ENGINEERING CHEMISTRY (BT-101) NOTES

UNIT I: WATER ANALYSIS, TREATMENTS AND INDUSTRIAL APPLICATIONS

INTRODUCTION: For the existence of all living beings, water is very crucial. Almost all human
activities – domestic, agricultural and industrial demand use of water. Although water is nature’s most
wonderful and abundant compound but only less than 1% of the world’s water resources is available for
ready use. Hence, water has to be used carefully and economically.
SPECIFICATIONS OF WATER:
Different uses of water demand different specifications –
(i) Textile industry needs frequent dying of clothes and the water used by this industry should be
soft and free from organic matter. Hard water decreases the solubility of acidic dyes. Organic
matter imparts foal smell.
(ii) Laundries require soft water, free from colour, Mn and Fe, because hardness inc.
consumption of soaps, salts of Fe and Mn impart a grey or yellow shade to the fabric.
(iii) Boilers require eater of zero hardness otherwise efficient heat transfers is prevented by scale
formation. Untreated water can lead to corrosion of boiler material.
(iv) Paper industry requires water free from SiO2 as it produces cracks in paper; turbidity as it can
affect brightness and colour of paper; alkalinity as it consumes more alum; hardness as Ca2+
Mg. Salts increases the ash content of the paper.
(v) Sugar industry requires water free from hardness because hard water causes difficulty in the
crystallization of sugar.
(vi) Dairies and pharmaceutical industry require ultra pure water, which should be colorless,
tasteless, odorless and free from pathogenic organisms.
Therefore water needs to be treated to remove undesirable impurities. “Water treatment” is the process
by which all types of undesirable impurities are removed from water and making it fit for domestic or
industrial purposes.
Impurities in Water

Physical Chemical
Bacteriological

Suspended Colloidal Bacteria Fungi Algae

Dissolved gases Dissolved organic Dissolved inorganic

Salts Salts

Water sources: Sources of Water

Surface Water Rain Water Underground Water Sea Water

Flowing Still
Springs Tube wells Wells

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Water Water

Streams Rivers Sea Lakes Reservoirs Ponds

River water contains dissolved minerals like chlorides sulphates, bicarbonates of sodium, magnesium,
calcium and iron. Its composition is not constant. Lake water has high quantity of organic matter present
in it. Its chemical composition is also constant. Rain water, in the purest form of natural water. When it
comes down, it dissolves organic and inorganic suspended particles and some amount of industrial
gases.
Underground water is free from organic impurities and is clearer in appearance due to filtering action of
the soil. It has large amount of dissolved salts. Sea water is very impure due to continuous evaporation
and impurity thrown by rivers as they join sea.

HARDNESS OF WATER:
Hardness is defined as soap consuming capacity of water sample. It is that characteristic “which prevent
the lathering of soap.” It is due to presence of certain salts of Ca, Mg and other heavy metal ions like
al3+, Fe3+ and Mn2+ dissolved in it. A sample of hard water, when treated with soap (K or Na salt of
higher fatty acids like oleic, palmitic or stearic acid), does not produce lather, but forms insol. white
scum or ppt. which does not possess any detergent action, due to formation of insoluble soaps of
calcium and magnesium sulphates.
2C17 H35 C00 Na + CaCl2 (C17 H35 C00)2 Ca + 2 NaCl.
Soap (Hardness) Calcium Sterate
(Sodium Sterate) (Insoluble)
2C17 H35 C00 Na + MgSO4 (C17 H35 C00)2 Mg + Na2SO4
Soap (Hardness) Magnesium Sterate (Insoluble)
S.No HARD WATER SOFT WATER
Water which does not produce lather with Water which lather easily on shaking with
1.
soap solution readily, but forms a ppt. soap solution, is called soft water.
2. It contains dissolved Ca & Mg salts in it. It does not contain Ca & Mg salts in it.
Cleansing quality in depressed and lot of Cleansing quality is not depressed and so
3.
soap is wasted. not soap is wasted.
Boiling point of water is elevated, and more Less fuel and time are required for cooking
4.
fuel and time are required for cooking. in soft water.
Water is said to hard when hardness is In soft water hardness is below 100 mg. /
5.
above 100 mg. / ltr. ltr.

TYPES OF HARDNESS: It is of following types

1. Temporary Hardness:
(a) It is caused by presence of dissolved bicarbonates of Ca, Mg and other heavy metals and the
carbonates of Iron. Example – Ca (HCO3)2 and Mg (HCO3)2.
(b) It can be removed by boiling of water, when bicarbonates decompose to yield insoluble
carbonates or hydroxides, which gets deposited as a crust at the bottom of vessel.
Ca (HCO3)2 CaCO3 + H2O + CO2
Mg (HCO3)2 Mg (OH)2 + 2CO2
(c) It is also known as carbonate hardness or alkaline hardness.
(d) It is determined by titration with HCl using methyl orange as indicator.

