardness Hardness

EXAMPLES : EXAMPLES :
Ca(HCO3)2, Mg(HCO3)2, CaCO3 et c. CaCl2, CaSo4, MgCl2, MgSo4 etc.
 Temporary and permanent hardness:

Temporary Hardness has the usual cations and

primarily bicarbonate as the anion, it can be softened
by boiling with the production of scale.

Permanent Hardness has the usual cations and

primarily non-bicarbonate as the anion, it cannot be
softened by boiling. Nitrate and sulfate ions are not
scaled out.
EFFECTS OF HARD WATER IN INDUSTRIES

SUGAR INDUSTRY

PAPER INDUSTRY

TEXTILE INDUSTTRY

DYEING INDUSTRY

PHARMACEUTICAL INDUSTRY

STEAM GENRATION
ESTIMATION OF HARDNESS BY EDTA METHOD
PRINCIPAL :
If the PH value of solution is made 10 & Eriochrome
Black-T (EBT indicator) is added in the presence of Ca++ &
Mg++ ions a weak complex of wine red colored is formed. The
addition of EDTA break this complex, forming a stable
complex with Ca++ & Mg++ ions, setting deep dye free, which
marks the end point.
REACTIONS :
[Ca++] Ca
Or + E.B.-T → Or – E.B.-T
[Mg++] Mg
UNSTABLE WINE RED COLOUR COMPLEX
 Ca Ca
Or – E.B.-T + E.D.T.A. → Or E.D.T.A. + E.B.-T
Mg Mg

UNSTABLE WINE RED STABL COMPLEX BLUE

COLOUR COMPLEX

TOTAL PERMANEN TEPMORARY

- = HARDNESS
HARDNESS T HARDNESS
Structure of EDTA and EBT
PROCEDURE :

2. ADD 1 T.T. BUFFER

SOLN. OF PH 10

3. ADD 3-5 DROPS OF

E.B.T. INDICATOR

1. 50 ML. SAMPLE OF
WATER

READINGS :

50 ML STANDARD HARD WATER = V1 ML. OF EDTA

50 ML. OF SAMPLE HARD WATER = V2 ML. OF EDTA
50 ML. OF BOILED SAMPLE OF WATER = V3 ML. OF EDTA
PART –I : STANDARDISATON OF EDTA

50 ml. STD. HARD WATER = V1 ml. Of EDTA

= 50 mg. Of CaCo3 equivalent
 1 ml. EDTA = (50/V1) mg. Of CaCo3 equivalent

PART- II : ESTIMATION OF TOTAL HARDNESS

50 ml. SAMPLE OF HARD WATER = V2 ml. Of EDTA

= (V2 * 50/ V1) mg. Of CaCo3 equivalent
 For 1000 ml sample of hard water = (V2 * 1000/V1) mg. Of CaCo3 equiv./lit.

PART- III : ESTIMATION OF PERMANENT HARDNESS

50 ml. Boiled, filtered sample of hard water = V3 ml. Of EDTA

= (V3 * 50/ V1) mg. Of CaCo3 equivalent
 For 1000 ml sample of hard water = (V3 * 1000/V1) mg. Of CaCo3 equiv./lit.
PART- IV : ESTIMATION OF TEMPORARY HARDNESS

TEMP. HARDNESS = TOTAL HARDNESS – PERM. HARDNESS

 Temp. Hardness = (V2 * 1000/V1) - (V3 * 1000/V1) mg. Of CaCo3 equiv./lit.

 Temp. Hardness = (1000 * (V2- V3 ) / V1 ) mg. Of CaCo3 equiv./lit.

ADVANTAGES :

1. Method is suitable for all types of water.

2. Method is simple & accurate.
3. Method is not time consuming.
 ION-EXCHANGE METHOD

Ion Exchangers are insoluble granular substances, which have,

in their molecular structure acidic or basic radicals that can be
exchanged. The positive or negative ions fixed on these radicals
are replaced by ions of the same sign in solution in the liquid in
contact with them.

