Engineering Chemistry

Dr. Jianping Hu
Employment ID: 15381

Office: 201C or G01A13, SJT Annex

Email: [email protected]
Text Book(s):

1. Sashi Chawla, A Text book of Engineering Chemistry, Dhanpat Rai Publishing Co., Pvt.
Ltd., Educational and Technical Publishers, New Delhi, 3rd Edition, 2015.
2. O.G. Palanna, McGraw Hill Education (India) Private Limited, 9th Reprint, 2015.
3. B. Sivasankar, Engineering Chemistry 1st Edition, Mc Graw Hill Education (India),
2008
4. "Photovoltaic solar energy : From fundamentals to Applications", Angële Reinders,
Pierre Verlinden, Wilfried van Sark, Alexandre Freundlich, Wiley publishers, 2017.

Reference Books:

1. O.V. Roussak and H.D. Gesser, Applied Chemistry-A Text Book for Engineers and
Technologists, Springer Science Business Media, New York, 2nd Edition, 2013.
2. S. S. Dara, A Text book of Engineering Chemistry, S. Chand & Co Ltd., New Delhi, 20th
Edition, 2013.
 Module 1: Water
Technology
● 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.
Characteristics of hard water - hardness, DO, TDS in
water and their determination
Types of impurities in water
 Sources of Water
● Naturally available water can be classified as:

♦ Surface water: Flowing water: streams, rivers and

Still water: ponds, lakes and reservoirs.
♦ Underground water: From springs and wells and from coal mining
cuttings.
♦ Sea water: It is the most impure form of water containing about 3.5%
dissolved salts of which about 6% is NaCl. Other salts present include
sulphates, bicarbonates, bromides of sodium, potassium, magnesium etc
♦ Rain water: It is the purest form of natural water but contains dissolved
toxic gases like CO2, SO2, NO2 etc. and other solids. Also its supply is
unpredictable.

It is therefore, necessary to depend on ground and surface water after

removing different impurities that are present in them, as required.
 Impurities in Water

● Suspended Impurities:
♦ Particles in water give rise to turbidity:
Debris
Colloids

● Dissolved Impurities:
♦ Total Dissolved solids (TDS):
Inorganic salts
Organic Matter
♦ Dissolved Gases

● Biological Impurities:
♦ Microorganism:
Pathogens
 Impurities in water
Water has different physical, chemical and biological Impurities
which can cause problems in both domestic and industrial
applications.
● Physical:
♦ Inorganic such as clay, sand
♦ Organic such as oil globules, vegetable/animal matter
♦ Colloidal such as Fe(OH)3, Complex proteins, amines
● Chemical
♦ Anions such as Cl-, SO42-, CO32-,HCO3-, NO3- bonded to Ca2+ & Mg2+
♦ Cations such as Ca2+, Mg2+, Na+, K+, Fe3+, Al3+
♦ Dissolved gases such as O2, N2, CO2, H2S, NH3
(NaCl, Na2SO4, KCl, SiO2, Fe2O3 does not impart any hardness to water. )

● Biological
♦ Micro-organisms such as algae, fungi, bacteria
(Pathogenic causing malaria, diarrhea, typhoid etc.)
 Impurities in water
● Natural water is contaminated mostly by three major types of
impurities:
♦ Physical impurities
♦ Chemical impurities
♦ Biological impurities
Physical Chemical Biological
impurities impurities impurities
Color Acidity Micro-
Turbidity Gases organisms

Taste Minerals
Odor
Can be removed by
Can be removed by Can be removed by chlorination.
Sedimentation, Coagulation, Chemical treatment.
Adsorption or Filtration
 Impurities in water

● Municipal water supplied to Homes: Physical and

Biological impurities (major removal) + Chemical impurities
(minor removal)

● Water supplied to Industries: Physical and Chemical

impurities (major removal) + Biological impurities (negligibly
removed)
Other factors that control water characteristics:
pH, DO, TDS, COD and BOD in water
 pH and water quality

● Pure water’s pH=7 at 25 °C; value varies with temperature.

pH of pure water at 50°C is 6.55.
● When an acid or base is dissolved in water, the pH will be less or greater
than pure water. pH will be 0 to 14,
 ♦ Water that has been exposed to air is mildly acidic as it absorbs carbon
dioxide and converted into bicarbonate and hydrogen ions (essentially
creating carbonic acid).
 ♦ The pH of seawater plays an important role in the ocean's carbon
cycle, ocean acidification caused by carbon dioxide emissions.
 ♦ High pH causes a bitter taste, water pipes and water-using appliances
become encrusted with deposits, Low-pH water will corrode or dissolve
metals and other substances.
 ♦ Pollution can change pH, which in turn can harm animals and plants
living in the water. For instance, water coming out of an abandoned coal
mine can have a pH of 2, which is very acidic.
 pH and water quality
● pH of water in the range <6.5 or >8.5 is considered
as harmful.
● The sources to impart such pH are carbonates,
bicarbonates, CO2, industrial contaminants (pH 3.6-
8.4), mineral acids (pH 3.5 or below).
● Highly acidic water (pH<6.5) causes corrosion to
pipes, highly basic water (pH >8.5) causes staining.
● Highly acidic water is treated using calcite(CaCO3)
neutralizer and alkaline water is by dealkalyzer.
Dissolved oxygen (DO)
 Dissolved oxygen (DO)
● Dissolved oxygen gets into the
water by diffusion from the
atmosphere, aeration of the
water as it tumbles over falls
and rapids, and as a waste
product of photosynthesis.

● Dissolved oxygen (DO) is the

amount of oxygen dissolved in a
given quantity of water at a
particular temperature and
atmospheric pressure.

● DO: Amount of oxygen

dissolved in one liter of water-
expressed as mg/L (ppm).

● One of the best indicators to

Henry's Law: Henry's law states that at a constant temperature,
understand the health of the the amount of a gas that dissolves in a liquid is directly
water body and life sustaining proportional to the partial pressure of that gas in equilibrium
ability. with that liquid. It was formulated by William Henry in 1803.
 Dissolved oxygen (DO)
● Factors affecting DO levels:
♦ Aeration
♦ Water temperature: Temperature of the water body
♦ Organic wastes
♦ Aquatic plant populations
♦ Photosynthetic activity of the water
♦ Respiration of animals and plants
♦ Speed of water flow
♦ Roughness of surface over which water flows
♦ Altitude(atmospheric pressure)
♦ Human activities
♦ Salt concentration: The solubility of oxygen decreases with increase in
concentration of the salt under a pressure of one atmosphere, the solubility is
less in saline water.
♦ Other dissolved gases concentrations: Dissolved N2, CO2 etc reduces DO.

Henry's Law: Henry's law states that at a constant temperature, the amount of
a gas that dissolves in a liquid is directly proportional to the partial pressure of
that gas in equilibrium with that liquid. It was formulated by William Henry in 1803.
Dissolved oxygen (DO)
 Dissolved oxygen (DO)
● Dissolved oxygen is
essential for all animal
life. To maintain healthy
water the amount of
oxygen must be as high
as possible.

● Most life supporting

water systems: 4-6
mg/L of DO.
 Dissolved oxygen
● When the maximum amount of oxygen possible is dissolved in water,
it is said to be saturated.
♦ The saturation concentration decreases with increasing
temperature and is smaller for salt water than for sea-water.
e.g. at 25 oC the saturation concentration of oxygen in fresh water is
8.3 mg.L-1 , while in salt water it is 6.7 mg.L -1 .
♦ The concentration of dissolved oxygen is also temperature
dependent: at 10 oC the saturated concentration of oxygen in fresh
water is 11.3 mg.L-1 while at 20 oC it is 9.2 mg.L-1 .

● Any reduction in the amount of oxygen in a body of water, caused by a

rise in temperature or by pollution, may mean that certain animals can
no longer live there. The concentration of dissolved oxygen can
therefore be taken as a measure of the ability of water to support living
things. lf the oxygen concentration is less than half the maximum
concentration then the water is of poor quality. Water in rivers flowing
over water-falls may have a higher than normal level of dissolved
oxygen.
 Estimation of DO by Winkler’s method
● Theory of Winkler’s Method:
♦ Oxygen in the water sample oxidizes iodide ion (I-) to iodine (I2)
quantitatively.
♦ The amount of iodine generated is then determined by titration
with a standard thiosulfate (S2O3-2) solution.
♦ The endpoint is determined by using starch as a visual indicator.
♦ The amount of oxygen can then be computed from the titre values.
 Dissolved oxygen
Winkler method (Winkler titration)

Summary of Winkler method:

● Oxygen in the water sample oxidizes iodide ion (I- ) to iodine (I2) quantitatively. The
amount of iodine generated is then determined by titration with a standard thiosulfate
(S2O3 2-) solution. The endpoint is determined by using starch as a visual indicator. The
amount of oxygen can then be computed from the titer: one mole of O2 reacts with
four moles of thiosulfate (n(O2):n(S2O3 2- )=1:4).

● At the time of sampling, dissolved oxygen is fixed by the addition of Mn(II) (as a
catalyst) under basic conditions, resulting in a brown precipitate, manganic hydroxide
(MnO(OH)2). Prior to analysis, the sample is acidified to pH 1.0-2.5. This causes the
precipitated hydroxides to dissolve, liberating Mn(III) ions. Mn(III) ions oxidize
previously added iodide ions to iodine. Iodine forms a complex (I3 - ) with surplus
iodide ions. Iodine and the complex exist in equilibrium; thus, I3 - serves as a reservoir
of I2. The iodine is then titrated with thiosulfate. Iodine is reduced to iodide and the
thiosulfate is oxidized to tetrathionate.
 Dissolved oxygen
Winkler method (Winkler titration)
The stoichiometric equations for the reactions are:
MnSO4 + 2 KOH →Mn(OH)2+ K2SO4
2Mn(OH)2 + O2 → 2 MnO(OH)2 (oxidation of Mn(II) to Mn(III))
MnO(OH)2 + H2SO4 → MnSO4 + 2 H2O + [O]
2 KI + H2SO4 + [O] → K2SO4 + H2O + I2 (oxidation of I- to I2)
I2+ 2 Na2S2O3 → Na2S4O6 + 2NaI (oxidation of S2O32-to S4O62-; reduction
of I2 to I-)

Or taking into account of the formation of I3-:

I2 + I- ↔ I3-
I3-+ 2 S2O32- → S4O62- + 3I- (oxidation of S2O32- to S4O62-; reduction of I3- to
I-)
 Dissolved oxygen
Winkler method (Winkler titration)
Standardization of the thiosulphate solution:
● The thiosulfate solution is not stable and therefore must be standardized with a
primary standard, typically potassium iodate (KIO3). Standardization is based on the
co-proportionation reaction of iodide with iodate, thereby forming iodine. As
described above, the iodine binds with excess iodide, and the complex is titrated with
thiosulfate. One mole of iodate produces three moles iodine, which are consumed by
six moles of thiosulfate.

IO3- + 8I- + 6H+ → 3I3- + 3H2O

I3-+ 2 S2O32- → 3I- + S4O62-

 Dissolved oxygen
Winkler method (Winkler titration)
Calculation and expression of results:
The calculation of oxygen concentration (mL O2 .L-1 ) from this analysis
follows in principle the procedure outlined by Carpenter (1965).
O2 (mL.L-1)=((R-Rblank)*VIO3*NIO3*E)/((Rstandard-Rblank)*(Vsamplebottle-Vreagents))-DOreagents
Where:
R = Volume of thiosulfate used to titrate the sample (mL);
Rstandard= Volume of thiosulfate used to titrate the KIO3 standard (mL);
Rblank = Volume of thiosulfate used to titrate the blank as measured above (mL);
NIO3 = Normality of standard KIO3 (equiv/L);
VIO3 = Volume of KIO3 standard (mL);
E = 5598 mL O2 / equivalent;
Vsamplebottle = Volume of sample bottle (mL);
DOreagents = Oxygen added with reagents**;
Vreagents = Volume of reagents.

**DOreagents depends on the flasks, reagents and reaction conditions. DOreagents=0.018

in Carpenter’s set-up(1965). The additional correction for DOreagents of 0.0017 mL
oxygen added in 1 mL manganese chloride and 1 mL of alkaline iodide has been
suggested by Murray, Riley and Wilson (1968).
Total dissolved solids
 Total dissolved solids
● Total dissolved solids (TDS):
♦ Total dissolved solids (TDS) is the amount of particles
dissolved in water.
♦ It is a measure of the combined content of
all inorganic and organic substances contained in a liquid in
molecular, ionized or micro-granular (colloidal sol) suspended
form.

