Module-7:

WATER TECHNOLOGY

Engineering Chemistry
(BCHY101L)

Dr. Kiran Kumar Tadi

Assistant Professor
Department of Chemistry
School of Advanced Sciences (SAS)
Vellore Institute of Technology, Chennai
 Classification of Impurities in Water
Water has different physical, chemical and biological Impurities
which can cause problems in both domestic and industrial
applications.
o Physical
- Inorganic such as clay, sand
- Organic such as oil globules, vegetable/animal matter
- Colloidal such as Fe(OH)3, Complex proteins, amines
o Chemical
- Anions such as Cl-, 𝑆𝑂42− , 𝐶𝑂32− , 𝐻𝐶𝑂3− , 𝑁𝑂3− of Ca & Mg
- Cations such as Ca2+, Mg2+, Na+, K+, Fe3+, Al3+
- Dissolved gases such as O2, N2, CO2, H2S, NH3
o Biological
- Microorganisms such as algae, fungi, bacteria
-(Pathogenic causing Malaria, diarrhoea, typhoid etc.)
 Hardness of Water
o 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.

o 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.

o 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.
 Types of Hardness
o Hardness of water is due to dissolved salts of mainly calcium
and magnesium as well as iron and other heavy metals.

o Hardness is two types:

a) Temporary :

- Due to the presence of dissolved bicarbonates of calcium and

magnesium and other heavy metals and carbonates of iron.
Hence it is also called as carbonate or alkaline hardness.

- Can be easily removed by boiling where CO2 gas gets expelled

removing

the hardness.
 Types of Hardness

Heat
Mg(HCO3)2 Mg(OH)2 + 2CO2
Insoluble Precipitate
b) Permanent:

- Due to the presence of dissolved chlorides and sulphates of

calcium and magnesium and other heavy metals. Also called as
non-carbonate or non-alakaline hardness.

- Can be removed through zeolite, Lime-soda, ion-exchange

processes.
Total hardness = Temporary hardness + permanent hardness
WATER TREATMENT

9
 Module 2: Water Treatment

 Water softening methods: -

 Zeolite or Permuitit Method
 Ion-exchange method
 Reverse osmosis
 Methods of Softening and Demineralization
o Common modes of water treatments are

1. Internal treatment/ Internal conditioning - Addition of chemicals

2. External treatment/ External conditioning – Zeolite, Ion-exchange

3. Desalination

1. Internal Conditioning: Internal conditioning is treating the water after

feeding into the boiler by adding chemicals (boiler compounds).

Principle: To convert scale forming precipitate to sludge forming

precipitates which can be removed by blow down operation. To
increase the solubility of the impurities and prevent it from
precipitating

Example: Phosphate conditioning (Addition of Sodium phosphate),

Calgon (Sodium hexa meta phosphate), Colloidal (Tannin, Lignin,
Kerosene etc)
 2. External Treatment/conditioning of water
External softening of hard water can be done by the following methods
1. Lime soda process
2. Zeolite methods
3. Ion exchange resin method
4. Mixed bed deionizer method

1. Lime soda process

It is a process in which Lime (Ca(OH)2) and soda (Na2CO3) are added to the hard water to convert
the soluble calcium and magnesium salts to insoluble compounds by a chemical reaction. The
CaCO3 and Mg(OH)2 so precipitated are filtered off and removed easily.

It is further divided in to two types

1. Cold lime soda process
2. Hot lime soda process

12
 Zeolite (Permutit) method of Softening of Water
Zeolite is a Hydrated Sodium Alumino Silicate (HSAS),
capable of exchanging reversibly its sodium ions for
hardness producing ions in water.

The general chemical structure of zeolite is given

below Na2O.Al2O3.xSiO2.yH2O (x = 2-10 and y = 2-6)

Why synthetic zeolite is better than natural zeolite for the

softening of water?
Micro pores of Zeolite

oSynthetic zeolites are more porous, glassy particles

having higher softening capacity compared to green
sand.
oThey are prepared by heating china clay (hydrated
aluminium silicate), feldspar (KAlSi3O8-NaAlSi3O8 –
Porous Structure of zeolite
CaAl2Si2O8) are a group of rock-forming tectosilicate
minerals which make up as much as 60% of the earth’s
crust) and soda ash (Na2CO3).
13
Natural Zeolite

Natrolite
 Artificial Zeolite
Used for softening purpose. These are porous and
glassy and have greater softening capacity. They are
prepared by heating together with china clay,
feldspar and soda ash.

