BSH21BS05/BSH22BS05

RELEVANCE OF
CHEMISTRY
Catalysts
Censors
Superconductors Memory
chips
Display devices
Technology
Nanomaterial
GreenTechnology
Energy storage
Corrosion Control.
Fuel Cells
Solar Cells
 Syllabus Structure : Total 30 lectures

Unit 1: Water Technology and Green Chemistry (8L)

Unit 2: Fuels and Combustion (7L)
Unit 3:Corrosion and corrosion control (8L)
Unit 4: Chemistry of Polymers & (7L)
Novel Carbon Compounds
 Reference / Text Books
1. Engineering Chemistry, Wiley India Pvt. Ltd
2. Inorganic Chemistry, 5 ed by Shriver and Atkins, Oxford
University Press
3. Basic Concept of Analytical Chemistry, 2ed , S. M.
Khopkar, New Age-International Publisher
4. Instrumental Methods of Chemical Analysis, G. R.
Chatwal& S. K. Anand, Himalaya Publishing House
5. Spectroscopy of organic compounds, 2 ed, P. S. Kalsi,
New Age-International Ltd., Publisher
6. Polymer Science, V. R. Gowarikar, N. V. Viswanathan,
jayadevSreedhar, Wiley Eastern Limited
 After learning Engineering Chemistry, student will be able to:

1. Analyse the water quality, interpret techniques of water purification and compare
green over traditional synthesis of polycarbonate.
2. Perceive the fuel quality and understand the scope of derived alternate fuels
3. Relate the preventive methods of corrosion to real-life problems.
4. Interpret the chemical structure, properties and synthesis of various polymers and
nanomaterials and their uses
TEACHING AND EVALUATION SCHEME

Theory : 2 Credit (BSH21BS05/BSH22BS05)

Lecture : 2 lectures per week
Lab. : 2 Credit(BSH21BS06/BSH22BS06)
Duration : 4 hours per week

FA1 = 10 marks TW = 50
FA2 = 10 marks Pr = 50
SA = 30 marks Total : 100
-------------------------
Total : 50 marks
 Unit - 1

Water Technology
&
Green Chemistry
 Hardness of water: Determination by EDTA method,
Alkalinity of water its determination and their numerical.
Effects of hard water in boiler. Priming, foaming, scale
sludge and caustic embrittlement.
Boiler feed water treatment. External treatment- a) Zeolite
process and its numerical b) Ion-exchange method.
Techniques for desalination of water
a) by Reverse osmosis.
b) by electro dialysis.
BOD & COD
Green Chemistry: 12 principles and Green Synthesis of
Polycarbonate
 Dissolved impurities
1) Gases: like O2, SO2, NH3, H2S, CO2 and metal
salts are soluble in water.
Mode of Separation Of Gases
- By warming up the water
- Mechanical aeration techniques

2) Cations like K+, Na+, Ca++, Mg++, Fe++, Mn++

Anions Cl-, SO42-, NO-3, HCO3- etc are present
when water comes in contact with soil, rocks etc.

3) Mode of Separation of Organic solids

- By oxidation or biochemical oxidation
 Hard Water

It is the water which interferes with Lather (foam)

formation during washing with soap. Instead of foam,
scum (curdy white ppt) is formed.

This happens due to presence of minerals it water.

 Hardness of Water
. Hard Water Soft Water

Do not form lather with soap rather Forms lather with soap
Precipitate is formed

Contains heavier cations like Ca2+ Contains lighter cation like

Mg2+, Fe2+, Mn2+, Al3+ , Li+, Na+

These cations make water hard These ions do not make

water hard

Such water is harmful for boiler This water is safe for

Machine need not to mention industrial as well as domestic
their harm on human bodies use
 Types of Hardness of Water

Permanent and Temporary Hardness

Total Hardness = Permanent hardness + Temporary Hardness

Temporary Hardness (Alkaline hardness): due to alkaline nature

of water i.e. they have bicarbonates, Carbonates or hydroxides of
Ca and Mg ions also called as alkaline hardness.
Ca(HCO3)2, CaCO3, Ca(OH)2, Mg(HCO3)2, MgCO3
Mode of Removal: By boiling water
 Permanent Hardness
Also known as non-alkaline hardness:

Ca and Mg ions sulphates, chlorides and nitrates

MgCl2, MgSO4, CaCl2, CaSO4, CaNO3, MgNO3

Not removed by filtration but requires chemical

methods for separation and making hard water
soft.
 Units of Hardness:
1) Parts per million = 1 part CaCO3 equivalent hardness in
1000000 parts of water

2) Milligram per litre (mg/l) = no. of milligram equivalent

hardness per liter.