EXCHANGERS

CATION ANION
EXCHANGERS EXCHANGERS

H2R (OH)2R
 ION-EXCHANGE METHOD

WATER +ACID WATER+GASES GASES

HARD
WATER

H2R (OH)2R DEGAS

IFIRE

SOFT
WASHING WASHING WATER

ALK.SOLN.
ACID FOR
REGENRATION FOR REGN.
ION-EXCHANGE PLANT
 Ion exchange reactions:
• A: Softening Reactions (with cation exchanger)
• RH2 +Ca2+ RCa + 2H+
• RH2 +Mg2+ RMg + 2H+

• Softening Reactions (with anion exchanger)

• R’(OH)2 + SO42- R’ SO42- +2OH-

• R’(OH)2 + 2Cl- R’ Cl2- +2OH-
 Regeneration reactions
• The exhausted cation exchanger regeneration with dil. Acid:
• RCa +2HCl 2RH + CaCl2
• RMg +H2SO4 2RH +MgSO4

• The exhausted anion exchanger regeneration with dil.alkali:

• R’Cl2 +2NaOH R’(OH)2 +2NaCl
• R’ SO42-+2NaOH R’(OH)2 +Na2SO4
 ADVANTAGES :

1.The process can be used to soften highly acidic or alkaline

water.
2. It produces water of low hardness (2 ppm.), therefore it is
good for high pressure boiler.

DISADVANTAGES :

1. The equipment is costly.

2. If water contain turbidity, then the output of process is
reduced
Turbidity should be below 10 ppm.
 REQUIRMENT OF LIME & SODA

SALT Hard. Lime Soda SALTs Hard. Lime Soda

Ca(HCO3)2 T Y N Al2(SO4)3 P Y Y
Mg(HCO3)2 T Y N CO2 T Y N
MgCO3 T Y N HCO3- T Y N
CaCl2 P N Y NaHCO3 T Y N
CaSO4 P N Y KCl N - -
MgCl2 P Y Y NaCl N - -
MgSO4 P Y Y K2SO4 N - -
HCl P Y Y Na2SO4 N - -
H2SO4 P Y Y SiO2 N - -
HNO3 P Y Y
FeSO4 P Y Y
 NUMERICALS ON ION EXCHANGE

• Ex.1.After treating 104 Liters of water by ion exchanger,

the cationic resin required 200 L of 0.1N HCL and anionic
resin required 200 L of 0.1 N NaOH solutions. Find the
hardness of the above sample of water.
• Solution : In an ion exchanger, all hardness causing cations
are removed by cation exchanger. Anion exchanger
removes anions of the constituents present in water.
• Consequently, the amount of acid used for regeneration of
cation resin refers hardness part.
Hardness in 104 L of water =200L of 0.1N-HCl
=200x0.1L of 1N-CaCO3 eq.
=20x50g of CaCO3 eq.
=1000g of CaCO3 eq.
Therefore in 1 L of water=1000/ 104 g of CaCO3 eq.
=0.1 g of CaCO3 eq.
=0.1x1000 mg of CaCO3 eq.
Hence, Hardness =100mg/l or ppm
• After treating 105 Liters of water by ion
exchanger, the cationic resin required 400
Liter of 0.2 N HCL and anionic resin
required 300 Liter of 0.2 N NaOH solutions.
Find the hardness of the above sample of
water.

• Ans=40 ppm
 BOD-Biological oxygen Demand
1.BOD is measure of amount of oxygen required for the biological oxidation of
organic matter under aerobic(oxygen is present) conditions, at 20oC and a period
of five days.

2.It represents the amount of oxygen consumed by bacteria and other

microorganisms while they decompose organic matter under aerobic conditions at
a specified temperature.
3.BOD is a measure of the organic pollution of water
Significance:
BOD is used, often in wastewater-treatment plants, as an index of the degree of
organic pollution in water.
From the BOD value, self purifying capacity of streams can be determined.
 BOD calculations

• BOD=(DO)1-(DO)2 x dilution factor

• ==(DO)1-(DO)2x Volume of sample
after dilution/ Volume of sample before
dilution
• =(900-450) x 100/50
• =900 ppm
 COD-Chemical oxygen Demand

COD: The amount of oxygen required by organic(biologically

oxidable and oxidizable inorganic matter (biologically inert) by
strong oxidizing agent is known as COD of sample.
It takes 2-3 hours (fast process)

Significance:
The most common application of COD is in quantifying the
amount of oxidizable pollutants found in surface
water (e.g. lakes and rivers) or wastewater.
It helps in designing the water treatment plants.
 Calculations of COD

The following formula is used to calculate COD:

COD =(V2-V1)x N x 8 x1000/V
=ppm
Where,
V1=Volume of FAS for sample titration
V2=Volume of FAS for blank titration
V=Volume of sample taken for the test
N=Normality of FAS solution
 Numerical on COD