● It is expressed in units of mg per unit volume of water

(mg/L) or as parts per million (ppm).

● TDS is directly related to the purity and the quality of water

purification systems.
Total dissolved solids
 Total dissolved solids
 Sources:
 ● Organic sources:
silt, plankton, and industrial waste and sewage.

 ● Inorganic sources:
weathering and dissolution of rocks and soils and air that may contain
calcium bicarbonate, nitrogen, iron phosphorous, sulfur, and other minerals.

 ● Other sources:
♦ runoff from urban areas, agricultural and residential
♦ runoff road salts used on street during the winter
♦ fertilizers and pesticides used on lawns and farms
♦ discharge from industrial or sewage treatment plants
♦ lead or copper as they travel through pipes used to distribute water to
consumers
♦ Industrial waste and sewage as well as runoff from urban sources
 Total Dissolved Solids (TDS)
● A constant level of minerals, eg. phosphorous, nitrogen and
sulphur, is necessary for aquatic life.

● Concentration of dissolved solids should not be too high or

too low which can affect the growth and leads to death of
many aquatic organisms.

● High concentration of dissolved solids reduces the clarity of

water and can decrease the photosynthesis and raises the
water temperature.
 Total Dissolved Solids
● Recommended TDS for drinking water is 25-250 mg/L.

● At any cost drinking water TDS should not exceed 500 mg/L.

● TDS for distilled water will be 0.5-1.5 mg/L.

● TDS ranges from 100-20,000 mg/L in river water and will be generally
higher in ground water.

● Sea water will have 3500 mg/L of TDS.

● Lakes and streams will have a TDS of 20-250 mg/L.

 Total dissolved solids
 ● The two principal methods of measuring total dissolved solids
are gravimetry and conductivity.

● Electrical conductivity of water is directly related to the concentration of

dissolved ionized solids in the water, which can be measured using a
conventional conductivity meter or TDS meter.

 ● Different governments have different regulations for the TDS level. The U.S. EPA
sets the maximum contaminant level for TDS 500 ppm
 Total Dissolved Solids (TDS)
(Gravimetry, gravimetric method or gravimetric analysis)
Gravimetric methods are the most accurate and involve evaporating the
liquid solvent and measuring the mass of residues left. This method is generally the
best, although it is time-consuming. If inorganic salts comprise the great majority of
TDS, gravimetric methods are appropriate.

● The source of dissolved solids is various kinds of minerals present in water.

● It can be determined taking a known amount (say 100 mL) of water and by
evaporating the contents carefully to dryness.
● The residue (W grams) left after evaporation of the filtered sample shows the total
dissolved solids present in that particular water sample.
● TDS must be less than 500 ppm in potable water.

TDS = (W/100) x 106 mg/L or ppm

 Total Dissolved Solids (TDS)
(Electrical conductivity)
● Electrical conductivity of water is directly related to the concentration of
dissolved ionized solids in the water. Ions from the dissolved solids in water
create the ability for that water to conduct an electric current, which can be
measured using a conventional conductivity meter or TDS meter. When
correlated with laboratory TDS measurements, conductivity provides an
approximate value for the TDS concentration, usually to within ten-percent
accuracy.
● The relationship of TDS and specific conductance of groundwater can be
approximated by the following equation:
TDS = keEC,
where TDS is expressed in mg/L and EC is the electrical conductivity in
microsiemens per centimeter at 25 °C. The correlation factor ke varies between
0.55 and 0.8(It depends on sample conductivities.).
COD and BOD
 COD and BOD
● Oxygen Demanding Wastes:
♦ Chemical Oxygen Demand (COD):
Chemicals/Organic wastes present in water consume the DO.
♦ Biological Oxygen Demand (BOD):
Organic wastes reaching water consume oxygen from water bodies for
their decomposition by bacteria through biochemical oxidation.

♦ These are useful measures to check water quality.

 Chemical oxygen demand (COD)

● It is a measure of the total quantity of oxygen required to oxidize all

inorganic and organic material into carbon dioxide and water. Chemical oxygen
demand is “a measure of the oxygen equivalent of the organic matter content of a
sample that is susceptible to oxidation by a strong chemical oxidant.”
● Or it is the capacity of water to consume oxygen during the decomposition
of organic matter and the oxidation of inorganic chemicals.
● A COD test measures all organic carbon with the exception of certain
aromatics (benzene, toluene, phenol, etc.) which are not completely oxidized in the
reaction.
● COD measurements are commonly made on samples of waste waters or of
natural waters contaminated by domestic or industrial wastes.
● Chemical oxygen demand is measured utilizing a strong chemical oxidant
under specific conditions of temperature and for a particular period of time.
● A commonly used oxidant in COD assays is potassium dichromate (K2Cr2O7)
which is used in combination with boiling sulfuric acid (H2SO4) and mercuric sulphate
(HgSO4) .
● The test is not adversely affected by toxic substances, and test data is
available in 1-1/2 to 3 hours, providing faster water quality assessment and process
control.
 Biochemical oxygen demand(BOD)
 ● Most natural waters contain small quantities of organic compounds and
aquatic microorganisms use these compounds as food.

 ● Microorganisms living in oxygenated waters use dissolved oxygen to oxidatively

degrade the organic compounds, releasing energy which is used for growth and
reproduction.

Organic matter+microorganisms+O2+ nutrients→ CO2(gas)+H2O+microorganisms

 ● Biochemical oxygen demand (BOD) is the amount of dissolved
oxygen needed by aerobic biological organisms in a body of water to break down
organic material present in a given water sample of oxygen required to carbon
dioxide and water through generations of microbial growth, death, decay, and
cannibalism at certain temperature over a specific time period.

 ● It is expressed in milligrams of oxygen consumed per liter of sample during 5

days of incubation at 20 °C.
[BOD]= mg O2/L or ppm
 Biochemical oxygen demand(BOD)

Under:
● Specified Time: 5 Days

● Specified Temperature: 20±10 C

● Specified Conditions: In the Darkness.

In the Presence
of Bacteria.
 Biochemical oxygen demand(BOD)

● Significance of BOD
♦ It is very useful in designing of treatment plants and
calculation of waste load.

♦ BOD gives a qualitative index of the organic substances

which are degraded quickly in a short period of time.
 Biochemical oxygen demand(BOD)

● Total Biochemical Oxygen Demand (TBOD):

When a measurement is made of all oxygen consuming materials in a
sample, the result is termed “Total Biochemical Oxygen Demand”
(TBOD), or often just simply “Biochemical Oxygen Demand” (BOD).
Because the test is performed over a five day period, it is often referred
to as a “Five Day BOD”, or a BOD5.

● Carbonaceous Biochemical Oxygen Demand (CBOD):

Sometimes it is advantageous to measure just the oxygen demand
exerted by organic (carbonaceous) compounds, excluding the oxygen
demand exerted by the nitrogenous compounds. To accomplish this,
the nitrifying organisms can be inhibited from using oxygen by the
addition of a nitrification inhibitor to the samples. The result is termed
“Carbonaceous Biochemical Oxygen Demand”, or CBOD.
BOD Procedure (Based on DO measurement)
Fill bottle (with dilution water)

Measure initial DO (DOIn )

Set up stopper (No Air Bubbles)

Set up seal (Water and Cover)

Incubate: 20 ± 1°C
5 Days ± 6 hour

Measure final (residual)DO(DOout)

 BOD Procedure (Based on DO measurement)

● BOD Calculation
DOIn - DOOut = Depletion
= Oxygen Demand of Diluted Sample
For dilution water: Maximum depletion should be 0.2 mg/L.
Depletion
BODSample = x Volume of diluted sample
Sample Volume taken (mL)

Minimum Depletion: 2.0 mg/L

Minimum Residual: 1.0 mg/L

Numerical problem:
Calculate the BOD:
Initial Sample D.O. = 8.1 mg/L
5-Day Sample D.O. = 2.1 mg/L
Volume of sample in 300 mL Bottle = 60 mL
BOD(mg/L) = DO Depletion(mg/L) X 300 mL
Volume Sample(mL)

= Initial DO- Residual DO X 300 mL

Volume Sample(mL)

= 8.1 mg/L - 2.1 mg/L X 300 mL

60 mL

= 6.0 mg/L X 300 mL

60 mL

= 0.1 mg/L X 300 = 30 mg/L

 Biochemical oxygen demand(BOD)
BOD Measurement System (Based on CO2 absorption)

Working principle:

● Respirometric methods provide direct

measurements of the oxygen consumed by
microorganisms from an air or oxygen-enriched
environment in a closed vessel under conditions of
constant temperature and agitation.

● Carbon dioxide produced metabolically by the

bacteria is chemically bound by the potassium
hydroxide solution contained in the seal cup in the
bottle.

● The result is a pressure drop in the system, which

is directly proportional to the BOD value and is
measured by the BOD sensor. The BOD level is then
displayed directly in mg/L.
 Biochemical oxygen demand(BOD)
● Some common ranges of BOD results are as follows, in mg/L (or ppm):
♦ Influent 150-400
♦ Primary Effluent 60-160
♦ Secondary Effluent 10-60
♦ Digester Supernatant 1000-4000+
♦ Industrial Wastes 100-3000+
♦ Domestic sewage 320
♦ Cow shed sewage 3010
♦ Paper mills 8190
♦ Tannery effluents 12360

● CBOD results are almost always lower than BOD (TBOD) results. For a highly nitrified effluent
sample, the difference can be as great as 50%.
 Biochemical oxygen demand(BOD)

● BOD is similar in function to chemical oxygen demand (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.

● Total BOD is of more significance to food webs than to water quality.

 BOD and COD
● COD:
♦ It is the total measurement of all oxidizable chemicals (organics &
inorganics) in the water / waste water.
♦ COD is the total amount of oxygen required to chemically oxidize the
biodegradable and non-biodegradable matter.

● BOD:
♦ The amount of oxygen required for the microorganisms(bacteria) to
degrade the biodegradable organic components present in water /
waste water.

● The ratio of COD/BOD:

♦ COD is higher than BOD. Maximum of this ratio is up to 4 in medium
scale industries.
♦ But it varies based on the industrial process and nature of the raw
materials used.
 BOD and COD
● In such industries where effluents are cellulose or other non-
biodegradable organic matter, COD value reveals the real pollution
potential.
● It is a very important parameter in designing and management of the
treatment plants.
● COD test does not differentiate between bio-inert and biodegradable
materials.
● COD tests does not indicate the rate at which biologically oxidizable
material stabilize.
● As BOD is only a measurement of consumed oxygen by aquatic
microorganisms to decompose or oxidize biodegradable organic
matter and COD refers the requirement of dissolved oxygen for the
oxidation of organic and inorganic constituents both.

– Hence COD must be greater than BOD.

 COD vs. BOD
Parameter COD BOD
Oxidant Used K2Cr2O7, Mn2(SO4)3 Oxidation by microorganisms

Most Suitable Use Rapid and frequent monitoring of treatment plant Modeling treatment plant process and the
efficiency and water quality effects of organic compounds on the dissolved
oxygen content of receiving waters

Test Completion 1-1/2 to 3 hours 5 days (for standard BOD test)

Time
Accuracy and 5 - 10% relative standard deviation; may be higher 15% relative standard deviation; not considered
Precision when samples contain suspended solids; sample highly accurate
homogenization can be important

Advantages • Correlates with BOD on waste with constant • Most closely models the natural environment
composition. when used with the proper “seed”
• Toxic materials do not affect oxidant.
• Changes in the COD value between influent and
effluent may parallel BOD content and supplement
BOD results.
• Short analysis time
Disadvantages • Interference from chloride ions. • Toxic materials kill microorganisms.
• Some organic compounds are not oxidized • Microorganisms do not oxidize all materials
completely. present in waste.
• Inaccuracies when used with improper “seed”.
• Lengthy test period.
 Comparing all of our “oxygens”

Dissolved oxygen: Amount of actual oxygen dissolved in a water sample.

Higher number = purer water

BOD5: Actual amount of dissolved oxygen metabolized over 5 days.