China clay
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

16
 Process of softening by Zeolite method

For the purification of water by the zeolite softener, hard water is passed through the zeolite bed at a
specified rate. The hardness causing ions such as Ca2+, Mg2+ are retained by the zeolite bed as CaZe
and MgZe respectively; while the outgoing water contains sodium salts. The following reactions takes
place during softening process

To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3 Scale formation

Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained

17
Limitations of Zeolite process

1. If the water is turbid ---- then the turbidity causing particles clogs the pores of the Zeolite and
makes it inactive
2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which can not be regenerated that
easily
3. Any acid present in water (acidic water) should be neutralized with soda before admitting the water
to the plant

Advantages of Zeolite process

1. Soft water of 10ppm can be produced by this method

2. The equipment occupies less space
3. No impurities are precipitated, hence no danger of sludge formation in the treated water
4. It does not require more time and more skill

Disadvantages of Zeolite process

1. Soft water contains more sodium salts than in lime soda process
2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions like HCO3- and CO32- in
the softened water (then it may form NaHCO3 and Na2CO3 which releases CO2 when the water
is boiled and causes corrosion)
3. It also causes caustic embitterment when sodium carbonate hydrolyses to give NaOH
18
19
Ion-Exchange Resin (or) Deionization (or) Demineralization Process

Ion exchange resin

Ion exchange resins are insoluble, cross linked, long

chain organic polymers with a microporous structure,
and the functional groups attached to the chain is
responsible for the “ion-exchange” properties.
Cation Resin after
exchange Resin treatment
III. Ion-Exchange resin (or) deionization
20
In general the resins containing acidic functional groups (-COOH, -SO3H
etc) are capable of exchanging their H+ ions with other cations, which
comes in their contact; whereas those containing basic functional groups
( -NH2, =NH as hydrochlorides) are capable of exchanging their anions
with other ions, which comes in their contact.

Based on the above fact the resins are classified into two
types
1. Cation exchange resin (RH+)
2. Anion Exchange resin (ROH-)

21
 Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin

¯H SO3¯H
SO3 +
+
RH+ ROH-

SO3 ¯H SO3¯H
+
+

Copolymer of Styrene-divinyl benzene

Copolymer of Styrene-divinyl benzene
with sulphonation or carboxylation
with quaternary ammonium ions

22
 Ion-Exchange Purifier (or) Softener

Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

Acid solution
for Wastages to
regeneration sink Alkaline solution for
of resin Wastages to
regeneration of resin
sink
pump

Soft water 23
H2O

24
 Process of softening

Reactions occurring at Cation exchange resin

2 RH+ + Ca2+ (hard water) R2Ca2+ + 2 H+

2 RH+ + Mg2+ (hard water) R2Mg2+ + 2 H+

Reactions occurring at Anion exchange resin

2 ROH- + SO42- (hard water) R2SO42+ + 2 OH-

ROH- + Cl- (hard water) RCl + OH-

At the end of the process

H+ + OH- H2O

25
Regeneration of ion exchange resins

Regeneration of Cation exchange resin

R2Ca2+ + 2H+ (dil. HCl (or) H2SO4) 2 RH+ + Ca2+ (CaCl2, washings)

Regeneration of Anion exchange resin

R2SO42- + 2OH- (dil. NaOH) 2 ROH- + SO42- (Na2SO4, washings)

Advantages
1. The process can be used to soften highly acidic or alkaline waters
2. It produces water of very low hardness of 2ppm. So the treated waters by
this method can be used in high pressure boilers

Disadvantages
1. The setup is costly and it uses costly chemicals
2. The water should not be turbid and the turbidity level should not be more
than 10ppm
26
 Softening of Water by Mixed Ion Bed Deionizer
Description and process of mixed bed deionizer
1. It is a single cylindrical chamber containing a mixture of anion and cation exchange resins bed

2. When the hard water is passed through this bed slowly the cations and anions of the hard water comes in to
contact with the two kind of resins many number of times

3. Hence, it is equivalent to passing the hard water many number of times through a series of cation and anion
exchange resins.