• 10ml of waste water was refluxed with 20ml of K2Cr2O7

and after refluxing the excess unreacted dichromate
required 26.2ml of 0.1N FAS solution. A blank of 10ml of
distilled water on refluxing with 20ml of K2Cr2O7 solution
required 36ml of 0.1N FAS solution. Calculate the COD of
waste water sample.
• Solution:
COD =(V2-V1)x N x 8 x1000/V
=(36-26.2) x 0.1 x 8x100
= 784 ppm
Activated Sludge Process
 Steps involved in ASP
• 1.Preliminary treatment : includes removal of suspended solid
matter, sand and oil
• 2.Primary treatment :includes sedimentation process
• (chemicals like alum, hydrated lime etc.)
• 3.Secondary or Biological treatment-(aerobic chemical
oxidation) : Trickling filters are used.
• OR Activated Sludge process-Oxidation of organic matter
under highly aerobic conditions, in presence of a part of sludge
from previous process.
• 4.Tertiary treatment :a)Precipitation
• b)Disinfection-like chlorination
• Sludge is used as fertilizer or for synthesis of biogas
Water purification-Membrane technology
• 1.Electrodialysis:is a membrane based process involving
transport of ions through ion selective semipermeable
membrane using an applied electrical field.
 Applications of ED

• 1.De-salination of brackish water

• 2.Small and medium scale

• 3.Food processing

• 4.Agriculture
 Advantages and disadvantages:
• Advantages: easy operation, compact unit, separation of
salts and ions without adding chemicals and economical
process as the cost of installation and operational expenses are
less.
• Disadvantages : non charged and high molecular weight
species cannot be removed significantly.
• Sometimes pretreatment is required before the ED.
• electrodialysis systems require feed pretreatment to remove
species that coat, precipitate onto, or otherwise "foul" the
surface of the ion-exchange membranes
 Reverse Osmosis (RO)
• Reverse osmosis (RO) is a water purification process that
uses a semi permeable membrane to separate ions,
unwanted molecules and larger particles from drinking
water.
• “The reversal of solvent low, from higher concentration
solution to lower concentration solution through a
semipermeable membrane, by applying external pressure
slightly higher than the osmotic pressure of higher
concentration solution ,is known as reverse osmosis”.
Reverse Osmosis (RO)
 Applications of RO

1.The application of reverse osmosis in the food industry is a

clear example where it is widely used; from concentrates
of egg whites, fruit juices and gelatins, to removal of
bacteria and brine in meat or alcohol removal from spirits.
Dairy, starch and sugar industries are also users of the RO
plant working process.
2.Desalination of brackish water and seawater
3.Waste water treatment.
 Advantages:
• It is the best method for water softening.
• The semipermeable membrane will block all ion particles.
• The maintenance of the system is very simple.
• It gives us clean and pure water by blocking all contaminants.
• The available RO systems are very compact, and it requires
little space.
• The useful life of the full system, including the membrane, is
over two years.
• This system does not require any use of chemicals to purify
water.
• The energy requirement for the RO system is very low.
• RO systems are totally automated and are designed to start
and stop on their own.
 Disadvantages :
• Sometimes reverse osmosis leads to clogging of the whole
system.
• It requires routine filter changes and maintenance.
• The installation cost of a reverse osmosis system is high.
• The whole process is very slow when it comes to household
application, as the pressure used is very low.
• The process does not help in disinfecting the water. You will
require a separate process to disinfect the water.
• Hard water can damage the system.
• The damaged membrane will allow any small microorganism
to pass through it.
• The applied pressure has to be more than the osmotic pressure,
or the system won’t work.
 Ultrafiltration (UF)

• Ultrafiltration (UF) : is a water purification process in

which water is forced through a semipermeable membrane.
Suspended solids and high-molecular-weight solutes
remain on one side of the membrane, the retentate side,
while water and low-molecular-weight solutes filter
through the membrane to the permeate side. UF does this
by pressuring the solution flow, which is tangential to the
surface of supported membrane.
• The membrane with pore size in the range of 0.1 to 0.001
micron.
 Applications:
• Filtration of effluent from paper pulp mill
• Cheese manufacture, see ultrafiltered milk.
• Removal of some bacterias from milk
• Process and waste water treatment
• Enzyme recovery
• Fruit juice concentration and clarification
• Dialysis and other blood treatments
• Desalting and solvent-exchange of proteins (via diafiltration)
• Laboratory grade manufacturing
• Radiocarbon dating of bone collagen
 Advantages:
• 1.Low applied pressures are sufficient to achieve high flux
rates from an UF membrane.
• 2.As only high molecular weight species are removed, the
osmotic pressure differential cross the membrane surface is
negligible.
• 3.It removes high molecular weight substances, colloidal
materials, organic and inorganic polymeric materials.
 Disadvantages:
• The main disadvantages of the membrane
processes are the lowered hydraulic
performance of the membrane caused by
adverse effects of the filtration process (i.e.,
concentration polarization), development of a
gel layer on the surface of the membrane,
accumulation of dirt on the surface of the
membrane or inside it.