Higher number = dirtier

COD: Actual amount of oxygen required to completely oxidize organic

waste CHEMICALLY. Higher number = dirtier.
Hardness of Water
 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 don’t produce
precipitates of Mg and Ca
the exact shades)
C17H35COONa + H2O C17H35COOH + NaOH
● Sugar Industry
C17H35COOH + C17H35COONa Lather
(water containing sulphates, nitrates, alkali
● Bathing carbonates etc. causes difficulties in sugar
Cleansing quality of soap is poor. crystallization)

● Cooking ● Concrete making

elevated boiling point; more fuel for (poor hydration of cement as well as
cooking concrete strength)

● Drinking ● Pharmaceutical Industry

bad effect in digestive system; possibility of (May produce undesirable substance)
forming calcium oxalate crystals in urinary tracks
 Hardness of water
● Hardness of water is the characteristic of preventing lather formation
of water with soap. Generally salts like chlorides, bicarbonates and
sulfates of Ca2+, Mg2+ and Fe2+ make water hard.

● This hard water on treatment with soap which is stearic or palmitic

acid salts of sodium or potassium causes white precipitate formation
of calcium or magnesium stearate or palmitate.

● Thus the cause of hardness is the precipitation of the soap and hence
prevents lathering at first. When the hardness causing ions are
removed as insoluble soaps, water becomes soft and forms lather.
 Hardness of Water
Water Hardness: Characteristic that prevents the lathering of soap
(Caused by dissolved salts of Ca and Mg)

2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl

2C17H35COONa + MgSO4 (C17H35COO)2Mg + 2NaSO4

 Types of Hardness
● Hardness of water is due to dissolved salts of mainly calcium and magnesium as
well as iron and other heavy metals.
● Hardness has two types:
a) Temporary :
♦ Due to dissolved bicarbonates of calcium and magnesium and carbonates of
iron and other heavy metals. Hence it is also called as carbonate hardness.
♦ Can be easily removed by boiling where CO2 gas gets expelled removing
the hardness.

b) Permanent:
♦ Due to dissolved chlorides and sulphates of calcium and magnesium. Also
called as non-carbonate hardness.
♦ Can be removed through zeolite, Lime-soda, ion-exchange processes.
 Types of water hardness

Temporary Hardness (or) Permanent Hardness (or)

carbonate hardness noncarbonate hardness
● Presence of chlorides and sulphates of
● Dissolved bicarbonate salts of Ca and Mg ● Ca, Mg and other heavy metals
and other heavy metals such as iron Also called as non-carbonate hardness.
● Can be removed easily by boiling ● Can be removed through zeolite, Lime-
soda, ion-exchange processes.
● Can’t be removed by simple
Ca(HCO3)2 CaCO3 + H2O + CO2 boiling

Mg(HCO3)2 Mg(OH)2 + 2CO2

Total hardness = Temporary hardness + Permanent hardness

 Types of water hardness
Pseudo- hardness
● Sea, brackish, and other waters that contain appreciable
amounts of Na+ interfere with the normal behavior of soap
because of the common ion effect. Soap may not lather.
Sodium(Na+) is not a hardness-causing cation, and so this
action which it exhibits when present in water in high
concentration is termed pseudo-hardness.
The common ion effect is responsible for the reduction
in the solubility of an ionic precipitate when a soluble
compound containing one of the ions of the precipitate is
added to the solution in equilibrium with the precipitate.

● When there is high concentration of Na+ or K+ in water.  It

interferes with normal behavior of soap.
 Units of water hardness
● Parts per million (ppm):
Parts of CaCO3 equivalent hardness per 106 parts of water
● 1 ppm= (1 part of hardness)/(106 parts of water)

● Milligrams per liter (mg/L):

No. of milligrams of CaCO3 equivalent hardness present per liter of water.
● Degree Clark (°Cl):
No. of grains (1/7000 lb) of CaCO3 equivalent hardness per gallon (10 lb) of
Water (or) parts of CaCO3 equivalent hardness per 70,000 parts of water.
♦ 1 Clark=(1 grain of hardness)/(1 gallon or 70,000 grains)=1/(7 x 104)
1 grain (64.8 milligrams) of calcium carbonate dissolved in 1 US gallon of water (3.785412 L)

● Degree French (° Fr):

Parts of CaCO3 equivalent hardness per 105 parts of water.
♦ 1 French Degree of hardness=(1 part of hardness)/(105 parts of water)
● Milliequivalent per litre (meq/L):
Milli equivalents of hardness per liter
1 meq/L = 1 meq of CaCO3 per liter
 Units of Water hardness

Relation between various units of water hardness:

1 ppm = 1 mg/L = 0.1 ˚Fr =0.07 ˚Cl

1 mg/L = 1 ppm = 0.1 ˚Fr =0.07 ˚Cl
1 ˚Cl= 1.43 ˚Fr = 14.3 ppm = 14.3 mg/L
1 ˚Fr = 10 ppm = 10 mg/L = 0.7 ˚Cl
Numerical Problem:
If the hardness of water is 210.5 ppm Calculate its hardness in o Cl

Solution:
1 ppm = 0.07 o Cl
210.5 ppm = 0. 07 × 210.5
= 14.735o Cl
 Measurement of hardness of water
● Hardness of water is measured in parts per millions (ppm) as calcium
carbonate equivalents.

● Reasons for expressing hardness in CaCO3 equivalents:

♦ Its molecular weight is 100 ; equivalent weight is 50.
♦ It is the most common insoluble impurity in water.

● Units of hardness:
♦ parts per million in CaCO3 equivalents (1 mg/L is 1ppm.).

If 146 mg/L of MgSO4 is present in water, the hardness of

water is 146 ppm. as MgSO4. But it is inconvenient.
 Water hardness
Hardness as well as non-hardness constituting ions are generally
expressed in terms of equivalent amount of CaCO3. Temporary and
permanent hardness are expressed in ppm as CaCO3 equivalent. The
choice of CaCO3 is due to the fact that its molecular weight is 100
and equivalent weight is 50 and it is the most insoluble salt in water.
The equivalents of CaCO3 (in ppm or mg/L)

Amount(concentration) of hardness producing substance (given in the numerical) x Equivalent weight of CaCO3 (which is 100/2)
=
Equivalent weight of hardness producing substance (molar mass of hardness producing substance/its oxidation number)

Amount(concentration) of hardness producing substance (given in the numerical) x 50

=
Equivalent weight of hardness producing substance (molar mass of hardness producing substance/its oxidation number)

=Amount(concentration) of hardness producing substance (given in the numerical) x X factor for CaCO3 Equivalent
Dissolved salt/ion Molar Oxidation X factor for CaCO3 Equivalent
Mass No.

Ca(HCO3)2 162 +2 (100/2) x (2/162) = 100/162

CaSO4 136 +2 (100/2) x (2/136) = 100/136
CaCl2 111 +2 (100/2) x (2/111) = 100/111 Element Atomic
MgSO4 120 +2 (100/2) x (2/120) = 100/120 Mass
MgCl2 95 +2 (100/2) x (2/95) = 100/95 H 1
Ca(NO3)2 164 +2 (100/2) x (2/164) = 100/164 C 12
HCO3- 61 +1 (100/2) x (1/61) = 100/122 N 14
OH- 17 +1 (100/2) x (1/17) = 100/34 O 16
CaCO3 100 +2 (100/2) x (2/100) = 100/100 Na 23
MgCO3 84 +2 (100/2) x (2/84) = 100/84 Mg 24
CO32- 60 +2 (100/2) x (2/60) = 100/60 Al 27
NaAlO2 82 +1 (100/2) x (1/82) = 100/164 S 32
Al2(SO4)3 342 +6 (100/2) x (6/342) = 300/342 = Cl 35.45
100/114
Ca 40
FeSO4.7H2O 278 +2 (100/2) x (2/278) = 100/278
Fe 56
H+ 1 +1 (100/2) x (1/1) = 100/2
HCl 36.5 +1 (100/2) x (1/36.5) = 100/73
 Examples of hardness calculations
Numerical problem:
A sample hard water contains,
8.1 mg/L Ca(HCO3)2 ; 7.5 mg/L Mg(HCO3)2; 13.6 mg/L CaSO4;
12.0 mg/L MgSO4 and 2.0 mg/L MgCl2.

To calculate the hardness and express in CaCO3 equivalents:

Solution:

Constituent Multiplication CaCO3 equivalents

factor
Ca(HCO3)2= 8.1 mg/L 100/162 8.1 x 100/162 = 5.0 mg/L
Mg(HCO3)2 = 7.5 mg/L 100/146 7.5 x 100/146 = 5.14 mg/L
CaSO4= 13.6 mg/L 100/136 13.6 x 100/136 = 5.0 mg/L
MgSO4= 12.0 mg/L 100/120 12.0 x 100/120 =10.0 mg/L
MgCl2 = 2.0 mg/L 100/95 2.0 x 100/95 = 2.11 mg/L
63
Numerical problem 1: Calculate the temporary hardness and permanent hardness of a sample
of water containing Mg(HCO3)2 = 7.3 mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L; CaSO4 =
13.6 mg/L.

Solution: Convert the hardness causing salts into their CaCO3 equivalents!

Constituent X factor CaCO3 equivalent Hardness type

Mg(HCO3)2 = 7.3 mg/L 100/146 7.3 x 100/146 = 5 mg/L Temp. Mg2+
Ca(HCO3)2 = 16.2 mg/L 100/162 16.2 x 100/162 = 10 mg/L Temp. Ca2+
MgCl2 = 9.5 mg/L 100/95 9.5 x 100/95 = 10 mg/L Perm. Mg2+
CaSO4 = 13.6 mg/L 100/136 13.6 x 100/136 = 10 mg/L Perm. Ca2+

H 1
Final Answer:
C 12 Temporary hardness = 5+10 = 15 mg/L or ppm
O 16 Permanent Hardness = 10+10 = 20 mg/L or ppm
Mg 24 Total hardness = 35 mg/L or ppm
Cl 35.45
S 32
Ca 40
Numerical problem:
How many grams of FeSO4 dissolved per liter gives 210.5 ppm of
hardness?
(Atomic weights: Fe = 56, S = 32, O = 16, Ca = 40, C = 12).

Solution:
FeSO4 CaCO3
(56 + 32 + 64 = 152g) 100g
100 ppm of hardness is given by 152 ppm of FeSO4

To give 210.5 ppm of hardness, 152 × 210.5 = 319.9 ppm of FeSO4

100
= 319.9 mg/L or 0.319 g/L of FeSO4 is needed.
 Estimation of water hardness-EDTA method
● Principle:
♦ Ethylene diamine tetraacetic acid (EDTA)disodium salt (Molecular weight=
336.208 g/mol, C10H14N2Na2O8) is used as a strong complexing agent(chelating
agent) with Ca2+ and Mg2+ in hard water. EDTA is employed as its disodium salt.

♦ The structure of EDTA disodium salt is:

NaOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COONa

♦ EDTA forms permanent stable complex with Ca2+ and Mg2+ present in the hard
water.

♦ EDTA solution is colorless.

 Estimation of water hardness-EDTA method
● Principle:
♦ Initially, Ca2+ and Mg2+ are treated with Eriochrome black T(C20H12N3NaO7S,
Molecular weight= 461.381 g/mol) (EBT) indicator using ammonia buffer
(ammonium chloride / ammonia, to maintain pH between 9-10) to get an unstable
complex of Ca2+ and Mg2+ formed with EBT.

The structure of EBT is:

EBT is blue in a buffered solution at pH 10, it turns red when Ca2+ ions were added.

pH 9-10
Ca2+/Mg2+ + EBT Ca2+/Mg2+ EBT
(unstable complex – wine red)
 EDTA method of water hardness estimation
● Principle:
♦ After titration with EDTA, EBT gets replaced with EDTA since EDTA
forms a stronger complex with the metal ions. The characteristic
blue end-point is reached when sufficient EDTA is added and metal
ions is chelated by EDTA, leaving the free indicator molecule.