4. The quality of water obtained from mixed bed is appreciably higher than the water produced from two bed
plants.

5. The soft water from this method contains less than 1ppm of dissolved salts and hence more suitable for boilers

Hard water

c a c a Anion exchange
resin
c Mixed bed Mixed resin
a deionizer a bed
a
c a cc Cation exchange
resin

27
Demineralised
The outgoing water from the mixed-bed contains even less than 1 ppm of
dissolved salts

28
Regeneration of Mixed Bed
NaOH wash
R
C
C C
C
RC R R
R C R
H2SO
R
C
R
C

C
R
C

R
C C

R
C
R
C

C C C

R
C
C C C R C C
RCC C C R
R
C

C R R R R
RCC
R
C

R
C
RR C R C RCC

R
C

R
C
R C R C

R
C

R
C
RR

R
C
R R R RR
R
Compressed Air
Back wash water

Forcing with
R
C

C C
C Compressed air
RC R
for mixing
R
C

R
R
R
C
R
C

C
C
R
C

R
C
R C C
C C R
R R
R
C

C C RCC

R
C
C R C

R
C
R
C
RCC
R
C

C R R RR
R
R
C

R RR
After wash it is regenerated
Regenerated Mix bed read for use
 Regeneration:
The mixed bed is back washed by forcing water in the upward
direction. This separate the cation and anion exchanges from the
mixed bed. Being lighter the cation resin occupies upper part and
the denser on at the bottom.
Now they layers will be washed with NaOH and H2SO4 respectively
to regenerate anion and cation exchange resins. After regeneration
again they are mixed by forcing compressed air.

Generally soften water (eg RO, etc) will be further purified by this method

30
Advantages & Disadvantages of ion-exchange process

o Advantages:
- Can be used for highly acid and highly alkaline water
- Residual hardness of water is as low as 2 ppm.
- Very good for treating water for high pressure boilers

o Disadvantages:
- Expensive equipment and chemicals
- Turbidity of water should be < 10 ppm. Otherwise output will
reduce; turbidity needs to be coagulated before treatment.
- Needs skilled labour

31
Specifications of different materials in drinking water (ICMR and WHO)
S.No. Parameter/Material WHO Standards/ppm ICMR/BIS Standards/ppm

1 Colour Clear Clear

2 Odour Pleasant Pleasant
3 Turbidity 2.5 2.5
4 pH 6.0 – 8.5 6.0 – 8.5
5 TDS 300 500
6 Total Hardness as CaCO3 200 300

7 Calcium 75 75
8 Chlorides 200 200
9 Sulphates 200 200
10 Fluoride 0.5 1.0
11 Mercury 0.006 0.001
12 Cadmium 0.003 0.01
13 Arsenic 0.01 0.02
14 Chromium as hexavalent 0.01 0.1
15 Lead 0.01 0.01
16 E.Coli No colony Should be present in No colony Should be
100 mL water present in 100 mL water
 Different filtration processes
A. Ultrafiltration:
o An ultrafiltration filter has a pore size around 0.01 micron.
o A microfiltration filter has a pore size around 0.1 micron, so when water undergoes
microfiltration, many microorganisms are removed, but viruses remain in the water.
Ultrafiltration would remove these larger particles, and may remove some viruses.
o Neither microfiltration nor ultrafiltration can remove dissolved substances unless they
are first adsorbed (with activated carbon) or coagulated (with alum or iron salts).

B. Nanofiltration
o A nanofiltration filter has a pore size around 0.001 micron.
o Nanofiltration removes most organic molecules, nearly all viruses, most of the natural
organic matter and a range of salts.
o Nanofiltration removes divalent ions, which make water hard, so nanofiltration is often
used to soften hard water.

