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Engineering Chemistry
Module - I
(Water Technology)
Dr. D. PRABHAKARAN
Cabin: TT 218
Mobile: 9003137247
E-mail: prabhakaran.d@vit.ac.in
1
MODULE -1
Characteristics of hard water - hardness,
DO, TDS in water and their determination.
Numerical problems in hardness
determination by EDTA.
Modern techniques of water analysis for
industrial use - Disadvantages of hard water
in industries.
2
WATER
“Without food, human can survive for number of days,
but water is such an essential that without it one
cannot survive”.
“Although water is nature’s most wonderful, abundant
and useful compound yet is also the most misused
one”.
3
Distribution of water
4
Sources of Water
A) Surface Waters
Rain Water - Pure but contaminated with gases
River Water - High dissolved salts moderate organics
Lake Water - Const. composition but high organics
Sea Water - High salinity and organics
B) Underground Waters
Spring/Well Water - Crystal clear but high dissolved
salts and less impurity from organics
5
Deep Ground Water No pathogens, rich in
dissolved solids
carbonates & sulphates Ca
and Mg or Fe
Shallow Ground Variable bacteriological
water quality, soluble materials
including toxic metals of
As, Zn & Cu
Upland Lakes & Bacteria levels usually low,
Reservoirs rich in organic & inorganic
matters, pH adjustment
required
Rivers, Canals & Low Significant Bacterial levels,
land Reservoirs suspended solids &
dissolved constituents
Classification of Impurities in water
Physical Impurities - Dissolved Solids/Salts
Chemical Impurities - Inorganic & Organic Chemicals
Biological Impurities - Pathogens, algae, fungi,viruses...
1) Acidity (pH)
1) Colour 2) Gases (CO2-
2) Turbidity 1) Microorganisms
O2, NH3) 2) Algae
3) Taste 3) Minerals
4) Odour 3) fungi
4) Salinity
5) Conductivity 5) Alkalinity
6) Temperature
6) Hardness 7
Impurities in water
Physical Biological
Temperature, Microorganisms
Dust Bacteria
Clay Chemical
Fungi
Sand Algae
Other suspended Acid rain
Dissolved CO2 Pathogens
particles
Minerals
Dissolved salts
Synthetic organic compounds
Radioactive substances
Oxygen demanding wastes
Plant nutrients
Colour
• Colour in water is due to metallic salts of Fe, Mn and due to organic
substances like humus, peat, algae, weed …
• Industrial activities such as textile, paper & pulp, dyeing, tanneries
• Colour intensities of water sample can be measured using
tintometer using Platinum cobalt standard colour complex
Turbidity
• It is due to colloidal, extremely fine suspension such as clay, slit,
finely divided matters, sometimes microorganisms…
• It reflects the optical properties of water in terms of light scattering
ability instead of transmitting in straight lines.
Conductivity
• The ability of water to conduct electricity, indicates the amount
of dissolved minerals and gases in water.
• Conductivity measured in micro mhos/cm or MicroSiemns/cm3
9
Taste
• Presence of dissolved salts and gases imparts bitter, soapy, brackish
and palatable taste which is normally co-related with odour.
• Bitter (Fe, Al, Mn, SO42-, Ca(OH)2)
• Soapy (NaHCO3)
• Brackish (High salt content - NaCl)
• Palatable (CO2 and NO3-)
Odour
• Domestic and industries activities cause undesirable odour to water
• Industrial effluent of organics, sewage discharge, presence of N, S
and P contains compounds, metal ion pollution like Fe
• Substances like algae, peat, bacteria
• Grassy odour, peaty odour, offensive odour
10
MAJOR IMPURITIES OF WATER
Alkalinity
Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2
Magnesium Carbonate other suspended matter H2S
Hydroxide NH3
Sodium Color, Plankton CH4
Potassium Sulfate Organic matter, O2
Ammonium Chloride Colloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria
11
Total Dissolved Solids
Total Dissolved Solids (TDS) are the total amount of mobile charged
ions, including minerals, salts or metals dissolved in a given volume of
water, expressed in units of mg per unit volume of water (mg/L), also
referred to as parts per million (ppm).