1mg/l = 1 mg of CaCO3 in 1 litre of water

we know 1000ml of water = 1000 g = 1000x1000mg of
water

Therefore
1mg/litre = 1 ppm (1mg of CaCO3 equivalent in 1000000mg
of water)
3) Degree Clarke (˚Cl): It is the number of equivalent parts of
CaCO3 present per 70,000 parts of water or 1 gallon of water.

1 ppm = 0.07˚Cl

4) Degree French (˚Fr): It is the number of equivalent parts of

CaCO3 present per 105 parts of water.

1 ppm = 0.1˚Fr
 CaCO3 Equivalence of Few chemicals

Hardness of water = weight of chemical x 100

mol. Wt. of chemical

or = weight of chemical x 50
equiv. Wt. of chemical

Remember: 1mol of CaSO4 = 1mol CaCO3,

1mol Mg(HCO3)2 = 1mol CaCO3,

1mol MgCl2 = 1mol CaCO3
Calculate their CaCO3 equiv. of following in 1liter of
water sample.

CaSO4 = 20mg,
Mg(HCO3)2 = 14.6 mg,
MgCl2 = 12.5 mg

Mol wt. :
CaSO4 = 136,
Mg(HCO3)2 = 146,
MgCl2 = 95g/mol
CaCO3 equiv. of CaSO4 = 20 x 100 = 14.7mg/l
136

CaCO3 equiv. of Mg(HCO3)2 = 14.6 x 100 = 10mg/l

146

CaCO3 equiv. of MgCl2 = 12.5 x 100 = 13.6mg/l

95
 Hardness of water

Hardness Nature of Water

< 50 ppm Soft water

50 – 100 ppm Moderately soft

100 – 150 ppm Slightly hard

200 – 300 ppm Hard water

> 300 ppm Very Hard water

 Determination of Hardness by EDTA method

What is EDTA: Ethylene diamine Tetra acetic acid. It forms

soluble complex with metal ion.

COOH
N
N
HOOC COOH
COOH
n+
EDTA M EDTA-Metal complex
 Method
1. Pipette out 50 ml of given water sample in 250ml conical flask
2. Add 3-5 ml of ammonia-ammonium chloride buffer for pH 10
3. Add 1-2 dps of Eriochrome black indicator colors is wine red
4. Titrate against 0.01 M EDTA till wine red changes to blue coloration
Record volume of EDTA added in V ml and calculate hardness of water

Reactions:

i) M++ + EBT M-EBT + 2H+

Pink-red
ii) M++ + EDTA M-EDTA + 2H+
colorless
iii) M-EBT + EDTA M-EDTA + EBT
pink red colorless blue
Calculations:
1000ml 1 M EDTA = 1 mole of CaCO3 = 100gm of CaCO3
“v”ml M2 M EDTA = v x M2x 100 of CaCO3
1000
if V ml of hard water sample contains = v x M2 x 100 g of CaCO3
1000

then 1000ml of hard water sample contains = v x M2 x 100 g

V

Total Hardness of Water sample = v x M2 x 105 mg of CaCO per lit

3

V
Where,
v: ml of EDTA used in titration
M2: molarity of EDTA
V: volume of hard water sample
 Numerical based on EDTA titration

PROBLEM: 50 ml of water sample requires 12.2 ml of 0.02 M EDTA during

the titration. 50 ml of boiled water sample requires 8.2 ml of EDTA. Calculate
temporary, permanent and total hardness.