♦ This is indicated by the formation of a steel blue colored

complex.
pH 9-10
Ca2+/Mg2+ EBT + EDTA Ca2+/Mg2+ EDTA + EBT
(unstable complex – wine red) (Stable complex) (Steel blue)
(Colorless)
 Stable complex formed by EDTA chelation

+ + 2 H+
Ca2+

H2EDTA2- Ca2+ ion chelated by

EDTA
 EDTA method of water hardness estimation

● Brief procedure of hardness measurement:

♦ First EDTA Solution is standardized using standard hard water (1 mg/ml of CaCO3
equivalents is prepared as standard hard water).
♦ For this, first known aliquot of Standard hard water is taken and 10-15 mL of
ammonia buffer is added to bring the pH between 9-10.
♦ Then a few drops of EBT solution is added to form the unstable complex giving
wine red color.
♦ This solution is titrated with the EDTA solution till the solution turns to steel blue
indicating the formation of stable EDTA-Metal ion complex.
♦ This volume of EDTA is noted as V1.
♦ The above procedure is repeated with sample hard water of unknown hardness.
♦ Volume of EDTA is noted as V2.
♦ Then sample hard water of 250 mL is taken and evaporated to a volume of 50mL
when the temporary hard salts settle down.
♦ The solution is filtered and washed thoroughly and made up again to 250mL.
♦ From this solution, 50 mL is pipetted out and titrated in similar manner as done
with standard hard water.
♦ Volume of EDTA is noted as V3.
 Experimental procedure(Detailed)

1. Preparation of EDTA solution (0.01 M):

i.e. dissolve 3.72 g of sodium salt of EDTA crystals in 1 litre of
distilled water
2. Preparation of standard Hard Water:
a. Dissolve 1.0 g of pure, dry CaCO3 in small quantity of
concentrated HCl and evaporate the solution to dryness
b. Dissolve the residue in distilled water (1 liter)
1ml of this solution contains 1 mg of CaCO3 equivalent hardness.

3. Preparation of buffer solution:

Add 67.5 g of NH4Cl to 570 ml of concentrated Ammonia
solution and dilute with distilled water to 1 liter.
4. Preparation of indicator:
Dissolve 0.5 g of EBT in 100 ml alcohol
 5. Standardization of EDTA solution:

Burette: EDTA solution (0.01 M)

50 ml of 10-15 ml of few drops of

Conical Flask: standard + ammonia + EBT indicator
hard water buffer
Volume of EDTA consumed = V1 ml
6.Estimation of total Hardness:
50 ml of 10-15 ml of few drops of
Conical Flask: sample hard + ammonia + EBT indicator
water buffer

Volume of EDTA consumed = V2 ml

 7.Estimation of permanent Hardness:
♦ Boiled water preparation:
▲ Take 250mL of Hard water sample, boil it, reduce the volume to about
50mL.
▲ Bicarbonates are decomposed to insoluble CaCO3 and Mg(OH)2.
▲ Filter, wash the precipitate with distilled water, collect the filtrate,
make up to 250mL.
▲ Take 50mL of boiled water + EDTA

♦ Titration:
50 ml of 10-15 ml of
Conical Flask: + few drops of
boiled ammonia +
EBT indicator
sample buffer
hard water
Volume of EDTA consumed = V3 ml
 Calculation: (a)Estimation of Total Hardness
● V1 mL of EDTA is consumed by 50 mL of std. hard water
So, 50ml of standard hard water(SHW)= 50 mg of CaCO3 = V1 mL of
EDTA
Hence, 1mL of EDTA = 50 / V1 mg of CaCO3 equivalent.
● EDTA consumed by sample hard water = V2 mL
So, V2 mL of EDTA= 50ml of given hard water
= V2 X 50 / V1 mg of CaCO3 equivalent.

Therefore,
1mL of Given hard water = V2 X 50 / V1X 50 mg of CaCO3 equivalent.

1000mL of Given hard water = 1000 x V2 / V1 mg of CaCO3 equivalent.

● Total Hardness of water = 1000 x V2 / V1 mg/L

= 1000 x V2 / V1 ppm
 Calculation: (b)Estimation of Permanent Hardness
● 50 mL of sample hard water after removing temporary hardness
consumed V3 mL of EDTA.
It means: V3 mL of EDTA= 50ml of boiled water.
Since, 1 mL of EDTA = 50/V1 mg of CaCO3 equivalent.

Therefore, V3 mL of EDTA = V3 X 50 / V1 mg of CaCO3 equivalent.

It means: 50 mL of sample hard water after boiling contained 50/V1
x V3 mg of CaCO3 equivalent.
Hence,
1mL of boiled water = V3 X 50 / V1X 50 mg of CaCO3 equivalent.

1000mL of boiled water = 1000 x V3 / V1 mg of CaCO3 equivalent.

● Permanent Hardness of water = 1000 x V3 / V1 mg/L

= 1000 x V3 / V1 ppm
 Calculation: (c)Estimation of Temporary Hardness

● Temporary Hardness of water

=Total hardness– Permanent hardness
= 1000 x V2 / V1 - 1000 x V3 / V1
= 1000{ (V2-V3)/V1} ppm

● Temporary Hardness of water= 1000{ (V2-V3)/V1} ppm

Numerical problem:
0.5 g of CaCO3 was dissolved in HCl and the solution made up to 500 ml with
distilled water. 50 ml of the solution required 48 ml of EDTA solution for
titration. 50 ml of hard water sample requires 15 ml EDTA and after boiling
and filtering requires 10 ml of EDTA solution. Calculate the hardness.
Solution:
1 ml of standard hard water contain 1 mg of CaCO3
Then 50 ml of standard hard water contains 50 mg of CaCO3.

50 ml of standard hard water consumes 48 ml of EDTA (V1)

48 ml of EDTA = 50 mg of CaCO3 equivalent hardness
1 ml of EDTA = 50 mg of CaCO3 equivalent hardness
48

78
 Continued
Calculation of total hardness:
50 ml of water sample consumes 15 ml of EDTA (V2)

Total Hardness = (15/48) x 1000 x 1 mg of CaCO3

= 312.5 ppm

Permanent hardness: (non – carbonate hardness)

50ml of water sample = 10 ml of EDTA (V3)

Permanent Hardness = (10/48) x 1000 x 1 mg of CaCO3

= 208.4 ppm

Temporary Hardness (1L) = Total hardness – Permanent hardness

= 312.5 – 208.4 = 104.1 ppm
Numerical problem: 0.5 g (or 500 mg) of CaCO3 was dissolved in HCl and the solution was
made up to 500 ml with distilled water. 50 ml of the solution required 48 ml of EDTA for
standardization titration. 50 ml of hard water sample required 15 ml of EDTA and after boiling
and filtering, required 10 ml of EDTA solution. Calculate the hardness.

Another calculation method: At first, 500 ml of SHW ≡ 500 mg of CaCO3 eq.

1 ml of SHW ≡ 1 mg of CaCO3 eq.
a) Standardization of EDTA:
50 ml of standard hard water (SHW) is consumed by 48 ml (V1ml) of EDTA
1 ml of EDTA = 50/48 mg of CaCO3 eq.
b) Estimation of total hardness:
50 ml of sample hard water = 15 ml (V2 ml) of EDTA
50 ml of sample hard water = 15 x 50/48 mg of CaCO3
Therefore, 1000mL of sample hard water = 15 x 50/48 x 1000/50 mg/L
Total hardness of sample hard water = 312.5 mg/L (ppm) of CaCO3
(c) Estimation of Permanent (non-carbonate) hardness:
50 ml of boiled hard water = 10 ml (V3 ml) x 50/48 mg of CaCO3
Therefore, 1000 ml of sample hard water = 10 x 50/48 x 1000/50 mg/L of CaCO3 (ppm)
Therefore, Permanent hardness = 208.3 mg/L (ppm) of CaCO3
d) Estimation of Temporary (carbonate) hardness :
Temporary hardness = Total hardness – permanent hardness = 104.2 ppm
Numerical problem:
In an EDTA titration, 50 ml of standard hard water sample(1mg CaCO3 in 1ml)
consumed 25 ml of EDTA, 50 ml of hard water sample consumed 35 ml of EDTA and
the 50ml sample hard water (after boiling, cooling and filtering) required 10ml EDTA .
Calculate the permanent and temporary hardness of the given water sample.
Solution:
● 1 mL standard hard water = 1mg CaCO3
50 mL standard hard water = 25 mL EDTA (V1)
Therefore, 1 mL EDTA = (50/25) x 1mg CaCO3

● 50 ml of hard water = 35 ml of EDTA (V2)

1000 mL of hardwater contains = ( 35/25) x 1000 x 1mg CaCO3
Total hardness = 1400 ppm

● After boiling, EDTA consumed = 10 mL

50 mL of hard water sample = 10 mL of EDTA (V3)
1000 mL of hard water sample after boiling contains = (10/25) x 1000 x 1mg CaCO3
Permanent hardness = 400 ppm

● Therefore, temporary hardness = 1400 - 400 = 1000 ppm

Numerical problem:

Calculate Total, Temporary and Permanent hardness of the given hard water
sample with following analysis report:
[i] 50 mL of standard hard water sample consume 42 mL of EDTA solution.
[ii] 50 mL of hard water sample consume 19.9 mL of EDTA solution before
boiling.
[iii] 50 mL of hard water sample consume 8.9 mL of EDTA solution after boiling.
Standard hard water is prepared by dissolving 1.5 gram of CaCO3 per liter.

Solution:
1mL of standard hard water contains 1.5mg of CaCO3
[i] For 1mL of EDTA
[ii] total hardness: 710.7 ppm
[iii] permanent hardness: 317.8 ppm
Temporary hardness: 392.9

82
Numerical problem. 50 ml of a sample water consumed 15 ml of 0.01 M (or 0.02 N) – EDTA
before boiling and 5 ml of the same EDTA after boiling. Calculate the Total hardness; Permanent
hardness and Temporary hardness.
Important points to remember:
In complexometric titrations(here): Normality of EDTA = 2 * Molarity of EDTA
In Acid – Base titrations: Normality of EDTA = 4 * Molarity of EDTA

a) Estimation of total hardness:

50 ml of water sample = 15 ml of 0.01 M of EDTA
1000 mL of water sample = 15 x 1000/50 ml = 300 ml of 0.01 M EDTA which is
2 x 300 ml = 600 ml or 0.6 L of 0.01 N EDTA (Normality of EDTA = 2 * Molarity of EDTA)
Total hardness = 0.6 L of 0.01 CaCO3 equivalent = 0.6 x 0.01 x 50 g CaCO3 equivalent= 0.3
g/L or 300 mg/L or 300 ppm of CaCO3 equivalent.
b) Estimation of permanent hardness:
Now, 50 ml of water sample = 5 ml of 0.01 M of EDTA
1000 mL of water sample = 5 x 1000/50 ml = 100 ml of 0.01 M EDTA which is
2 x 100 ml = 200 ml or 0.2 L of 0.01 N EDTA (Normality of EDTA = 2 * Molarity of EDTA)
Permanent hardness = 0.2 L of 0.01 CaCO3 equivalent =0.2 x 0.01 x 50 g CaCO3
equivalent= 0.1 g/L or 100 mg/L or 100 ppm of CaCO3 equivalent.
Hence, Temporary hardness = (300-100) ppm = 200 ppm.
 Note:

NaCl, KCl, Na2SO4, SiO2, Fe2O3 do not cause any

hardness and so, don’t include them in the
calculation.
Modern methods of water analysis
 Modern methods of water analysis
● Importance of Water Analysis:

Water analysis is essential to ensure its quality or to detect pollutants that should be removed

by water treatment. However, water quality does not mean making the water suitable for

human consumption; it depends on its end use. For example, completely different quality

standards are applied in case of industrial water compared to those applied to drink water, i.e.,

drinking water must be fit for human consumption, while industrial water should be free from

any contaminants that may corrode or damage equipment.

● Limitations of Traditional Methods of Water Analysis:

The traditional analysis includes chemical analysis, colorimetry, spectrometry,

chromatography, and atomic absorption. Although these techniques differ in sensitivity and

accuracy, most of them are highly accurate. Nevertheless, they require sampling, expensive

devices, and manpower; besides, they are time-consuming and difficult to conduct onsite.
 Modern methods of water analysis
Lab-on-a-chip
● A lab-on-a-chip (LOC) is a device that integrates one or several laboratory functions on a single
integrated circuit (commonly called a "chip") of only millimeters to a few square centimeters
to achieve automation and high-throughput screening
● Lab-on-a-chip devices are a subset of microelectromechanical systems (MEMS) devices and
sometimes called "micro total analysis systems" (µTAS)
● LOCs may provide advantages, which are specific to their application. Typical advantages are:
a) low fluid volumes consumption (less waste, lower reagents costs, and fewer sample
volumes)
b) faster analysis and response time due to short diffusion distance & high surface to volume
ratio.
c) better process control because of a faster response of the system compactness of the
systems due to the integration of much functionality and small volumes
d) lower fabrication costs, allowing cost-effective disposable chips, fabricated in mass
production
e) safer platform for chemical, radioactive or biological studies because of integration of
functionality, smaller fluid volumes, and stored energies
 Lab-on-a-chip
● Microfluidics and Lab-On-A-Chip for Water Analysis

♦ Microfluidics and lab-on-a-chip systems are advanced technologies that may

replace the traditional methods of water analysis in the near future.
♦ Lab-on-a-chip technology employs microfluidics, which deals with very
minute amounts of fluids in microchannels, to perform the analysis.
♦ The lab-on-a-chip device is a chip that resembles electronic chips, but with
micro-channels instead of electrical circuits.
♦ It shrinks the lab to the chip size and can perform complete analysis or even
series of analysis.