Total dissolved solids are normally discussed only for freshwater systems,
as salinity includes some of the ions constituting the definition of TDS.
More exotic and harmful elements of TDS are pesticides arising from
surface runoff.
14
DO levels
15
DO vs Aquatic life
16
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DO determination - Winkler’s method
• Iodometric titration
• Redox chemistry is involved
• Sources of error – presence of nitrites and hydrogen
sulphide in the water sample.
18
Calculation - DO
19
Biological Oxygen Demand
Biological oxygen demand (BOD) is the amount of dissolved oxygen
needed by aerobic biological organisms in a water body to break down
organic material present in a given water sample at certain
temperature over a specific time period.
The BOD value is most commonly expressed in milligrams of oxygen
consumed per litre of sample for the biologically oxidizable impurities
during 5 days of incubation at 20 °C and is often used as a robust
surrogate to determine the degree of biodegradable organic pollution
in water.
BOD is similar in function to COD, in that both measure the amount of
organic compounds in water. However, COD is less specific, since it
measures everything that can be chemically oxidized, rather than just
levels of biologically active organic matter.
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Chemical Oxygen Demand (COD)
Chemical oxygen demand (COD) test is commonly used to
indirectly measure the amount of organic compounds in water.
The basis for the COD test is that nearly all organic compounds
can be fully oxidized to carbon dioxide with a strong oxidizing
agent under acidic conditions. The amount of oxygen required to
oxidize an organic compound to carbon dioxide, ammonia, and
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water.
COD Estimation
The difference in the amount of FAS needed to titrate the blank and the
sample is proportional to COD.
22
Calculation
COD of water (mg/L) = (A-B) x M x 8 x 1000
V
23
Hard Water
What’s hard water?
mg/L (ppm)
Soft 0-17
Moderately hard (Medium) 60-120
Hard 120-180
Very hard 180 & over
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Why be concerned about Hard Water?
• Hard water does cause soap scum, clogs pipes and clogs
boilers as lime scale
25
Disadvantages of Hard water
Domestic Use Industrial Use
Washing Textile industry
do not lather with soap, silky (wastage of soap, precipitates of Ca
& Mg adhered to the fabric- which
precipitates of Mg and Ca
don’t produce the exact shades)
C17H35COONa + H2O C17H35COOH + NaOH
Sugar Industry
Lather
C17H35COOH + C17H35COONa
(water containing sulphates,
Bathing nitrates, alkali carbonates etc.
Cleansing quality of soap is poor causes difficulties in sugar
crystallization)
Cooking
elevated boiling point; more fuel for Concrete making
cooking (hydration of cement as well as
concrete strength)
Drinking
bad effect in digestive Pharmaceutical Industry
system; possibility of forming calcium (May produce undesirable
oxalate crystals in urinary tracks substance)
Hard water and soap
27
Hardness of Water
• Type of Hardness
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Types of Hardness
Solution :
204 X 100
Calcium carbonate equivalent hardness = = 150 mg of CaCO3/L
136
= 150 ppm
32
Units of Hardness
Most Commonly used
• Parts per million (ppm)
1ppm=1 part of CaCO3 equivalence hardness causing substance present in
106 parts of water
1mg/L=1ppm
Relationship; 1L water = 1Kg = 1000 g = 1000 X 1000 mg = 106 mg
1mg/L = 1mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1ppm
• Clarke's Degree(oCl)
1o Clarke= 1part of CaCO3 equivalent hardness in 70000 parts of water
35
Problems
1. A water sample from an industry in Bombay had the following data
Mg(HCO3)2 = 16.8mg/L, MgCl2 = 19 mg/L, Ca(HCO3)2 = 20 ppm, MgSO4
=24.0mg/L and KOH = 1 ppm. Calculate the temporary, permanent and total
hardness of the water sample.