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2. Permanent Hardness:
(a) It is due to presence of dissolved chlorides and sulphates of calcium, magnesium, iron and
other heavy metals, eg. CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2 (SO4)3 etc.
(b) It cannot be destroyed by boiling. It can removed by-
(i) Lime – Soda Process: CaCl2 + Na2CO3 CaCO3 + 2NaCl
Soda
(ii) Zeolite Process: CaSO4 + Na2Ze CaZe + Na2SO4
Sodium Zeolite
(iii) Ion – exchange Process:
2 RCOOH+ + Mg2+ (RCOO)2 Mg2+ + 2H+
+ - -
R N (CH3)3 OH + Cl R+N (CH3)3 Cl- + OH-
(c) Permanent hardness is also known as non-carbonate or non-alkaline hardness.

3. Total Hardness = Carbonate Hardness (Temporary) + Non-carbonate Hardness (Permanent)

DEGREE OF HARDNESS:
Although hardness of water is never present in form of calcium carbonate because it is insoluble in
water and calcium is not the only cation calving hardness but hardness is expressed in terms of
equivalent amount (equivalents) of CaCO3 i.e., the mg CaCO3 / Litre.
The CaCO3 is chosen as standard because:
1. CaCO3 is chosen as the standard mainly because it is having great convenience to calculate as the
molecular weight in 100 and its equivalent weight is 50.
2. It is sparingly soluble salt in water, thus, can be easily precipitated in the lime soda processes of
softening water.
Therefore, all the hardness-causing impurities are first converted in terms of their respective weights
equivalent to CaCO3 and is expressed in parts per million.
Multiplication factors for different salts are:
Constituent Molar n – factor Chemical Multiplication factor for
Salt / ion Mass equivalent = converting into equivalents of
molar mass CaCO3
n – factor

Ca (HCO3)2 162 (divalent) 162/2 = 81 100/2 x 81 = 100/162

2
Mg (HCO3)2 146 2 146/2 = 73 100/2 x 73 = 100/146
CaSO4 136 2 136/2 = 68 100/2 x 68 = 100/136
MgSO4 120 2 120/2 = 60 100/2 x 60 = 100/120
CaCl2 111 2 111/2 = 47.5 100/2 x 47.5 = 100/111
MgCl2 95 2 95/2 = 47.5 100/2 x 50 = 100/95
CaCO3 100 2 100/2 = 50 100/2 x 50 = 100/100
MgC03 84 2 84/2 = 42 100/2 x 42 = 100/84
CO2 44 2 44/2 = 22 100/2 x 22 = 100/44
Mg (NO3)2 148 2 148/2 = 74 100/2 x 74 = 100/148
HCO3 61 (monovalent) 61/1 = 61 100/2 x 61 = 100/122
1
OH- 17 1 17/1 = 17 100/2 x 17 = 100/34
CO32 - 60 2 60/2 = 30 100/2 x 30 = 100/60
NaAlO2 82 1 82/2 = 82 82/2 x 82 = 100/164

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Al2 (SO4)3 342 6 342/6 = 57 100/2 x 57 = 100/114

FeSO4 . 7H2O 278 2 278/2 = 139 100/2 x 139 = 100/278
+
H 1 1 1/1 = 1 100/2 x 1 = 100/2
UNITS OF HARDNESS:
Parts per million (ppm): ppm is the parts of calcium carbonate equivalent hardness per 10 6 parts of
water.
1. Milligrams per litre (mg/L): It is the number of milligrams of CaCO 3 equivalent hardness
present per litre of water.
1 mg / L. = 1 mg of CaCO3 eq. Hardness / L of water
But 1 L of water weights = 1000 gms.
= 1000 x 1000 mg.
1 mg / L = 1 mg / 106 mg = 1 ppm.
2. Clarke’s degree ( Cl): It is the number of grains of CaCO3 equivalent hardness per gallon of
0

water. It is the parts of CaCO3 equivalent hardness per 70,000 parts of water.
3. Degree French (0Fr): It is the parts of CaCO3 eq. Hardness per 105 parts of water.
Relationship between units:
1 PPm = 1 mg / L = 0.1 0Fr = 0.07 0Cl
0
1 Fr = 10 PPm = 10 mg / L = 0.7 0Cl
1 0Cl = 14.3 PPm = 14.3 mg/L = 1.43 0Fr

Determination of Hardness by EDTA Method

 EDTA is abbreviation of Ethylene diamine tetra acetic acid.
 EDTA dissolves in water with great difficulty and in a very very small quantity.
 On the contrary its di-sodium salt dissolves in water quickly and completely. Hence for common
experimental purpose, in place of EDTA, its di-sodium derivative is used.
 EDTA is a hexadentate ligand. It binds the metal ions in water i.e Ca 2+ or Mg2+ to give highly
stable chelate complex. (These metal ions are bonded via oxygen or nitrogen from EDTA
molecule). Therefore this method is called as Complexometric Titration.