● Advantages of using lab-on-a-chip for water analysis:

♦ It can reduce time and manpower in the sampling process because this
technology can offer immediate, onsite results.
♦ In addition, this technique is much less expensive and offers higher
accuracy, because of the small volumes analyzed and the possibility of
eliminating the sampling process, which reduces the human error.
 Components of Lab-on-a-chip systems
● Main components: The main components of a lab-on-a-chip system for water analysis are;
a liquid delivery system (injector and fluidic transporter), mixer, reactor, separator, and power
supply.
♦ The Injector is used to deliver precise volumes into the chip. The most common types of the
injectors are syringe pumps and robotic pipets.
♦ Transporters control all aspects of the flow. They can be active, which need an energy source, or
passive, which are achieved by manipulating the geometries of the channels and do not require
any energy source. The choice between the active and passive types is based on the application.
There are multiple types of active transporters, but the most preferred is electrochemical
pumping systems, such as microsyringe pumps, because they eliminate the design complexity.
♦ Mixers are used to mix different fluids into the channels. Similar to the transporters, the types of
mixers are divided into passive, which are achieved by design manipulation, and active, which
require power.
♦ The reactor is where the reaction takes place. There are three types of reactors used in lab-on-a-
chip systems: gas phase, liquid phase, and packed-bed reactors.
♦ Controllers are used for controlling all types of activities in the chip as well as data acquisition and
signal processing.
♦ Power supplies, such as batteries, are essential to run the lab-on-a-chip systems. Many research
studies focus on finding more advanced power supplies because some types of lab-on-a-chip
systems require high voltage.
 Current Applications in Water Analysis
● Lab-on-a-chip technology is rapidly developing and being used in different
industrial and research fields.

● Most biological lab-on-a-chip devices are commercialized, while those for

water analysis are still developing.

● However, some lab-on-a-chip applications in water analysis are already

established, such as pH testing and detection of various chemicals (e.g.,
nitrates and nitrites, manganese, phosphates, and silicates).

● For example, the microfluidic pH analysis uses sulfonephthalein as the main

indicator.

● It includes the absorption cell, a static mixer, as well as a syringe pump and
four valves attached to the chip to regulate the flow.
References:
1. J. Cleary, C. Slater, D. Diamond, Analysis of phosphate in wastewater using an autonomous
microfluidics-based analyser, World Acad. Sci. Eng. Technol. 52 (2009) 196–199.
2. R. Paul Payel, “Lab on a Chip” Systems for Environmental Analysis, University of Stavanger, 2014.
Disadvantages of hard water
 Problems of hard water for domestic use
● Washing:
♦ Hard water, when used for washing purposes, does not lather freely
with soap.
♦ It produces sticky precipitates of calcium and magnesium soaps.
♦ Similar problem exists in bathing.

● Cooking:
♦ Due to the presence of dissolved hardness producing salts the
boiling point of water is elevated.
♦ Consequently more fuel is and time are required for cooking.

● Drinking:
♦ Hard water causes bad effect on our digestive system.
♦ The possibility of forming calcium oxalate crystals in urinary tracks is
increased (Kidney stones).
 Disadvantages of hard water in industries
● Paper Industry:
♦ The presence of calcium and magnesium has impact on the properties and quality
of paper and their products
● Textile industry :
♦ Hard water cause much of the soap to go as waste.
♦ During dyeing process, calcium and magnesium salts present in water make the
quality of the shades very poor.
● Sugar industry :
♦ If nitrates, sulphates of calcium and magnesium are present, they cause hindrance
to crystallization of sugar
● Concrete making :
♦ Water containing chlorides and sulphates, if used for concrete making, affects the
hydration of the cement and the final strength of the hardened concrete.
● In steam generation in boilers:
♦ If the hard water is fed directly to the boilers, which led to the many problems
such as formation of scales which corrodes the boiler, formation of sludge, wastage of
fuel etc.
Boiler troubles
 Boiler and Boiler feed water
● The setup used to produce steam in industries is known as ‘Boiler’.

● In most of the industries, water is used for production of steam. This water
should be free from dissolved Ca and Mg salts. Such water is called BOILER
FEED WATER.
● Boiler troubles: If boiler water contains impurities beyond prescribed
limit, they lead to following problems.
Sludge, scale, caustic embrittlement, boiler corrosion, priming and
foaming are collectively known as boiler troubles.
Sl. No. Requirements for boiler water If not, it will cause

1 Free from hardness causing salts Sludge and scale

2 Free from oil and greases Foaming

3 Free from dissolved salts, suspended Caustic embrittlement

impurities
4 Free from dissolved gases, suspended salts Boiler corrosion
Scale and sludge
 Scale & Sludge Formation in Boilers
● 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.

♦ Sludge: If the precipitate is soft, loose and slimy.

♦ Scale: If the precipitate is hard, adhering crust/coating on the inner walls of the
boiler.