Solution: Given: Molarity of EDTA solution = M = 0.02M

Volume of Hard water = V = 50 ml
Volume of EDTA before boiling = v1 = 12.2 ml
Volume of EDTA after boiling = v2 = 8.2 ml

a) Total Hardness (before boiling): = v1 x M x 105 = 12.2 x 0.02 x 105

V 50
= 488 ppm CaCO3 eq.

b) Permanent Hardness (after boiling): = v2 x M x 105 = 8.2x 0.02 x 105

V 50
= 328 ppm CaCO3 eq.
 Alkalinity of Water and its Determination

“It means the acid-neutralizing capacity of water sample”

Alkalinity of water is because of carbonates (CO32-), Bicarbonates

(HCO3-), and OH- content and often interpreted in terms of their
concentration

Why determination of alkalinity of water important?

For determining suitability for irrigation, industrial use, raw water or

waste water monitoring.

 It is important indicator of water body’s ability to resist pH change

due to accidental acid spill or acid ppt.
 Types of Alkalinity

Five possibilities for alkaline water are:

i) Only hydroxide (OH-)

ii) Only Carbonates (CO32-)
iii) Only bicarbonate (HCO3-)
iv) Hydroxide and carbonate (OH- & CO32-)
v) Carbonate and bicarbonate (CO32- & (HCO3-)

Combination of hydroxide and bicarbonate is not possible since they

combine to form carbonate

OH- + HCO3- H2O + CO32-

 Principle
Alkalinity of water can be determined by titrating it against standard acid
using indicators phenolphthalein and methyl orange. Hence it is
aneutralization titration.

Reactions:

I) OH- + H+ H2O
ii) CO32-+ H+ HCO3-
Iii) HCO3- + H+ H2O + CO2
Phenolphthalein end point: Titrating alkaline water with acid using
phenolphthalein indicator will indicate completion of reaction i + ii
The end point (V1) marks the complete neutralization of OH - and half
neutralization of CO32- (since carbonate neutralizes in two steps)

Methyl orange end point: Continuing titration with methyl orange against
acid up to methyl orange end point (V2) indicate completion of reaction
i+ii+iii. It indicates total neutralization.
 Determination

Take 100 ml of water sample in 250 ml Conical flask

Adjust pH > 8.3

Add few dps of phenolphthalein indicator

Titrate with 0.02 N H2SO4/HCl till pH endpoint

i.e. colorless solution obtained

Note V1 Volume of acid needed it is P (phenolphthalein alkalinity)

If pH < 8.3 add bromocresol or methyl orange indicator

Continue titration with 0.02 N H2SO4 or HCl till pH 4.5

V2 ml acid required to reach end point it is M (total alkalinity)

or methyl orange alkalinity
Calculations for total alkalinity T
 Calculations
a) Phenolphthalein alkalinity (P): Alkalinity is expressed as parts per million in terms of
CaCO3

As 1000ml of 1N HCl = 50 gm of CaCO3

“V1”ml of N normality Acid = V1 x N x 50 = A gm of CaCO3
1000
If V ml of alkaline water sample contains = A gm of CaCO3

then 1000ml of alkaline water sample contains = A x 1000/V = V1 x N x 50 gm of

CaCO3 V

Therefore,

P = V1 x N x 50 x103 mg of CaCO3 per litre

V
b) Methyl orange alkalinity (M): Similarly if “V2” ml of N normal acid required
for methyl orange end point then methyl orange alkalinty M is

M = V2 x N x 50 x103 mg of CaCO3 per litre

V
 Sample Numerical
100 ml of water require d 20 ml N/50 H 2 SO 4 for ne utra liz a tion to
phenolphthalein end point After this methyl orange indicator was added and
further acid required 20 ml. Calculate alkalinity of water as CaCO3 in ppm.
Solution: Given: V = volume of water = 100ml, Normality of acid = N = 0.02N
V1 = 20 ml, V2 = 40 ml. Hence

P = V1 x N x 50 x 1000
Volume of water sample

P = 20 x 0.02 x 50,000 = 200mg equiv./lit.

100

M = V2 x N x 50 x 1000
Volume of water sample

M = 40 x 0.02 x 50,000 = 400mg equiv./lit.

