CHAPTER-I

WATER AND ITS TREATMENT

INTRODUCTION

Mani sources of water: rain, rivers and lakes (surface water), wells and springs (underground water),
sea water.

Water Technology: The process of removing all types of impurities from water and making it fit for
domestic or industrial purpose is called water technology or water treatment.

TYPES OF WATER

HARD WATER (does not produced lather with soap) SOFT WATER

2C17H35COONa + Ca2+ (C17H35COO2) Ca + 2Na+ produced lather readily,

due to absence of Ca and Mg

Detection of hardness
1. It prevents lathering and forms white scum.
2. Give wine red colour with Eriochrome Black-T indicator at pH 9 -10.

Types of hardness:

1. Temporary hardness (or) Carbonate hardness(CH) (or) Alkaline hardness

Removed by i) boiling the water Ca (HCO3)2 Δ CaCO3 + H2O + CO2

ii) Adding lime to the water Mg (HCO3)2 + 2Ca(OH)2 Mg(OH) + 2CaCO3 + 2H2O

2. Permanent hardness (or) Non-carbonate hardness (NCH) (or) Non-alkaline hardness

Presence of Cl, S, Ca, Mg. Removed by
1. Lime-soda CaCl2 + Na2CO3 CaCO3 + 2NaCl

2. Zeolite CaSO4 + Na2Ze CaZe + Na2SO4

Expression of hardness in terms of equivalent of CaCO3
Amount of hardness producing salt x Equivalent weight of CaCO 3
Amount equivalent of CaCO3 =
Equivalent weight of hardness producing salt

Units of Hardness

1. Parts per million (ppm)

It is defined as the number of parts of CaCO 3 equivalent hardness per 10 parts of water.

2. Milligrams per litre (mg/lit)

 It is defined as the number of milligrams of CaCO3 equivalent hardness per 1 litre of water

Relationship between various units

1 ppm = 1 mg/lit = 0.1° Fr = 007° CI

Hour 2

Estimation of Hardness of water by EDTA

 EDTA is Ethylene Diamine Tetra Acetic acid.

 The structure of EDTA is

 The amount of hardness causing ions (Ca2+ and Mg2+) can be estimated by titrating the water
sample against EDTA Eriochrome – Black-T indicator (EBT) at pH of 8-10.

 In order to maintain the pH, buffer solution (NH 4CI – NH4OH mixture) is added. Only at this pH
such a complexation is possible.

 When the EBT indicator is added to the water sample, it forms wine red coloured weak complex
with Ca2+ and Mg2+ ions.

Wine red coloured weak complex

 When this solution is titrated against EDTA, it replaces the indicator from the weak complex form
stable EDTA complex.

 When all the hardness causing ions are complexed by EDTA, the indicator is set free.

The colour of the free indicator is steel blue. Thus the end point is the change of colour from wine
red to steel blue

Wine red coloured weak complex

(i). Standardisation of EDTA

 Pipette out 50 ml of standard hard water into a clean conical flask.

 Add 10 ml of buffer solution and 4-5 drops of EBT indicator and titrate it against EDTA solution
taken in the burette.The end point is the change of colour from wine red to steel blue

 Let the volume of EDTA consumed be V1 ml

 (ii). Estimation of total hardness of water sample

  Pipette out 50 ml of the given hard water sample into a clean conical flask and titrate it against
EDTA as before.

 C Let the volume of EDTA consumed be V2 ml

 (iii). Estimation of permanent hardness of water sample

 Take 100 ml of the same hard water sample in a 250 ml beaker. Boil it for 15 minutes.

 During boiling temporary hardness gets removed. Cool and filter the solution and make upto 100
ml in a standard flask by adding distilled water.

 Pipette out 50 ml of the made up solution into a clean conical flask and titrate it against EDTA as
before.