C. Reverse osmosis
o Reverse osmosis filters have a pore size around 0.0001 micron.
o After water passes through a reverse osmosis filter, it is essentially pure water. In
addition to removing all organic molecules and viruses, reverse osmosis also removes
most minerals that are present in the water.
o Reverse osmosis removes monovalent ions, which means that it desalinates the water.
 Reverse Osmosis

oWhen two solutions of unequal concentrations are separated by a

Semipermeable membrane, solvent will flow from lower conc. to higher conc. due
to osmotic pressure

oThis phenomenon can be reversed by making the solvent to flow in the opposite
direction by applying hydrostatic pressure on the concentrated side (Reverse
Osmosis)

oIn reverse osmosis, pressure of 15-40 kg/cm2 is applied on the contaminated

water compartment.

oThe water gets forced through the semipermeable membrane leaving behind the
dissolved solids.

oThus water is separated from the contaminants rather than removing

contaminants from water.

oBoth ionic and non-ionic impurities as well as colloidal impurities are left behind.

oThis process is also called as “Super-filtration” or “Hyper-filtration”

Advantages of Reverse Osmosis
o Advantage is in removing ionic, non-ionic, colloidal and high
molecular wt. organic matter.

o It removes colloidal silica (which is not removed during

demineralisation)

o Cost is only the replacement cost of membranes (life is 2 years)

o Membrane replacement is fast and hence uninterrupted water

supply can be ensured

o Because of the above reasons this process is being adopted for

converting sea water into potable water and for high pressure
boilers.

o It can be used as desalination process for removing salt from sea

water.

38
 MODULE-7
FUELS, PROTECTIVE COATINGS
AND CORROSION CONTROL

1
 OUTLINE OF THIS MODULE
 Calorific value - Definition of LCV, HCV

 Determination of calorific value using

 Bomb calorimeter
 Boy’s calorimeter
 Numerical problems

 Knocking in IC engines-Octane and Cetane number - Antiknocking

agents.

2
 Fuel
What is fuel?
a combustible substance, upon burning in air/O2 gives large amount of heat.
Ex. wood, charcoal, petrol, LPG, etc.

What is combustion?
a process in which a substance burn in air/O2 with evolution of heat.

Domestic fuels - Hydrocarbons (C & H as main constituent)

ex.

3
 Fuel
When you burn hydrocarbons in air/O2, C-combusted to CO2 and H to
H2O with simultaneous release of heat.

Thus energy released during the combustion process is the difference in

the energy of the reactant and that of products formed.

4
 Classification of fuels

Fuels

Origin Physical state

Primary fuels Solid

ex. coal, petroleum etc. Liquid
Gaseous
Secondary fuels
(derived from primary
fuels ex. kerosene,
diesel, etc. 5
 Calorific Value (CV) of a fuel
Efficiency of a fuel - based on their CV

CV of fuel - quantity of heat evolved by complete combustion of unit

quantity of fuel in air or O2.

Units of heat - Calories (cal), Kilo calories (kcal)

1 Calorie – quantity of heat required to raise the temp. of 1 g of H2O by
1 °C

6
 Calorific Value (CV) of a fuel

Unit of CV of solid and liquid fuels - calories/gram (cal/g) or

kilocalories/kilogram (kcal/kg)

Unit of CV of gaseous fuel

cal/cm3 or kcal/m3 at given T & P.

Since volume of gas varies with T & P. CV of gaseous

fuel includes T & P.

7
 Calorific Value (CV) of a fuel

CV of fuel generally expressed in two ways

Calorific Value
(CV)

Gross/High Calorific Value Net/Low Calorific Value

(GCV/HCV) (NCV/LCV)

8
 Gross/Higher Calorific Value (GCV/HCV)
GCV = Quantity of heat evolved by complete combustion of unit mass of
fuel + latent heat of condensation of steam

GCV = Heat of combustion of fuel + latent heat of condensation of steam

9
 Net/Lower Calorific Value (NCV/LCV)
NCV = Quantity of heat evolved when unit mass of fuel is burnt
completely and the products are permitted to escape.

NCV = GCV – latent heat of steam

10
 Characteristics of a good fuel
High calorific value

Moderate ignition temperature

Low moisture content

Low non-combustible matter

Combustion should be easily controllable

Products of combustion should not be harmful & easy to transport,

store and handle.
11
Determination of Calorific Value of Fuel by
Bomb Calorimeter

12
 Apparatus-Bomb Calorimeter
Bomb Calorimeter – used to determine CV
value of solid & non-volatile liquid fuels

13
14
 Working Procedure-Bomb Calorimeter
Known mass (1 g) of fuel taken in crucible.

Fine Mg wire bent into loop & made to

touch the fuel sample & stretched across
electrodes.