100
Since P = ½ M
Hence type is: CO3- only
 Hard water Treatment

Effects of hard water in boilers:

give rise to major problems in boilers like:

a) Corrosion

a) Priming and foaming

a) Sludges and scale formation

a) Caustic embrittlement
CORROSION
 Corrosion
 Serious problem
 Reduced boiler life , Leakage of joints and values
 Increased cost for repair and maintenance

Reason:
1)Dissolved gases: Oxygen: corrodes iron of boiler by following reaction

2Fe + 2H2O + ½ O2 2Fe(OH)2 Fe2O3

rust
Removal:

a) Add Na2SO3 (sodium sulphite) or hydrazine NH2.NH2

Na2SO3 + ½ O2 Na2SO4
NH2-NH2 + O2 N2 + 2H2O

b) Mechanical deaeration
 Corrosion contd.

2) Carbon dioxie (CO2):

If water containing CO2 is fed to boiler, it forms carbonic acid H2CO3
which is very harmful for boiler.

Removal:

a) Add NH3

CO2 + 2NH3 + H2O (NH4)2CO3

b) Mechanical de-aeration

3) Hydrolysis of salts: e.g. MgCl2, FeCl2

Dissolved magnesium salts liberate acid on hydrolysis. The acid then
reacts with iron metal of the boiler in a chain reaction producing HCl again
and again. Hence even small amount of Mg-salts can cause considerable
corrosion of boiler metal.
 Corrosion contd.

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

Fe(m + 2HCl FeCl2 + H2

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

Solution to the problem of hydrolysis of salts:

 Boiler water should not have salts. They should be removed by Zeolite or
ion-exchange process.

 Maintain pH 8.5-9.0 to avoid acid problems

 Corrosion contd.

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

Fe(m + 2HCl FeCl2 + H2

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

Solution to the problem of hydrolysis of salts:

 Boiler water should not have salts. They should be removed by Zeolite.

 Maintain pH 8.5-9.0 to avoid acid problems

B) Priming and Foaming (carry over)

 Due to fast steam production, some water droplets carried along with steam
makes “Wet steam” is called priming.

 Formation of continuous foam or bubbles on the surface of water is

called “Foaming”.

Reasons for Priming:

 Very high level of boiler-feed water
 + nce of excessive foam
 High speed steam generation
 Faulty boiler design
 sudden drop in pressure
 Reason for Foaming
-High conc. of dissolved salts in boiler feed water
-Presence of oil droplets and alkali
-Presence of finely dispersed suspended particles
-Violent agitation
Disadvantages:
 Actual height of water cannot be found well
 Salts deposit on evaporation of water leading to reduced efficiency of machinery

Prevention of priming and foaming

 By addition of antifoaming agents like castor oil or removing oil by adding
Chemicals like sodium aluminate and blow-down operation
 Priming – preventable by use of softened water
 Pressure changes
 Use of steam purifiers
 Priming Foaming

Normal bubble Carry-over bubble

C) Sludge and Scales Forming
In boiler, water evaporates, concentration salts left behind increases
and after saturation point get precipitated out

if ppt adheres strongly and form

If ppt is loose and slimy matter strong, bad conducting layer
it is called sludge inner side of boiler it is called
Scale
SLUDGE SCALE
What is Sludge?

Loose slimy mass of salts in boiler water formed in cooler parts

and loosely deposit, easy to remove by brushes, detergent
solution, blow down methods

Disadvantages:

--- Waste portion of heat --- reduce water flow rate

--- Extensive sludge disturbs working
of boiler and choke pipes

Prevention of sludges

--- Use water having low dissolved solids

--- Blow down technique i.e. replacing salts rich water with fresh
 Scales
 It is hard and strongly attached coating in inner surface of boiler.
 It is bad conductor of electricity.
 It is main source of boiler trouble.
Reasons for scale formation

1. Decomposition of bicarbonates: At high temperature bicarbonate

decomposes to form ppt as scale

Ca(HCO3)2 CaCO3 + H2O + CO2

Mg(HCO3)2 MgCO3 + H2O + CO2
2) Hydrolysis of Mg salt:

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

3) Silica : in form of Ca-Silicate & Mg-Silicate form colloidal particles and

deposit on walls.