Sludge Scale
● Sludge: soft, loose, slimy precipitate formed in the boiler
water, during the generation of steam.
♦ Can be washed easily using brush.
♦ Formed at comparatively colder places of the boiler.
♦ Collects in a system where the flow rate is slow like bends.
♦ Formed by the substances which have greater solubilities in
hot than cold water. (Examples: MgCO3, MgCl2, CaCl2, MgSO4).

~~~~
~~~~~~~~
~~~~ ~ ~
~~ ~ ~ ~~~~
~ ~
~~~~~~~~~ ~
~~~ ~ ~~ ~~
~~~~
~~~~ ~~~~
~ ~~~~~
~~ ~~
~ ~ ~ ~ ~~~~
~
~~~~~~~
~~~~
Heat
● Scales: hard, adhering crust/coating on the inner
walls of the boiler during steam generation .
♦ Hard deposits, stick very firmly to the inner
surfaces of the boiler.
♦ Difficult to remove even with the help of
hammer.
♦ Main source for the boiler corrosion
▲ Low pressure boilers Ca(HCO3)2, MgCl2
▲ High pressure boilers CaSO4, Silica

x
x
x

Heat
 Sludge Scale

Loose precipitate Boiler wall

suspended in water
scale

water

Heat Heat
Examples of Sludge and Scale
 Differences between sludge and scale
No Sludge Scale
1 Loose, slimy , non-adherent precipitate Hard, thick , strong adherent precipitate
2 Due to salts like MgSO4 , MgCl2 Due to salts like CaSO4 , Ca(HCO3)2
3 Due to poor conductance, they Due to poor conductance, they
decrease the boiler efficiency to decrease the boiler efficiency to
lesser extent and causing maximum extent, cause reduced fuel
chocking in the pipelines. economy , improper boiling, boiler
explosion etc.,
4 It can be prevented by periodical It can be prevented by special methods
replacement of concentrated hard Like:
water by fresh water. This process i)external treatment of ion exchange ,
is known as “blow down” method. ii)Internal carbonate, phosphate,
Calgon conditioning
iii)Mechanical hard scrubbing
methods.
5
 Sludge
● Disadvantages of Sludge Formation:
♦ Chocking of pipes
♦ Poor conductor of heat, wastage of fuel
♦ Low supply of heat
♦ If sludge formed along with the scale, sludge gets entrapped within
scale and both gets deposited as scale.
♦ Excessive sludge formation disturbs the working condition of the
boiler.

● Removal of Sludges:
♦ By brushing
♦ Frequent blow down process: Withdrawing portion of sludge
containing water and replacing with fresh water.
 Sludge

● Prevention of Sludge Formation:

♦ Frequent blow down Process: Withdrawing portion of sludge
containing water and replacing with fresh water.
♦ Using soft water.
 Formation of Scales
● Decomposition of calcium bicarbonate:
♦ Scales are the main source of boiler troubles. Scale composed
chiefly of calcium carbonate is soft and is the main cause of scale
formation in low-pressure boilers.
Heat
Ca(HCO3)2 → CaCO3↓+ H2O +CO2
Scale

♦ But in high-pressure boilers, CaCO3 is soluble.

CaCO3+ H2O Ca(OH)2 (Soluble) + CO2

 Formation of Scales
● Precipitation of calcium sulphate:
♦ The solubility of calcium sulphate in water decreases with increase of
temperature.

♦ The solubility of CaSO4 is 3,200 ppm at 15°C and it reduces to

55 ppm at 230°C and 27 ppm at 320°C. In other words, CaSO4 is soluble in
cold water, but almost completely insoluble in super-heated water.

♦ CaSO4 gets precipitated as hard scale on the heated portion of the boiler.
This is the main cause of scales in high-pressure boilers. Calcium
sulphate scale is quite adherent and difficult to remove, even with help of
hammer and chisel.
 Formation of Scales
● Hydrolysis of magnesium salts:
♦ Dissolved magnesium salts undergo hydrolysis forming magnesium
hydroxide precipitate which forms a soft type of scale.

MgCl2 + 2H2O Mg(OH)2 + 2HCl

● 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. One important source of silica is sand
filter.
 Scale
● Disadvantages of Scale Formation:
♦ Poor conductor of heat , wastage of fuel: Scale has a low thermal
conductivity, so the rate of heat transfer from boiler to inside water
is greatly decreased. In order to provide a steady supply of heat to
water, excessive or over-heating is done and this causes increase in
fuel consumption. The wastage of fuel depends upon the thickness
and the nature of scale.

Thickness of scale in (mm) 0.325 0.625 1.25 2.5 --

Wastage of fuel 10% 15% 50% 80% --

♦ Decreases in Efficiency: Scales may sometimes deposit in the valves

and condensers of the boiler and choke them partially. This results in
decrease in efficiency of the boiler.
 Scale
● Disadvantages of Scale Formation:
♦ Lowering of boiler safety: Due to scale formation, over-heating of boiler is
to be done in order to maintain a constant supply of steam. The over-
heating of the boiler tube makes the boiler material softer and weaker and
this causes distortion of boiler tube and makes the boiler unsafe to bear
the pressure of the steam, especially in high-pressure boilers.
♦ Danger of Explosion: If there is a crack on the scale, it may lead to
differential heating and increases the possibility of boiler explosion.
When thick scales crack, due to uneven expansion, the water comes
suddenly in contact with over-heated steam plates. This causes in
formation of a large amount of steam suddenly. So sudden high-pressure is
developed., which may even cause explosion of the boiler.
♦ Clogging: Boiler tubes may clog due to scale formation
♦ Corrosion
 Scale
● Removal of Scales:
♦ By scrapping: With the help of scraper or piece of wood or wire
brush, if the scales are loosely adhering.
♦ Giving thermal shocks (heating the boiler and then suddenly
cooling with cold water) if the scales are brittle.
♦ If the scales are adherent and hard dissolving them by using
chemicals.
▲ Calcium carbonate(CaCO3) scales can be removed by 5-10% HCl.
▲ Adding complexing agents. Example: Calcium sulphate(CaSO4)
scales can be dissolved by adding EDTA (ethylene diamine tetra
acetic acid) with which they form soluble complex.
♦ Frequent blow down process if the scales are loosely adhering :
Withdrawing portion of water and replacing with fresh water.
 Prevention of scale formation

a.Internal treatment: b. External treatment

(Sequestration)
Conditioning methods lime soda process, zeolite
or ion exchange process.

Sequestration:

♦ The process where suitable chemicals are added to the

boiler containing hard water with which scales are either
precipitated or converted in to soluble complexes.
♦ The chemical used is called Sequestrating agent.
 Prevention of scale formation
● Internal Treatment:
♦ Colloidal Conditioning.
♦ Phosphate conditioning.
♦ Carbonate conditioning.
♦ Calgon conditioning.
♦ Treatment with sodium aluminate.
♦ Blow down process.
etc.

● External Treatment:
♦ Treatment of water before entering into boiler.
♦ The treatment includes efficient ‘softening of water’: Removal
of Ca, Mg and Silica.
♦ Removing hardness-producing constituents of water
 Prevention of scale formation
● Internal treatment:
♦ In this process (also called sequestration), an ion is prohibited to
exhibit its original character by 'complexing' or converting it into other
more soluble salt by adding appropriate reagent.
♦ An internal treatment is accomplished by adding a proper chemical
to the boiler water either: (a) to precipitate the scale forming impurities
in the front of sludges, which can be removed by blow-down operation,
or (b) to convert them into compounds, which will stay in dissolved form
in water and thus do not cause any harm.
Notes: (i) Blow down operation is partial removal of hard water
through top at the bottom of boiler, when extent of hardness in the
boiler becomes alarmingly high. (ii) 'Make up' water is addition of fresh
softened water to boiler after blow down operation.
 Prevention of scale formation

● Internal treatment (Conditioning)

♦ Colloidal Conditioning.
♦ Phosphate Conditioning.
♦ Carbonate Conditioning.
♦ Calgon Conditioning.
♦ Treatment with sodium meta aluminate.
♦ Electrical conditioning.
♦ Radioactive conditioning.
♦ Complexometric method.
 Prevention of scale formation
♦ Colloidal Conditioning:
In low-pressure boilers, scale formation can be avoided by adding
organic substances.
▲ Adding kerosene, tannin, agar-agar (a gel). These organic
substances get covered over the scale forming precipitates to yield non-
sticky and loose deposits which can be removed by pre-determined
blow-down operations.
 Prevention of scale formation
♦ Phosphate Conditioning:
Used for high pressure boiler. No risk of CO2 liberation. Three types
of phosphate salts are used.
♦ Sodium phosphate reacts with Ca2+ and Mg2+ ions in water forming
non adherent and easily removable soft sludge of Ca and Mg
phosphates. The commonly used phosphates are NaH2PO4, Na2HPO4
and Na3PO4.

♦ The choice of salt depends upon the alkalinity of the boiler-feed

water. Calcium cannot be precipitated properly below a pH of 9.5, so
select a phosphate that adjusts pH to optimum value (9.5- 10.5).
Trisodium phosphate is most suitable for treatment, when alkalinity of
boiler water is low, as it is most alkaline in nature. If boil water's
alkalinity is sufficient, then disodium phosphate is more preferred. But if
the alkalinity of boil water is too high and requires to be reduced, then
monosodium phosphate, being acidic in nature, is preferred.
 Prevention of scale formation
♦ Phosphate Conditioning:

S. No. Salt Name Used for treating

1 Na3PO4 Tri sodium Phosphate highly acidic water
2 Na2HPO4 Di sodium hydrogen slightly acidic or
Phosphate weakly alkaline
water
3 NaH2PO4 Sodium di hydrogen highly alkaline water
phosphate

Sodium phosphate Optimal pH : 9.5 to 10.5

3CaSO4+ 2Na3PO4 -----------Ca3 (PO4)2 ↓+ 3 Na2SO4

NaH2PO4
3CaCl2+ 2Na3PO4 -----------Ca3 (PO4)2 ↓+ 6NaCl
Alkalinity
Na2HPO4
of boiler
Na3PO4 feed water
 Prevention of scale formation
♦ Carbonate Conditioning: Low-Pressure boilers:
In low pressure boilers, scale formation can be prevented by adding
Na2CO3 to boiler feed water. Ca salts are precipitated as loose sludge of
CaCO3 which can be removed by blow down operation. But some times
it produces NaOH, CO2 and hence carbonic acid. So it is less preferred.

Sodium carbonate
CaSO4+ Na2CO3 → CaCO3 + Na2SO4
 Prevention of scale formation
♦ Calgon Conditioning:
Calgon conditioning involves in adding Calgon(sodium hexameta
phosphate) to boiler water. It prevents the scale and sludge formation
by forming soluble complex compound with CaSO4.

Calgon: Sodium hexa meta phosphate: Na2 [Na4 (PO3)6]

Na2 [Na4 (PO3)6] ↔2Na+ + [Na4 (PO3)6]2-

2CaSO4+ [Na4 (PO3)6]2- →[Ca2 (PO3)6]2- + 2Na2SO4
soluble complex ion
(advantage)
Calgon is a brand registered trademark of water softener, and bath
and beauty products. Its name was a portmanteau derived from the
phrase "calcium gone". Today, the brand is owned by Reckitt
Benckiser for use in Europe as a water softener
 Prevention of scale formation
♦ Treatment with sodium meta aluminate(or called sodium
aluminate):
Boiler water is treated with sodium meta aluminate when NaOH and
gelatinous precipitate of Al(OH)3 are formed. NaOH precipitates Mg salt
as Mg(OH)2. Both Al(OH)3 and Mg(OH)2 precipitates formed entraps all
the scale forming materials. These loose precipitates formed can be
removed by blow down operation.
NaAlO2 +2H2O →NaOH+Al[OH]3↓
MgCl2 +2NaOH →2NaCl+Mg(OH)2↓
The flocculent precipitates of Mg(OH)2 plus Al(OH)3, produced
inside the boiler, entraps finely suspended and colloidal impurities,
including oil drops and silica. The loose precipitate can be removed by
pre-determined blow-down operation.
Sodium aluminate in thick solution form is available in plenty
and at a cheap rate from bauxite refining units and this can be
used as such for boiler- water treatment.
 Prevention of scale formation
♦ Electrical conditioning:
Sealed glass bulbs, containing mercury connected to a battery, are
set rotating in the boiler. When water boils, mercury bulbs emit
electrical discharges, which prevents scale forming particles to
adhere/stick together to form scale.

♦ Radioactive conditioning:
Tablets containing radioactive salts are placed inside the boiler water
at a few points. The energy radiations emitted by these salts prevent
scale formation.
 Prevention of scale formation
♦ Complexometric method:
It involves adding 1.5% alkaline (pH=8.5) solution of EDTA to feed-
water. The EDTA binds the scale-forming cations to form stable and
soluble complex. As a result, the sludge and scale formation in boiler is
prevented.

Moreover, this treatment:

(i) prevents the deposition of iron oxides in the boiler,
(ii) reduces the carry over of oxides with steam, and
(iii) protects the boiler units from corrosion by wet steam (steam
containing liquid water).
Caustic embrittlement
 Caustic Embrittlement
● Caustic Embrittlement (Inter crystalline cracking of boiler metal):
♦ The formation of irregular intergranular cracks on boiler metal
particularly at the point of high local stress by the use of highly
alkaline water in the boiler is called Caustic Embrittlement.
It is caused by using highly alkaline water in boiler
♦ It is a form of corrosion caused by high concentration of sodium
carbonate or sodium hydroxide in the boiler feed water.
♦ Caustic embrittlement is the phenomena in which the material of
a boiler becomes brittle due to accumulation
of caustic soda(NaOH).
♦ It is characterized by the formation of irregular inter-granular
cracks on the boiler metal, particularly at places of high local
stress such as bends and joints.

A tube damaged by caustic embrittlement. White caustic deposits can be seen inside.
 Caustic Embrittlement
● Causes of caustic embrittlement
♦ When water is softened by lime-soda process, free Na2CO3 is present in
softened water.
Boiler water usually contains a small amount of Na2CO3.
In high pressure boilers, Na2CO3 undergoes hydrolysis to produce NaOH. This
NaOH makes the water caustic.
Na2CO3 + H2O → 2NaOH +CO2
♦ This NaOH flows into and occupies the minute hairline cracks present on the
boiler material by capillary action. Here water evaporates and the
concentration of NaOH increases progressively which attacks the
surrounding area. NaOH dissolves the surrounding area of iron as sodium
ferrate, Na2FeO2.
Fe + 2NaOH → Na2FeO2 + H2
Thus it makes the cracks bigger.
3Na2FeO2 + 4H2O → 6NaOH + Fe3O4 + H2
6Na2FeO2 + 6H2O + O2 → 12NaOH + 2Fe3O4
So NaOH is regenerated in the process and its concentration is keep on
increasing maintaining a required environment. Thus corrosion process
develops cracks and making the metal brittle by the deposition of the
product. This makes the boiler parts brittle (embrittlement).
 Caustic Embrittlement
● Causes of caustic embrittlement
♦ This type of electrochemical corrosion occurs when the
concentration of NaOH is above 100ppm. This causes
brittlement of boiler parts, particularly the stressed
parts like bends, joints, rivets etc.
This causes embrittlement of
boiler parts particularly
stressed parts (bends, joints,
rivets, etc.)
Sodium Ferrate