 Let the volume of EDTA consumed be V3 ml

 Calculations

 (i). Standardisation of EDTA

 1 ml of Std. hard water = 1 mg of CaCO3

 50 ml of Std. hard water = 50 mgs of CaCO3

 50 ml of Std. hard water consumes = V1 ml of EDTA

 ~ V1 ml of EDTA = 50 mgs of CaCO3 equivalent hardness (OR)

 1 ml of EDTA = 50 mgs of CaCO3 equivalent hardness

V1

(ii). Estimation of total hardness of water sample

50 ml of the given hard water sample consumes V2 ml of EDTA

= V2 X 50 / V1 mgs of CaCO3 equivalent

hardness

Total hardness = 1000 X V2/ V1

(iii). Estimation of permanent hardness of water sample

Permanent hardness = 1000 V3 / V1 ppm

Numerical Problems Solving

 BOLER TROUBLES:

Boiler feed water

Water fed into the boiler for the production of steam is called boiler feed water. It should be free from
turbidity, oil, dissolved gases, alkali and hardness causing substances. If hard water is used in boilers
following troubles may arise.

Boiler troubles (or) disadvantages of using hardwater in boilers:

1. Scale and sludge formation, 2. Priming and foaming 3.Caustic embrittlement 4. Boiler corrosion.

Scale and sludge formation in boilers:

i) Sludge – ppt is loose and slimy it is called sludge, formed by substance like MgCl 2, MgCO3,
MgSO4 and CaCl all solubility in cool water. Dis.adv – decreases efficiency of boiler.
Prevention – use softened water, “blow-down operation”.

ii) Scale – ppt forms hard and adherent coating on the inner walls of the boiler, formed by substance
like Ca(HCO3)2, CaSO4 and Mg(OH)2. Dis.adv – decreases the efficiency of boiler, any crack on
scale leads to explosion. Prevention – use HCl, H2SO4, applying thermal shocks, scrapers, wire
brush etc.,

Comparison of Scales and Sludges

Sludge Scales

loose and slimy hard and adherent

MgCl2, MgCO3, MgSO4 and CaC Ca(HCO3)2, CaSO4 and Mg(OH)2

Poor conductors Thermal insulators

Prevention – by “blow-down operation” use of HCl, H2SO4, applying thermal shocks etc

Treatment of Boiler feed water: removing hardness producing salts form water

Internal treatment or internal conditioning of boiler compounds: removal of scale forming

substances
 1).Phosphate conditioning: 3CaSO4 + 2Na3PO4 Ca(PO4)2 + 3Na2SO4

Na3PO4,(too alkaline) Na2HPO4 ,(weakly alkaline) NaH2PO4 (acidic)

2). Colloidal Conditioning : This colloidal substances get coated over the scale forming
particles and thus the coalescence of this particles to a compact scale is prevented. Thus the
scale formed remains loose and non sticky and can be easily removable- starch and glue are
colloidal conditioning agents.

3). Sodium aluminate conditioning: When sodium aluminate is treated with boiler water, it
gets hydrolyzed give sodium hydroxide and a gelatinous precipitate of aluminum hydroxide.
NaAlO2 + 2H2O NaOH + Al(OH)3 ; 2NaOH + MgCl2 Mg(OH)2 + 2NaCl -----Al(OH)3 and
Mg(OH)2 entrap finely suspended and colloidal impurities like sand, oil drops -settle to the
bottom - removed easily

4). Calgon conditioning: 2CaSO4 + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2 Na2SO4

It’s prevents the ppt of scal forming salt.

2. External Treatment – removal of salt before feeding into the boiler. This external treatment
can be done by Ion-exchange process, Demineralization.

Ion-Exchange (or) Demineralization process: D.M water does not contain both anions and
cations ex-Ca2+, Mg2+, Na+, K+, SO42-, Cl- using ion exchange resins, which are long chain, cross
linked, insoluble organic polymer with a microporous structure. Functional group of chains are
responsible for the ion exchanging properties.