4) At high temperature solubility of CaSO4 decreases and precipitate

forms hard scale
Disadvantage:
i) Wastage of Fuel – scales are bad conductor of heat therefore
More the thickness of scale = more heat loss,
0.25 cm scale consume 2-3 times more heat

ii) Overheating of boiler

iii) Boiler safety compromised: Due to overheating boiler metal becomes soft
and fragile

iv) Therefore there is danger of explosion due to large amount of steam

formation due to uneven inner wall surface
 Removal of Scale:
 Use of Chemicals: EDTA, sodium phosphate, calgon to loosen scales
 Wire brush
 Hammer and chisel
 Thermal shock:
 Boiler is heated cooled suddenly on sudden cooling
boiler contract and scale cracks.

Prevention:
 Use of soft water,
 phosphate conditioning,
 blow down operation,
 Na-aluminate.
 Use of tannin (forms coating on inner wall of boiler)
D) Caustic Embrittlement

 Brittleness of Boiler due to accumulation of caustic substance

 It is fast corrosion of boiler due to high alkaline nature of water.
 Water evaporates and therefore Na2CO3 concentration increase

Na2CO3 + H2O 2NaOH + CO2

NaOH very corrosive attack cracks on inner surface and reacts with Fe

2Fe + 2NaOH + O2 2NaFeO2 + H2

 Cause embrittlement of boiler parts at stressed parts like bends, joints,
rivets and lead to failure of boiler.

 Cell formation Anodic part gets corroded.

Iron at joints / Higher conc. // lower conc. // Iron at plane surface

(stressed ) NaOH NaOH unstressed
Anode (+) cathode (-)

Prevention of caustic embrittlement

Use Na-phosphate for water softening instead of Na2CO3

Add Tannin/lignin – blocks cracks
Add Na2SO4 to keep Na2SO4 : NaOH (1:1 or 2:1)
Adjust pH 8-9 carefully
 Water Treatment
Raw water is converted to soft water before it is used for industrial
purpose by two types of treatments:

External treatment: Here scale forming and corrosive impurities are

removed from hard water before it enters the boiler.

Internal treatment: Here various substances are added to boiler feed

water to remove residual, non carbonate hardness to prevent scale
formation and boiler corrosion.

--------------------------------
-----------------------------------------
Raw water ---------Internal treatment------------
-------------------------------------------
---------------------------------

External treatment Boiler

A)Zeolite or Permutit : Cation Exchange
process
Zeolite: Natural mineral , insoluble in water, mixture of metal silicates
and metal aluminates. Two types of zeolites: Natural and Synthetic

Nax+ [(AlO2)x (SiO2)y zH2O) where, x = 2-10 and y = 2-6 or Na-Zeolite

 Principle
 Na-Zeolite has the property of exchanging ions present in them
mostly loosely held Na+ with the ions present in the solution like Ca2+,
Mg2+ etc. from Hard water.
 Process
Zeolite softener consists of cylindrical column with coarse gravel
Then fine gravel and then on top of it layer of zeolite layer.

A slow stream of hard water passed through the material

Ca2+, Mg2+ present in hard water are exchanged with Na+ ions in
Zeolite

Ca2+ + 2Na+(Al-silicate) Ca(Al-Silicate) + 2Na+

 Regeneration:
Over a period of time Na2Ze
converted to

Ca-Ze + Mg-Ze

Therefore zeolite softener gets exhausted and needs to be

regenerated for further Use

This is done by passing brine solution (NaCl) on Zeolite layer

Advantages :

 Easy to operate
 Low cost operating system
 Small space is required

Limitations:

 Warm water cannot be used

 Mn2+ , Fe2+ permanently captured by Zeolite so no regeneration
 Soft water has equivalent quantities of Na+
 Colloidal hard water cannot be used it may clog/block zeolite str.