Bomb lid closed & filled with O2 to 25 atm.

Bomb immersed in copper calorimeter with

known mass of water.

15
 Working Procedure-Bomb Calorimeter
Calorimeter vessel - placed in insulating
jacket.

Stirrer is operated & initial temp. of water

noted

Electrodes connected to 6V battery to

ignite fuel. Fuel burns & heat is liberated

Heat liberated rises temp. of water in

calorimeter. Uniform stirring of water is
continued & maximum temp. attained is
noted.
16
 Heat Capacity-Bomb Calorimeter
Specific heat capacity (SHC): Amount of heat needed to increase the
temperature of 1 g of a substance by 1 °C

SHC of water = 1 cal/g per 1 °C rise.

Heat capacity = mass of substance x SHC

17
 Calculation-Bomb Calorimeter
Heat liberated by fuel = Heat absorbed by water, calorimeter
mθ = (W+w) (t2-t1) x SHC

θ = GCV of fuel
m = mass of fuel taken
W = weight of water
w = water equivalent
t1 = initial temp. of water
t2 = final temp. of water
18
 Water Equivalent in Bomb Calorimeter
Water Equivalent - heat capacity of bomb
expressed in terms of thermal equivalence of
water.

Ex. assume, to bring about 1 °C rise in

temperature of calorimeter is 570 cal. This
same amount heat (570 cal) can bring 1 °C
rise in 570 g of water (we know SHC of
water,1 cal/g °C). Thus calorimeter is
thermally equivalent to 570 g of water or
simply its water equivalent is 570 g.

19
 Calculation Correction-Bomb Calorimeter
Corrections: For accurate results, the following correction are applied.

Fuse wire correction (tF): Heat liberated, as measured above, includes

the heat given out by ignition of the fuse wire used, which actually has to
be excluded from GCV.

Acid correction (tA): Fuel containing S and N are oxidized to H2SO4 and
HNO3, under high pressure and temperature of ignition.

20
 Calculation Correction-Bomb Calorimeter

Formation of these acids are exothermic reactions. So, the measured heat
also includes the heat given out during the acid formation.

The amount of these acids is analyzed from washing of bomb by titration.

H2SO4 alone is determined by reacting with BaCl2 or Ba(OH)2 to
precipitate as BaSO4 (correction for 1 mg of S is 2.25 cal). If it does not
form precipitate with Ba(OH)2, means H2SO4 absent. May only nitric acid is
present. Which can be determined by titration against a base (eg. NaOH).

For each ml of N/10 H2SO4 formed, 3.6 cal. should be subtracted

For each ml of N/10 HNO3 formed, 1.43 cal. should be subtracted
21
 Calculation Correction-Bomb Calorimeter

Cooling correction (tC): Time taken to cool the water in calorimeter from
maximum temperature to room temperature is noted, let it be (u) and
rate of cooling dt°/min, then cooling correction = u x dt° This should be
added to the observed raise in temperature.

(W+w) (t2−t1 + tC) x SHC of H2O

𝐺𝐶𝑉𝑜𝑓 𝑓𝑢𝑒𝑙 θ = − (𝑡𝐴 + 𝑡𝐹) cal/g (or kcal/kg)
𝑚

22
 Calculation-Bomb Calorimeter
NCV can be calculated if the % of hydrogen in the fuel is known. Let the
% of hydrogen be n

1 g of hydrogen produce 9 g of steam. So “n” gram of hydrogen produce

9n gram of steam.
If hydrogen is given in percentage (%). Divide the hydrogen percentage
𝟐
by 100 to convert to grams, ex. 2% hydrogen = = 0.02 g of hydrogen.
𝟏𝟎𝟎
Latent heat of condensation of steam = 587 cal/g.
𝐇
NCV = GCV – 9 x X 587 cal
𝟏𝟎𝟎
23
 Problems in Bomb Calorimeter
1)Calculate the CV of a fuel sample of coal 0.6 g. Water equivalent of
calorimeter 2200 g. Increase in temperature = 6.52 °C

Ans: GCV = 23906 cal/g 24

 Problems in Bomb Calorimeter
2)Calculate GCV and NCV of a fuel from the following data: Mass of fuel
burnt = 0.75 g, water equivalent of calorimeter = 350 g, mass of water
taken = 1150 g, rise in temperature = 3.02 °C, % of hydrogen in fuel = 2.8.