♦ Concentration cell formation inside the boiler.
▲ Iron surrounded by dilute NaOH becomes the
cathodic side(cathode).
▲ Iron in contact with concentrated NaOH becomes
anodic part(anode). The anodic part slowly corrodes
and dissolves.
 Caustic Embrittlement
Concentration cell formation inside the boiler
__
+
Iron at stressed Concentated Dilute NaOH Iron at plane
parts NaOH surfaces
(rivettes, bends, solution
solution (Stress less)
joints etc. under
stress)
Anode Cathode

Minute hairline cracks Caustic stress corrosion crack in carbon steel

 Caustic embrittlement can be avoided.
● By using sodium phosphate as softening reagent instead of sodium
carbonate. (phosphate conditioning).

● By adding tannin or lignin to the boiler water which block the hair
line cracks and pits. These prevent the infilteration of NaOH through
hair line cracks .

● By adding sodium sulphate to boiler water, which also blocks the

hair line cracks and pits.
[Na2SO4]
= 1:1 2:1 3:1
[NaOH]
Up to Up to Higher than
Boiler pressure: 10 atm 20 atm 20 atm
● Neutralization of excess alkali by suitable technique.
Boiler corrosion
 Boiler Corrosion
● It’s a decay of boiler material by chemical or electro-
chemical attack by its surrounding environment.

● Reasons for boiler corrosion are:

♦ Dissolved oxygen,
♦ Dissolved carbon dioxide,
♦ Acids from dissolved salts.
♦ Presence of free acids
 Boiler Corrosion
● Dissolved oxygen:
Dissolved oxygen in water at high temperature attack boiler
material.

Fe + 2H2O + O2 Fe(OH)2 Ferrous hydroxide

2 Fe(OH)2 + O2 Fe2O3.2H2O
(Ferrous hydroxide) (Rust)
 Boiler Corrosion
● Dissolved oxygen can be removed:
♦ By adding calculated quantity of sodium sulphite (Na2SO3),
hydrazine(N2H4) or sodium sulphide(Na2S).

Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2+ 2H2O
Na2S + 2O2 Na2SO4

Hydrazine removes O2 without increasing the concentration of

dissolved solids. The products (N2 and H2O) are also harmless. Hence,
hydrazine is the most efficient internal treatment chemical for the
removal of dissolved oxygen.

♦ By addition of alkali.
 Boiler Corrosion
● Dissolved oxygen can be removed:
♦ Removal of dissolved oxygen by de-aeration
Deaeration (Mechanical and Chemical):
Mechanical and chemical deaeration is an integral part of modern boiler water
protection and control. Deaeration, coupled with other aspects of external treatment,
provides the best and highest quality feed water for boiler use.

Simply speaking, the purposes of deaeration are:

▲ To remove oxygen, carbon dioxide and other non-condensable gases from feed
water.
▲ To heat the incoming makeup water and return condensate to an optimum
temperature for:
► Minimizing solubility of the undesirable gases.
► Providing the highest temperature water for injection to the boiler.
 Boiler Corrosion
● Dissolved oxygen can be removed:
♦ Removal of dissolved oxygen by mechanical de-aeration
DO can be removed by mechanical de-aeration also. Water spraying in a perforated plate-
fitted tower, heated from sides and connected to Vacuum pump. High temperature, low
pressure and large exposed surface reduces dissolved oxygen in water. Dissolved gases like CO2
and O2 can be removed by this method. Water undergoes deaeration at high temperature and
low pressure because: Solubility of gases in water α P /T.
 Boiler corrosion
● Dissolved CO2:
♦ Dissolved CO2 from the below reaction is hydrolyzed to form
carbonic acid (H2CO3) which corrodes the boiler.
Heat
Mg(HCO3)2 Mg(OH)2 + 2 CO2

CO2 + H2O H2CO3

♦ Removal of CO2:

▲ CO2 is removed by adding calculated quantity of aqueous

ammonia:
2 NH4OH + CO2 (NH4)2CO3 + H2O

▲ It is also removed by mechanical de-aeration along with oxygen.

 Boiler corrosion
● Acids from dissolved salts:

♦ Dissolved magnesium salts hydrolyze to form acids:

MgCl2 + 2 H2O  Mg(OH)2 + 2 HCl

♦ This acid reacts with boiler in chain-like reactions producing HCl:

Fe + 2 HCl FeCl2 + H2

FeCl2 + 2 H2O Fe(OH)2 + 2 HCl (regenerated)

♦ Even a small quantity of magnesium salts will cause large amount of
boiler corrosion.
♦ Neutralization:
Excess acidic nature is neutralized by adding alkalis and vice versa.
HCl + NaOH → NaCl + H2O
Priming and foaming
 Priming and foaming

● Steam sometimes may be associated with small droplets

of water. Such steam containing liquid water is called wet
steam.
● These droplets of water carry with them some dissolved
salts and sludge material present in water. This phenomenon
is called carry over. This occurs mainly due to priming and
foaming.
● Priming and foaming occur together.
 Priming and foaming
● Disadvantages:

♦ Water hammer which disrupts operation of the equipment.

♦ Uneven heating of water.

♦ Actual height of water column in the boiler can not be judged

properly, thereby maintenance of boiler pressure becomes difficult.

♦ Dissolved solids in boiler water are carried by the wet steam to

super heater and turbine blades where they get deposited as water
evaporates.
This deposit reduces the efficiency of the machine.

♦ Erosion of turbine blades.

 Priming
● Priming is the formation of wet steam by rapid boiling of
the water at the heating surfaces. Along with steam, some
particles of water are carried (wet steam) which is called
priming.
♦ Disadvantages:
▲ Lowers the energy efficiency.
▲ Soluble salts enter other parts of machinery along
with steam. Water evaporates and salt crystals get
deposited reduced life of boiler.
▲ The deposits choke the pipelines carrying steam.
 Priming
♦ Causes:
▲ Very high water level.
▲ High steam velocity.
▲ Sudden increase in steam production rate leading to sudden
boiling.
▲ Presence of large amount of dissolved solids and suspended
impurities.
▲ Improper boiler design.
 Priming
● Priming can be prevented by:
♦ Keeping the water level lower.
♦ Good boiler design with a mechanical steam purifier.
♦ Avoiding rapid changes in steam generation rate.
♦ Using treated water. Efficient softening.
♦ Filtration of the boiler-feed water.
♦ Installing mechanical steam purifiers.
♦ Blow down of the boiler.
 Foaming
● Foaming is the formation of stable(persistent) bubbles above the
surface of water in a boiler. These bubbles do not break easily. It may
occur when the pH of the solution is between 7 and 9. Boil feed water
is agitated.

♦ Disadvantages:
▲ Air-bubbles formed due to foaming are carried away with steam.
They hinder the constant flow of steam.
▲ Due to foaming actual water level can not be judged well.
 Foaming

♦ Causes:
▲ The presence of surface tension lowering
substances which reduce the surface tension of
water, like oils or greases in water.
▲ Fine sludge particles.
▲ Difference between concentrations of solute
and suspended matters.
 Foaming
● Foaming can be prevented by:

♦ Removing the foaming stabilizing agents such as salts, clay,

and organic matter from water by using anti-foaming agents
or chemicals like synthetic polyamides, castor oil. Besides
castor oil, gallic acid and tannic acids, corn oil, cotton seed oil,
sperm oil, bee wax, etc., are also used as antifoaming agents.
♦ Adding coagulants such as sodium aluminate, ferrous
sulphate, etc., to remove sludge particles.
♦ Removing oily particles from the boiler feed water by
using silicic acid (H4O4Si) and sodium aluminate.
♦ Blow down operation of the boiler can prevent foaming.
For your information
 Chemical oxygen demand (COD)
For your information
Digestion methods:
● Dichromate has been used to oxidize organic matter for more than 70 years. It has been preferred over
other oxidants because of its superior oxidizing ability on a large variety of samples, and for its ease of use.
The test measures the oxygen equivalent of the amount of organic matter oxidized by potassium dichromate
in a 50% sulfuric acid solution. Generally, a silver compound is added as a catalyst to promote the oxidation
of certain classes of organic compounds. A mercuric compound may be added to reduce the interference
from oxidation of chloride ions.
● There are two digestion methods used in the COD test: the older Macro Digestion Method, and the
Micro Digestion Method.
♦ The Macro Digestion Method requires a considerable amount of space, equipment and volume of
reagents for each test. Each set-up includes a flask, a glass condenser with hose, a hot plate, a laboratory
stand, and clamps. Sample volumes are also relatively large. Because of these inconveniences, the macro
method has been virtually replaced by the micro method.
♦ The Micro Digestion Method minimizes reagent consumption and reduces the required space and
equipment to one reactor block that will digest up to 25 samples at one time. Each test set-up is a self-
contained disposable vial, which is inserted into a block heater. Reagent and sample volumes are
considerably smaller, which decreases reagent cost and waste volume. The two-hour digestion time can be
reduced if caution is observed. Many types of waste are digested completely in 30 minutes or less at 150 °C,
the normal operating temperature. The time of complete digestion can be recognized through experience,
or by using a colorimetric reading with the micro method discussed later. In this approach, many consecutive
readings are taken on a single sample, allowing a final determination of when the reaction is complete. After
the oxidation step is completed, the amount of dichromate consumed is determined titrimetrically or
colorimetrically. Either the amount of reduced chromium (trivalent) or the amount of unreacted dichromate
(hexavalent) can be measured. End products of the reaction are carbon dioxide, water, and various states of
the chromium ion.
 Chemical oxygen demand (COD)
For your information
Digestion methods:

The Macro Digestion Method The Micro Digestion Method

The micro method has several advantages over the macro method, including the
capture of volatile organics, small sample size, elimination of cumbersome
equipment, and a reduction in the volume of expensive and hazardous reagents.
 Chemical oxygen demand (COD)
For your information
Dichromate COD Chemistry

● When organic matter is oxidized by dichromate in sulfuric acid,

most of the carbon is converted to CO2. Hydrogen present is converted
to H2O. The reaction is illustrated using the primary standard, potassium
acid phthalate (KHP), as an example:

2 KC8H5O4 + 10 K2Cr2O7 + 41 H2SO4—> 16 CO2 + 46 H2O + 10 Cr2 (SO4)3 + 11 K2SO4

♦ Dichromate ions (Cr2O72-) form orange-colored solutions.

♦ When dichromate is reduced to chromic ion (Cr3+), the solution
becomes green.
♦ Intermediate valence states may also occur.
 Chemical oxygen demand (COD)
For your information
● Pros and Cons of Dichromate:
♦ Pros:
► Dichromate accomplishes a complete oxidation when used with a catalyst and a
two-hour digestion period.
► Dichromate is stable at room temperature when protected from exposure to
light.
♦ Cons:
► Some organic compounds are only partially oxidized.
► Some organic compounds, such as pyridine, cannot be oxidized.
► There can be interference from inorganic pollutants, mainly chloride ions.
► Reaction temperature is limited by thermal decomposition of the oxidant.
► Dichromate is classified as a carcinogen.
● Improving the Dichromate COD Test :
Through careful research, many of the disadvantages to the COD test have been overcome or
reduced in significance.
♦ Incomplete oxidation of aliphatic hydrocarbons, organic acids or alcohols have been
improved by using silver ion as a catalyst. But some compounds cannot be oxidized even with
the catalyst.
♦ Disposal considerations play an increasingly important role in chemical testing. Although the
micro-method minimizes the volume of waste generated, the dichromate COD does contain
hexavalent chromium, which must be treated as hazardous wastes and mercury.
 Chemical oxygen demand (COD)
For your information
MANGANESE (III) for COD
A newly developed COD test using Mn (III) COD oxidizes organic compounds in water without
the disposal problems associated with the other method.

● Reagent Preparation:
♦ Reagent preparation methods can be divided into three groups: methods based on
chemical oxidation of Mn(II); methods based on electrochemical oxidation of Manganese(II);
and methods based upon dissolution of solid Mn(III).
♦ The most frequently used method for laboratory-scale preparations has been
the oxidation of manganous sulfate with potassium permanganate, as described by the
following equation:
2 KMnO4 + 8 MnSO4 + 8 H2SO4—>5 Mn2 (SO4)3 + K2SO4 + 8 H2O
The Manganese (III) COD solution has a broad absorption band in the region of 420 to 600
nm, with a maximum absorbance at 510 nm. For comparison, potassium permanganate
is an oxidant that has a visual appearance somewhat similar to the Manganese (III) COD. Both
solutions are purple in color, but the spectra are quite different.

A: Mn III Reagent blank solution, approximately

0.008 N Mn(III).
B: Potassium Permanganate solution, approximately
0.001 N, in deionized water.
 Chemical oxygen demand (COD)
For your information
MANGANESE (III) for COD
• Comparative Advantages:
♦ The one-hour digestion period is shorter than other methods.
♦ Correlates very well with Dichromate COD and BOD test results.
♦ Is not photosensitive.
♦ Is stable at room temperature.
♦ The reagent contains no hazardous metals and generates no
hazardous metal waste.

• There are three factors that should be noted about the Manganese
(III) COD Procedure.
♦ It oxidizes approximately 80% of most organic compounds.
♦ There is interference from some inorganic compounds, mainly
chloride ions.
♦ And the reaction temperature is limited by thermal decomposition
of the oxidant.
 Chemical oxygen demand (COD)
For your information
Theoretical oxygen demand and COD test calibration
● Theoretical Oxygen Demand of Potassium Acid Phthalate (KHP) - The Industry
Standard:
COD testing is based upon the theoretical amount of oxygen required to oxidize
organic compounds to CO2 and H2O. The most commonly used standard is potassium
hydrogen phthalate (KHP). The theoretical oxygen demand of KHP is stated by the
following equation:
KC8H5O4 + 7.5 O2—> 8 CO2 + 2 H2O + KOH
7.5 molecules of oxygen consume one molecule of KHP. On a weight basis, the
theoretical oxygen demand for KHP is 1.175 mg O2 per mg KHP. To prepare a 2000
mg/L stock COD standard solution from KHP, the standard concentration is divided by
the theoretical oxygen demand, resulting in the amount of KHP to be dissolved in one
liter of deionized water. The
equation below demonstrates this for a 2000 mg/L COD standard solution.
[2000mg/L COD(O2)]/[1.175 mg O2 / mg KHP]= 1,702 mg KHP/L
Additional standards can be made by preparing serial dilutions of this stock solution.
Test results are expressed as mg/L COD or mg/L O2. These expressions are equivalent.

2 KC8H5O4 + 10 K2Cr2O7 + 41 H2SO4—> 16 CO2 + 46 H2O + 10 Cr2 (SO4)3 + 11 K2SO4