1. Cation exchanger : Resins containing acidic functional group (-COOH, -SO 3H)

Ex- Sulphonated coats, Sulphonated polystyrene (R-SO3H; R-COOH=RH2).

Process – RH2 + CaCl2 RCa + 2HCl / RH + NaCl RNa + HCl

Regernation - RCa + 2HCl RH2 + CaCl2 (Ca instead of Na get NaCl2)

 2. Anion Exchanger: Resins containing basic functional group (-NH2, -OH)

Ex- Cross-linked quaternary ammonium salts, Urea-formaldehyde resin, (R-NR3OH, R-OH)

Process –R’(OH)2 + 2HCl (H2SO4) R’Cl2 (R’SO4) + 2H2O

Regernation - R’Cl2 + 2NaOH R’(OH)2 + 2NaCl

Advantages of ion-exchange process: -removal of acidic or alkaline water-very low hardness

-2ppm.

Disadvantage of ion-exchange process:

 Fe and Mn cannot treated with reduced output also.

 costly.

Zeolite or Permutit Process

Zeolites are of two types:

1. Natural zeolite :
 Natural zeolite are non-porous.for example,natrolite ,Na 2O.Al2O3.xSiO2.yH2O.

 2. Synthtic zeolite :Synthtic zeolite are porous and posses get structure.

 They are prepared by heating together china clay,feldspar and soda ash.

 such zeolites possess higher exchange capacity per unit weight than natural zeolites.

 For softening of water by zeolite process,hard water is percolated at a specified rate through a
bed of zeolite, kept in a cylinder.

 The hardness causing ions(Ca2+ ,Mg2+ ,etc.) are retained by the zeolite as CaZe and MgZe ; while
the outgoing water contains sodium salts.

 Reactions

 Na2Ze + Ca(HCO3)2 à CaZe + 2NaHCO3

 Na2Ze + Mg(HCO3)2 à MgZe + 2NaHCO3

 (Zeolite) (Hardness)

 Na2Ze + CaCl2 (or CaSO4) à CaZe + 2NaCl (or Na2SO4)

 Na2Ze + MgCl2 (or MgSO4) à MgZe + 2NaCl(or Na2SO4)

 (Zeolite) (Hardness)

 Regeneration

 After some time, the zeolite is completely converted into calcium and magnesium zeolite and it
ceases to soften water, i.e., it gets exhausted.

 At this stage, the supply of hard water is stopped and the exhausted zeolite is reclaimed by
treating the bed with a concentrated (10%) brine (NaCl) solution.

CaZe (or MgZe) + 2Nacl à Na2Ze + Cacl2 (or MgCl2)

(Exhausted zeolite) (Brine)

The washing (containing Cacl2 and MgCl2 ) are led to drain and the regenerated zeolite bed thus-
obtained is used again for softening purpose.

DESALINATION OF BRACKISH WATER: removing common salt (NaCl) is called

desalination, -- peculiar salty or brackish taste iscalled brackish water. Water grade – i) Fresh
water -1000ppm ii) Brackish water - >1000 but < 35,000 ppm iii) Sea water - >35,000 ppm of
dissolved solids. Desalination is carried out either by reverse osmosis or electrodialysis.

Reverse Osmosis (RO):

 Osmosis- water flows from lower concentration to higher concentration. Driving force is called
osmotic pressure.

 Water flows from higher concentration to lower is called reverse osmosis.

 (If a hydrostatic pressure in excess of osmotic pressure is applied on the higher concentration
side, the solvent flow is reversed i.e. solvent flows from higher concentration to lower
concentration.)

 This process is also known as super – filtration.

 The membranes used are cellulose acetate, cellulose butyrate.

Advantage –

 life time of membrane is high--replaced with in few minutes--Remove ionic, nonionic

and collidal impurities--Low cost –simplicity--low operating system.

Uses: Domestic watre purifiers and for converting sea water into drinking water.