Structure of EDTA (Ethylene diamine Tetra acetic acid)

Principle of EDTA Method:

 The di-sodium salt of EDTA forms complexes with Ca2+ and Mg2+, as well as with many other
metal cations, in aqueous solution.

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 Thus, the total hardness of a hard water sample, can be determined by titrating Ca 2+ and Mg2+
present in the sample with di-sodium salt of EDTA (Na2 EDTA) solution, using ammonical
buffer solution containing NH4Cl-NH4OH of pH 10 using Eriochrome Black-T (EBT) as the
metal indicator.

 At pH 10, EBT indicator from wine red coloured unstable complex with Ca 2+ and Mg2+ ions in
hard water.
 This complex is broken by EDTA solution during titration, giving stable complex with ions and
releasing EBT indicator solution which is blue in colour. Hence the colour change is from wine
red to blue (EBT’s own colour).
 Thus noting the colour change, the point of equivalence can be trapped and hardness of water
can be determined by this method.

Advantages of EDTA Method:

 Greater accuracy
 Highly rapid
 Highly convenient

Alkalinity and its determination:

Alkalinity:
 It can be defined as “the concentration of the salts present in water which increases the
concentration of OH- ions due to hydrolysis thereby rising pH of water to alkaline range”.
 Natural water when found alkaline, it is generally due to the presence of HCO 3-, SiO32- and
sometimes CO32- ions. In addition to the above the alkalinity of boiler water is also due to the
presence of OH- & PO42- ions.
 The extent of alkalinity depends on the presence of ions, which broadly can be categorized as
presence of
 (i) OH- only (ii) CO32- only (iii) HCO3 - only (iv) OH- & CO32- together (v) HCO3- & CO 2- 3
together.
 Hydroxide and bicarbonates do not exist together because hydroxyl ions react with bicarbonate
ions to form carbonate ions. Therefore existence of hydroxyl and bicarbonates ions together is
ruled out.

OH- + HCO3- CO32- + H2O

The alkalinity of natural water is due to the presence of hydroxides, carbonates and bicarbonates of
Calcium and Magnesium. Alkalinity is a measure of the ability of water to neutralize the acids. The
constituents causing alkalinity in natural water are as follows:

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This is determined by titrating the sample with a standard solution of a strong acid. When the pH of
the sample is above 8.3, titration is first carried out using phenolphthalein indicator. At the end point
when the indicator changes from pink to colorless, the pH is lowered to about 4.5 due to addition of
HCl. At this point complete neutralization of hydroxide and conversion of all the carbonate into
bicarbonate occurs. The alkalinity measured up to this point is called phenolphthalein alkalinity. [P]
Titration is continued using methyl orange indicator. The color changes from yellow to red and
shows complete neutralization of all the bicarbonate ions.

The total volume of acid used in both the stages corresponds to the neutralization of hydroxide,
carbonate and bicarbonate and is thus, a measure of Total Alkalinity. [M]

Calculation of Alkalinity of water by following table

--
Alkalinity OH- (ppm) CO3 (ppm) HCO3- (ppm)
P=0 0 0 M
P = 1/2M 0 2P 0
P < 1/2M 0 2P (M-2P)
P > 1/2M (2P-M) 2(M-P) 0
P=M P=M 0 0

Significance:
1) For calculating the amounts of lime and soda required for water softening.
2) In conditioning boiler feed water, highly alkaline waters may lead to Caustic Embrittlement and
also may cause deposition of precipitates and sludge in boiler tubes and pipes.
3) Bicarbonates of calcium and magnesium induce temporary hardness in water, which if
untreated, causes scale formation in boilers.

Numerical based on Hardness & Strength

Formula for Determination of Hardness:

Hardness = Strength (in mg/l) × Chemical equivalent wt. of CaCO 3

Chemical equivalent wt. of hardness producing salt

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Formula for Determination of Strength:

Strength = Hardness (in mg/l) × Chemical equivalent wt. of hardness producing salt
Chemical equivalent wt. of CaCO3

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