 Chemical oxygen demand (COD)
For your information
Theoretical oxygen demand and COD test calibration
● Calibrations based upon reference materials other than KHP
Occasionally, samples contain a major sample component which is incompletely oxidized, and
results will be lower than expected. It may be beneficial for COD results to
closely match the theoretical oxygen demand of the sample. In this situation, calibration
standards can be prepared from that sample component.
For example: An industrial wastewater sample contains acetone as a major sample
component and acetone is incompletely oxidized.
To obtain better results on this sample, a calibration curve can be prepared using acetone as
the reference material. To prepare the standard solution, first calculate the theoretical oxygen
demand of acetone.
C3H6O + 4 O2—> 3 CO2 + 3 H2O

Four molecules of oxygen consume one molecule of acetone and, on a weight basis, the
theoretical oxygen demand for acetone is calculated as follows:
4* (32 mg/mMole O2)/ (58 mg / mMole acetone) =2.21mg O2/(mg acetone)

A 1000 mg/L COD standard can be prepared from acetone as follows:

(1000 mg/L COD)/(2.21 mg O2 / mg acetone)= 452.5 mg acetone /L

Serial dilutions can be made for additional standards.

 Chemical oxygen demand (COD)
For your information
Theoretical oxygen demand and COD test calibration

● Theoretical Oxygen Demand of Nitrogen-Containing Compounds:

♦ Most nitrogen-containing compounds yield nitrogen as ammonia after oxidation.
This includes heterocyclic nitrogen-containing compounds, and is demonstrated using
pyrrole in the example below:
C4H5N + 4.5 O2—> 4 CO2+ H2O + NH3
4.5 molecules of oxygen consume one molecule of pyrrole. On a weight basis, the
theoretical oxygen demand for pyrrole is 2.149 mg O2 per mg pyrrole.

♦ Heterocyclic compounds containing two or more atoms of nitrogen in a molecule

are also easily oxidized. Generally, part of the nitrogen is split off as ammonia and part
is split off as diatomic nitrogen. This is demonstrated using Iimidazole in the following
example:
C3H4N2 + 3.25 O2—> 3 CO2 + 1/2 H2O + NH3 + N2
3.25 molecules of oxygen consumeone molecule of imidazole. On a weight basis,
the theoretical oxygen demand for imidazole is 1.507 mg O2 per mg imidazole.
 Chemical oxygen demand (COD)
For your information
Theoretical oxygen demand and COD test calibration

● Oxidation Efficiency of Organic Compounds

♦ The oxidation efficiency for a given organic compound can be easily determined. A
COD standard is prepared from the compound of interest and is tested. The result
of the test is then divided by the standard value and multiplied by 100 to determine
the percent recovery or oxidation efficiency.

♦ The dichromate COD procedure will oxidize most organic compounds with 90 -
100% efficiency. However, some compounds are not oxidized and others are only
partially oxidized, such as benzene, toluene, and ethylamines.
Examples of compounds that resist oxidation are pyridine, pyridine derivatives and
methylamines.
 Chemical oxygen demand (COD)
For your information
Catalysts
● Straight-chain aliphatic compounds are not effectively oxidized without a catalyst.
Several metals that have multiple valence states are generally effective as a catalyst
with dichromate. Silver, manganese, mercury, nickel, iron, cobalt and copper have all
demonstrated catalytic activity. Silver is the most effective catalyst for the greatest
variety of organic compounds, and manganese is reported to have a catalytic activity
comparable to silver on some compounds.

● The catalytic activity of silver is diminished through the formation of insoluble

silver halides when halides are present. These precipitates are partially oxidized, but
there is a significant loss of free silver ion which must be available for catalytic activity.
When sample chloride is complexed with mercury or removed through other
techniques, silver will be an effective catalyst.

● Catalysts have not produced significant improvement in recoveries of Manganese

(III) COD and also increase reagent cost. High silver concentrations increase recoveries
partially, but not significantly, and disposal problems increase.
 Chemical oxygen demand (COD)
For your information
Experiment
● Ferrous ammonium sulfate(Ammonium iron(II) sulfate, Mohr's salt, FAS):
Formula: (NH4)2Fe(SO4)2·6H2O
Molar mass: 392.13 g/mol
Solubility in water: 269 kg/m³
Appearance: Blue-green solid

● Ferroin:
Formula: C36H24FeN6SO4 or [Fe(o-phen)3]SO4 or [Fe(C12H8N2)3]SO4
Molar mass: 692.52 g/mol
Active ingredient: [Fe(o-phen)3]2+ or C36H24FeN62+ ion
Molar mass of ion: 596.27 g/mol
Ferroin is suitable as a redox indicator, as the color change is reversible, very pronounced
and rapid, and the ferroin solution is stable up to 60 °C. It is the main indicator used in cerimetry.

Reduced ↔ Oxidized
 Chemical oxygen demand (COD)
For your information
Experiment(Dichromate method)
Standardization of FAS
● Whenever a new solution of FAS is prepared it has to be standardized using Potassium
Dichromate as primary Standard.

♦ Potassium Dichromate solution:

►0.25 N Potassium Dichromate (12.259 grams Anhydrous K2Cr2O7 in 1 Liter of Distilled
water)
or
► 0.05 N Potassium Dichromate (2.452 grams Anhydrous K2Cr2O7 in 1 Liter of Distilled water)

♦ FAS solution:
► Weigh 39.2 grams of FAS and dissolve it in 1000ml of distilled water by adding 20.0ml of
concentrated sulphuric acid drop wise by cooling. Transfer it to 1000ml volumetric flask and
dilute it up to mark to get ~0.1N FAS solution

♦ Standardization titration:
► Take 10 ml of 0.25N Potassium Dichromate and 90 ml of distilled water
► Then add 30 ml of concentrated Sulphuric Acid (addition should be done by cooling
Simultaneously)
► Titrate this solution against freshly prepared FAS using Ferroin indicator
► Continue titrating till wine red color appears which the end point is.
 Chemical oxygen demand (COD)
For your information
Experiment(Dichromate method)
● COD measurement:
♦ Pipette out 10 mL of the given water sample into a clean sample tube.
♦ Add 20 mL of potassium dichromate solution, 30 mL of silver sulphate –
sulphuric acid mixture and 0.5 g of mercuric sulphate to it. While adding acid
keep the reaction vessel (COD vial) in ice bath to avoid loss of volatile
substances due to heat liberation.
♦ Add one porcelain bit to the reaction vessel.
♦ Insert the reaction vessel into one of the holes of COD digester, which has
attained 150 0C. Fix the air condenser on reaction vessel.
♦ Reflux the contents for 30 min, cool to room temperature and transfer the
contents to 200 mL conical flask.
♦ Titrate the excess potassium dichromate present with standard ferrous
ammonium sulphate solution using 4 to 5 drops of ferroin indicator. The end
point is the color change from yellow to reddish brown.
♦ Repeat the same procedure with blank using distilled water instead of
sample.
 Chemical oxygen demand (COD)
For your information
Calculation(Dichromate method)
● Standardization of FAS:
NFAS x VFAS = NDichromate x VDichromate
Where
NFAS = Normality of FAS
VFAS = Volume of FAS used for titration of Dichromate
NDichromate = Normality of Potassium Dichromate
VDichromate = Volume of Potassium Dichromate taken for titration
By putting the above values the Normality of FAS can be calculated
NFAS = (NDichromate x Vdichromate)/ VFAS

● COD as mg/l (or ppm) of oxygen consumed =(A-B) x Normality of FAS

x 8000 / ml. of sample taken
Where
A = Volume of FAS used for titration of blank (Unit: mL)
B = Volume of FAS used for titration of sample (Unit: mL)
 Chemical oxygen demand (COD)
For your information
Interferences
● Reduced inorganic materials may be oxidized by the COD reagent and constitute a
positive interference when present in significant amounts.
♦ Chloride.
♦ Nitrite nitrogen.
♦ Sulfide.
♦ Ferrous iron
● If necessary, a correction can be made for these interferences. After determining the
species concentration using a separate method, there are several ways to make
corrections:
♦ Determine the theoretical oxygen demand of the species and apply a mathematical
correction to the COD result;
♦ Prepare a standard from the species of interest, perform a COD test on the
standard, and apply a mathematical correction to the result;
♦ Spike the sample with the interfering species, perform a COD test on this sample,
and apply a mathematical correction to the COD result.
 Chemical oxygen demand (COD)
For your information
Interferences
Chloride interference
●Chloride is the most common interference and has the greatest effect on test results.
The theoretical oxygen demand of chloride is expressed by the following equation:
4 Cl– + O2 + 4 H+—>2 H2O + 2 Cl2
One molecule of oxygen consumes 4 molecules of chloride ions. On a weight basis, the
theoretical oxygen demand for chloride is 0.226 mg O2 per mg Cl–. A sample containing 1000
mg/L chloride will have a theoretical oxygen demand of 226 mg/L COD.
Pure chloride solutions are oxidized quantitatively by COD reagents which do not contain a
silver catalyst or a chloride masking agent. Silver ions partially mask chloride ions through the
formation of insoluble silver chloride. This results in erratic oxidation of chloride and diminishes
the ability of silver to function as a catalyst. When organic matter and chloride are both present
in a sample, the oxidation of chloride may also be erratic. This is why the technique of
determining the chloride concentration by a separate technique and adjusting the COD result
does not always provide accurate results.
When chloride is present with high concentrations of ammonia, organic amines, or
nitrogenous matter, the interference is severe. This is due to a series of cyclic changes from
chlorine to chloride through the formation of chloramine intermediates. Ammonia, organic
amines, or nitrogenous matter do not interfere when chloride is absent. Organic amines and
nitrogenous matter are a source of ammonia nitrogen after oxidation by the COD reagent. The
easiest remedy to this problem is to remove sample chloride.
 Chemical oxygen demand (COD)
For your information
Interferences
Chloride interference remedy
● An historical method for chloride removal is the addition of a reagent to precipitate chloride. This precipitate is
separated from the solution by settling, centrifuging or filtration, and a sample aliquot is taken for testing. While chloride is
effectively removed from the sample, suspended solids are also removed. These solids often contain oxidizable organic
material. The resulting COD is some fraction of the total and is referred to as soluble COD. The most common reagent used
for precipitation of chloride is a silver salt.

● Mercuric sulfate is the most widely used reagent for masking chloride interference and is most effective when the ratio
of mercuric sulfate to chloride is 10:1. For example, a 2 mL sample containing 2000 mg/L chloride (4 mg Cl–) will require 40
mg mercuric sulfate to effectively mask the chloride interference. In some instances, mercuric sulfate may not mask chloride
well enough to prevent the combined interference of chloride and high concentrations of ammonia or other nitrogenous
compounds. This occurs more often in strong dichromate solutions (high range reagents). One solution to this problem is to
dilute the sample to a level where it can be tested using a weaker dichromate solution (low range reagent). The combined
interference will usually not be observed with the lower-strength reagent.
Mercury is very toxic and disposal usually is not a legal option. The only legal method for waste mercury handling is
recycling, which can be expensive.

● A recent technique for chloride removal was developed in conjunction with the Manganese (III) COD reagent. The
sample is pretreated to remove chloride using a Chloride Removal Cartridge. The reagent bed contains the solid, non-water
soluble oxidant, sodium bismuthate. Chloride removal is optimized through the Chloride Removal Cartridge system, while
minimizing any effect the oxidant may have on other sample components. The Chloride Removal Cartridge system will
remove up to 1000 mg/L chloride.

Vacuum Pretreatment
Chloride Removal Device
Cartridge
 Chemical oxygen demand (COD)
For your information
Interferences
Nitrite nitrogen interference
● Nitrite nitrogen interferes with the test and has a theoretical oxygen
demand of 1.1 mg O2 per mg NO2 - N.

♦ Its concentrations rarely exceed 1 to 2 mg/L and the interference is

considered insignificant.

♦ When NO2 - N concentrations are present at higher levels, the

interference can be eliminated by the addition of 10 mg sulfamic acid
(H3NSO3) per mg NO2 - N. A separate blank must also be prepared
containing the same concentration of sulfamic acid.
 Chemical oxygen demand (COD)
For your information
Colorimetric determination (mainly for micro COD test)
● The measurement of COD test results can be done using colorimetric and titrimetric
procedures. Colorimetric procedures are easier and quicker to run and are generally more
accurate. However, when samples are turbid or colored, or if a spectrophotometer is not
available, a titrimetric procedure should be used. Titrimetric procedures require a higher degree
of operator skill and take longer to perform.
● Colorimetric Procedures
The micro COD test vial used for this digestion also serves as a cuvette for colorimetric
measurement. It is used with a test tube adapter in a spectrophotometer. Colorimetric
measurements allow the digestion to be monitored periodically for completeness. This means
that easy-to-digest samples can be analyzed with confidence in a short period of time.
Test tube (test vial, cuvette)

Spectrophotometer Test Tube Adapter

A spectrophotometer
and a Test Tube Adapter
 Chemical oxygen demand (COD)
For your information
Colorimetric determination (mainly for micro COD test)

Typical Digestion Curves - COD vs. Ultra Low Range COD scan using standards at 0, 10, 20,
30, 40 mg/L COD (Dichromate).
Time(Dichromate). It shows several scan overlays of COD standards at
It clearly demonstrates that COD various concentrations tested.
determinations made for process control The maximum sensitivity is at 345 nm, but the test
purposes can be conducted in a shorter measurement is made at 350 nm for instrumentation
digestion time than specified in the considerations. The calibration line for this test has a
procedure. For samples which are difficult negative slope. The amount of hexavalent chromium
to oxidize, the digestion time can be remaining after digestion is measured and it decreases as
extended up to four hours if a blank is also the COD concentration increases. High quality, organic-
free, deionized water is required for blanks and dilution
run for the same period of time. water with this test range.