Ans: GCV = 6040 cal/g, NCV = 5892.1 cal/g 25

 Problems in Bomb Calorimeter
3)0.6 g of a coal sample with 92% C, 5% hydrogen, and 3% ash, caused a
rise in the temperature of 2000 g water by 3.2 °C in a bomb calorimeter
experiment. Calculate the GCV and NCV of coal, given. Water equivalent
= 200 g.

Ans: GCV = 11733.3 cal/g, NCV = 11469.2 cal/g

26
4. 0.72 gram of a fuel containing 80% carbon, when burnt in a bomb calorimeter, increased the
temperature of water from 27.3o to 29.1oC. If the calorimeter contains 250 grams of water and
its water equivalents is 150 grams, calculate the HCV of the fuel. Give your answer in KJ/Kg.

Solution. Here x= 0.72 g, W = 250g, t1 = 27.3oC, t2 = 29.1oC.

HCV of fuel (L) = (W + w) (t1 - t2) Kcal/kg

x
= (250 + 150) × (29.1-27.3) kcal/kg = 1,000 × 4.2 kJ/Kg = 4,200 kJ/kg
0.72

27
5. On burning 0.83 of a solid fuel in a bomb calorimeter , the temperature of 3,500g of water
increased from 26.5 oC to 29.2 oC. Water equivalent of calorimeter and latent heat of steam are
385.0g of and 587.0 cal/g respectively. If the fuel contains 0.7% hydrogen, calculate its gross
and net calorific value.
Solution. Here wt. of fuel (x) = 0.83 g of ; wt of water (W) = 3,500 g; water
equivalent of calorimeter (w) = 385 g ; (t2 - t) = (29.2oC - 26.5oC) = 2.7oC ;
percentage of hydrogen (H) = 0.7% ; latent heat of steam = 587 cal/g

Gross calorific value = (W + w) (t1 - t2) cal/g

x
= (3,500 +385) × 2.7 = 12,638 cal/g
0.83

NCV = [GCV – 0.09 H × 587]

= (12,63 8– 0.09 × 0.7 × 587) cal/g
= (12,638 – 37) cal/g = 12,601 cal/g 28
 Problems in Bomb Calorimeter
5)Determine the water equivalent of the bomb calorimeter apparatus which
gave the following data in an experiment:
GCV of benzoic acid = 6324 cal/g
Wt. of benzoic acid taken = 1.364 g
Wt. of calorimeter = 1025 g
Wt. of calorimeter + water = 3025 g
Initial temperature = 11.872 C
Final temperature = 14.625 C
Cooling correction = 0.015 C
Heat from fuses = 22 cals
Washing of the bomb on analysis indicate the presence of 3.5 ml of N/10 HNO3
and there is no H2SO4 formed.
Ans: Water equivalent of calorimeter = 1126 g
29
Knocking and chemical structure, octane
number and cetane number
 Knocking
Knocking – simply refers to
metallic sound in combustion
engine

‘Knocking’ a type of noise in

internal combustion engine (ICE)
of a motor during combustion of
fuel
 Knocking

Gasoline(petrol)- complex mixture of hydrocarbons(100 different

compounds) ranging from C5 to C9. Most of these- branched-chain alkanes
and some are aromatic compounds. Its boiling range is 40-120 °C.

Diesel is a mixture of hydrocarbons ranging from C10 to C18 and boiling

range is 250-320 °C.

Diesel is hard to vaporize than petrol. This is why the two are not
interchangeable in car engines.

32
 Knocking
Gasoline - fuel in motors. Inside internal combustion engine (ICE) number
things happen to gasoline…

Compression of gasoline generates fine droplets

of gasoline vapor
Gasoline vapor is mixed with air and transfer to ICE
Petrol-air mixture is compressed
Petrol-air mixture, ignited by spark and it burns
Gases produced by combustion - expands
Expansion causes, piston to move i.e K.E is produced
The essential chemical reaction is oxidation of HCs
33
 Knocking
Normal combustion
To run the engine smoothly combustion of fuel- spark plug
air mixture inside ICE should proceed in
controlled fashion.
flame front

piston
Normal combustion
After ignition flame spread rapidly and
smoothly through gas mixture. The expanding
gas drives the piston down the cylinder.