Applications:

 Extensive use
 Remove toxic metal ion and dye cations from polluted water.
 Recover trace metal like Cu, Ag, Au etc.
 Simple, convenient but applicable to small scale use.
Sample – Numerical
An exhausted zeolite bed is regenerated by passing 4.8 litres of NaCl solution
Having concentration 100g/NaCl/litre. The bed gets exhausted by treatment
of 1200 litres of a water sample. Calculate hardness of water sample.

StepI : Find out amount of NaCl (In mg) in total 4.8 lit. of brine

100g of NaCl present in 1 litre of water

Therefore ? g of NaCl present in 4.8 lit
= 4.8 X 100 = 480g of NaCl = 4.8 x 105mg o NaCl

Step II: Find out CaCO3 equivalent in mg of NaCl

Molwt. Of NaCl: 58.5 g/mol

= mg of chemical X 50 = 4.8 x 105 x 50

eqviv. Wt. of chemical 58.5
= 4.1 x 105 mg CaCO3 eqvi.

Step III: Hardness of water

CaCO3 equiv.. = liters of Hard water x hardness of water

Hardness of water = 4.1 x 105 / 1200 = 341.9 ppm of CaCO3

 b) Ion Exchange Method (Use of Resin)
This process removes all cations and anions water and such water is called
demineralized or deionized water.
Resins are insoluble, crosslinked, long chain organic polymer with Micro
porous structure and with “functional groups” attached to the Main Chain
Which are responsibel for the ion-exchanging property.
 It has two main units -

Cation Exchange Resin & Anion exchange Resin

i) Cation Exchange resin: It is an polymer having Carboxylated or sulphonated

aromatic rings on the polymer chain.

CH2-CH-CH2 CH2-CH-CH2

SO3-H+ CO2-H+

These acidic groups have loosely held H+ ions which get displaced/exchanged
with M n+ from hard water.

Amberlite IR 120, Dowex 50 are some commercial examples

Gen. formula for Cation exchange resin is H2R

Reactions:

H2R + 2Na+ Na-R + 2H+

H2R + Ca2+ Ca-R + 2H+

Resin (Hard water) (exch. Resin)
ii) Anion Exchange Resin:

It is an polymer having aromatic rings containing

quaternary ammonium group with loosely held OH- anion.

CH2-CH-CH2

+ OH
-
H3C N CH3
CH3

Amberlite 400, Dowex 3 are some examples of this resin.

Reaction at Anion E.R.

R’(OH)2 + 2Cl- R’Cl2 + 2OH-

resin hard water exch. Resin

R’(OH)2 + SO42- R’SO4 + 2OH-

Regeneration
For Cation exchanger: By washing with dil. HCl solution

Na2R + 2HCl H2R + 2NaCl

Ca-R + 2HCl H2R + CaCl2
exhausted regen.resin
resin

For Anion exchanger: By washing with NaOH solution

R’Cl2 + 2NaOH R’(OH)2 + 2NaCl

R’SO4 + 2NaOH R’(OH)2 + Na2SO4
exhausted regen. resin
resin

 Hard water after passing through cation and anion exchange resin contains
only H+ and OH- which react to form H2O so no ions in soft water

 Therefore Ion-exchange method is also called Deionization method

Advantages of Ion-exchange Resin:
 This method gives zero hardness and no ionic impurities.

 O2, CO2 etc. gases also can be removed by passing through

degasifier

 Small space required

 Easy to operate.

Limitations:
 High expense

 Only for small scale purification of Hard water

BOD and COD of Waste Water
Wastewater – types, characteristics & regulation

a) Domestic: wastewater by residential, shop houses, offices, schools etc.

and normally generated from toilets, sinks and bathrooms.

b) Industrial: wastewater generated by industries. Quantity and quality

depends on the type of industry

c) Storm water: rainwater, may contain pollutants

 Why treat wastewater?

Untreated wastewater harmful to health

Breeding sites for insects, pests and micro organisms

Can cause environmental pollution and affect ecosystem

Normally, wastewater has high organic content. The

organic content are measured by Biochemical Oxygen
Demand (BOD) and Chemical Oxygen Demand (COD)
and the value is about 100 to 400 mg/While the BOD test
measures biochemically decomposable or degradable
organic matter, the other two measure total organics.
 Dissolved oxygen

The DO level in a surface water body is an important indicator of its

‘health’.