Solution
Step 1 conversion in to CaCO3 equivalent
Calculation
Total hardness, = (50 + 100 + 100+100) mg/L= 350 mg/L or 350 ppm
Eriochrome Black T
4. Preparation of indicator
Dissolve 0.5 g of EB-T in 100 ml alcohol
5. Standardization of EDTA solution
= V2 X 50 / V1 mg of CaCO3 eqvt.
= V3 X 50 / V1 mg of CaCO3 eqvt.
In boilers
– Concentration of the dissolved salts increases progressively when water
evaporates during continuous steam generation. When their
concentration reaches saturation point, the salts gets precipitated
probably on the inner walls of the boiler.
If the precipitate is
- Soft, Loose, slimy precipitate - Sludge
- Hard, adhering crust/coating on the inner walls of the boiler- Scale
Sludge Scale
Hard adhering
coating to the
Loose precipitate
suspended in water
Boiler wall inner walls of the
boiler
water
Heat Heat
Sludge
Slimy loose
precipitate called
sludge suspended in
water
wate
r
Boiler
wall
Sludge is a soft, loose and slimy precipitate formed within the
boiler. It can be easily scrapped off with a wire brush.
It is formed at comparatively colder portions of the boiler and
collects in areas of the system, where the flow rate is slow or
at bends.
It is formed by substances which have greater solubility's in
hot water than in cold water, e.g.
MgCO , MgCl , 53
Remedy: Sludges can be removed using
3 wire 2brush or
Disadvantages of sludges Prevention
• Poor conductor of heat – wastage of
energy •By using soft water
water
Boiler
wall
Scales are hard substances which sticks very firmly to the inner
surfaces of the boiler wall.
Scales are difficult to remove even with the help of a hammer
and chisel.
Examples: CaSO4, CaCO3, Mg(OH)2 55
Formation of Scales
Decomposition of calcium bicarbonate
56
Decomposition of calcium sulphate
• The solubility of calcium sulphate in water decreases
with increase of temperature (Why)
Presence of Silica
Presence of silica in small quantities deposits as calcium silicate
(CaSiO3) or magnesium silicate (MgSiO3). These deposits stick
very firmly on the inner side of the boiler surface and are very
difficult to remove.
58
Disadvantage of scale formation
• Decrease in efficiency
• Danger of explosion
59
Removal of Scales
60
Prevention of scale formation
• External Treatment
– The treatment includes efficient ‘softening of water’
– Removing hardness-producing constituents of
water
• Internal Treatment
– Phosphate conditioning
– Calgon conditioning
61
Prevention of scale formation
•Internal Treatment
In this process, an ion is prohibited to exhibit its
original character by ‘Complexing’ or converting into
other more stable salt by adding appropriate reagent.
Internal conditioning methods to prevent scale formation
65
3. Calgon conditioning
Na2[Na4(PO3) 6 ] 2Na+ +
[Na4(PO3Calgon
) 6]2-– sodium hexa meta
phosphate
NaOH has better mobility and can percolate into fine cracks
present in boiler walls.
Na2CO3 + H2O → 2 NaOH +
CO2
Sodium Ferrate
ANODE CATHODE
72
Dissolved oxygen – a nuisance for boiler
material
Fe + H2O + ½ O2 Fe(OH)2
Fe(OH)2 + O2 [Fe2O3.nH2O]
(Ferrous hydroxide) (Rust)
Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2+ 2H2O
Na2S + 2O2 Na2SO4
Removal of DO – By mechanical deaeration
Water feed
Removal of CO2
By adding calculated quantity of ammonia
The liberated acid reacts with iron of the boiler in chain-like reactions
producing HCl again and again. As a result presence of even a small
amount of MgCl2 will cause corrosion of iron to a large extent.
Fe + 2HCl FeCl2 + H2