Presence of DO in water is necessary for maintaining favorable

conditions for growth and reproduction of a normal population of fish
and other aquatic life.

The absence of a low level of DO in surface waters indicates

pollution by organic matter.

Under such conditions organic matter is decomposed by anaerobic

bacteria resulting in production of obnoxious end-products, such as
mercaptans, hydrogen sulphide, ammonia, etc .
 Biochemical Oxygen Demand (BOD)

The quantity of oxygen utilized by a mixed population of micro-

organisms to biologically degrade the organic matter in the
wastewater under aerobic condition.

BOD is the most important parameter in water pollution control

It is used as a measure of organic pollution as a basis for

estimating the oxygen needed for biological processes, and as an
indicator of process performance.

microorganism
Organic matter + O2 CO2 + H2O + new cells
BOD test, 5-day at 20°C, 3-day at 30°C
 Biochemical Oxygen Demand (BOD)
Procedure:

1. A water sample containing degradable organic matter is placed in a

BOD bottle.
2. If needed, add dilution water (known quantity). Dilution water is
prepared by adding phosphate buffer (pH 7.2), magnesium sulphate,
calcium chloride and ferric chloride into distilled water. Aerate the
dilution water to saturate it with oxygen before use.
3. Measure DO in the bottle after 15 minutes (DOi)
4. Closed the bottle and placed it in incubator for 5 days, at
temperature 20oC
5. After 5 days, measure DO in the bottle (DOt).
 Calculation of BOD

Where
BODt = biochemical oxygen demand, mg/L
DOi= initial DO of the diluted wastewater sample about 15 min. after
preparation, mg/L
DOt= final DO of the diluted wastewater sample after incubation for
five days, mg/L
P = dilution factor =

Need for Dilution:

For a valid BOD test, the final DO should not be less than 1
mg/L. BOD test is invalid if DOt value near zero.

Dilution can decrease organic strength of the sample. By using

dilution factor, the actual value can be obtained.

Dilution of wastes: - By direct pipetting into 300 mL BOD bottle

 BOD Analysis

In aerobic processes (O2 is present), heterotrophic bacteria oxidize

about 1/3 of the colloidal and dissolved organic matter to stable end
products (CO2 + H2O) and convert the remaining 2/3 into new
microbial cells that can be removed from the wastewater by settling.

The overall biological conversion proceeds sequentially, with oxidation

of carbonaceous material as the first step (known as carbonaceous
oxygen demand):

Organic matter + O2 → CO2 + H2O + new cells

Under continuing aerobic conditions, autotrophic bacteria then convert

the nitrogen in organic compounds to nitrates (known as nitrification
oxygen demand).

Organic-Nitrogen → Ammonia-Nitrogen (decomposition)

NH3 - N + O2 → Nitrate-Nitrogen (nitrification)

 Chemical Oxygen Demand

The quantity of oxygen needed to chemically oxidize the organic

compound in sample, converted to carbon dioxide and water.

Commonly used to define the strength of industrial waste waters.

 Procedure

1. Add measured quantities of potassium dichromate, sulphuric acid

reagent containing silver sulphate, and a measured volume of sample
into a flask.

2. The mixture is refluxed (vaporized and condensed) for two hours.

The oxidation of organic matter converts dichromate to trivalent
chromium,
Organic matter + Cr2O72- + H+ → CO2 + H2O + 2Cr3+

3. The mixture is titrated with ferrous ammonium sulphate (FAS) to

measure the excess dichromate remaining in sample.

4. A blank sample of distilled water is carried through the same COD

testing procedure as the wastewater sample.
 Calculations

COD is calculated from the following equation:

COD = 8000(a-b) x Normality of Fe(NH4)2(SO4)2

V
Where:

COD = chemical oxygen demand, mg/L

a = amount of ferrous ammonium sulphate
titrant added to blank, mL
b = amount of titrant added to sample, mL
V = volume of sample, mL
8000 = multiplier to express COD in mg/L of oxygen