In a properly functioning engine, the fuel burns

with the flame front progressing smoothly from
the point of ignition across the combustion
chamber. 34
 Knocking
Abnormal combustion
Last unburnt fuel-air mixture outside flame front may
get spontaneously ignited and combusted, rate of
oxidation is so great producing an explosive violence
sound - ‘knocking’ . It results in loss of efficiency.
or
At high compression ratio, some of the last
unburned fuel-air mixture may spontaneously ignite
ahead of the flame front and burn in an uncontrolled
manner, producing intense high-frequency pressure
waves. These pressure waves force parts of the
engine to vibrate, which produces an audible ‘knock’.
35
Rough representation of knocking

36
 Knocking

Compression ratio (CR) =

Efficiency of ICE depends on CR. Efficiency of ICE increases with

increase in CR.

Explosive reaction inside cylinder cause combustion

to stop before the optimum timing, causing a
decrease in performance.

CR depend on type of fuel and nature of constituent

present in gasoline used. Eg benzol has high CR.
37
 Knocking

Knock occurs after the passage of the spark

ignition.

While pre-ignition is the spontaneous

combustion of fuel-air mixture before the spark.

Knocking cause – damage to engine parts and

spark plug, decrease in efficiency, increase in fuel
consumption, undesirable rattling sound etc.

It can be avoided by adjusting CR, burning time, using high octane

number fuel and using anti-knocking agents. The most common method
to avoid knocking is to burn gasoline of higher octane number.
38
 Octane number
Knocking characteristics of gasoline is usually expressed in terms of
‘octane number’ higher the octane number – lesser is the knocking
tendency
Octane number of a fuel is measure of its ability to resist knocking.

Iso-octane has very little knocking, hence its anti-knock value (octane
number) is arbitrarily taken as 100.

39
 Octane number

n-heptane knocks very readily, hence its anti-knock value (octane

number) is arbitrarily taken as 0.

Octane number of any fuel is just comparison of its knocking value with
knocking value of iso-octane - n-heptane mixture.

Eg. 80-octane fuel is one which has the same combustion

characteristics as a 80:20 mixture of iso-octane and n-heptane.
40
 Chemical structure and knocking

Knocking tendency of gasoline…..

Hydrocarbons with branched-chains are more resistant to knocking than

the corresponding straight-chain paraffins.

Knocking tendency decrease with presence double bonds and cyclic

structure.
Eg. Olefins of same carbon-chain length posses better anti-knocking
property than the corresponding paraffins. Anti-knocking tendency
increase as the position of double bond approaches the center of chain.
41
 Chemical structure and knocking
Aromatic hydrocarbons (eg. benzene, toluene, xylene) have high octane
number.

Alcohols have high octane number

Naphthenes have high octane number than normal paraffins

Gasolines obtained by cracking have higher octane number than straight

run gasolines.

Alternately octane number of fuel can be increased by adding anti-

knocking agents. 42
 Anti-knocking agents
Substances added to control knocking is called anti-knocking agents eg.
tetra ethyl lead (TEL, (C2H5)4Pb)), tetra methyl lead (TML, (CH3)4Pb)),
diethyl telluride (C2H5)2Te.

They are added to motor fuel eg. about 0.5 ml/L of TEL is added to
gasoline as anti-knocking agent.

Mechanistic action of TEL

TEL converted into cloud of finely divided PbO particles, which reacts
with any hydrocarbon peroxides formed, thereby slowing down the chain
oxidation and decreasing the chances of any early detonation.

43
 Anti-knocking agents
Disadvantage of TEL
PbO formed is harmful to engine life. In order to eliminate PbO from the
engine a small amount of C2H4Br2 is also added with TEL in gasoline.

C2H4Br2 removes PbO as volatile PbBr2 with the exhaust gases. These
lead halides are poisonous to human beings and animals.

Also leaded gasoline cannot be used in automobiles equipped with

catalytic convertor because Pb present in exhaust gas poisons the
catalyst. 44
 Anti-knocking agents
Unleaded gasoline
Alternative methods of increasing octane number of gasoline is to add
high octane compounds like iso-pentane, iso-octane, ethyl benzene,
isopropyl benzene, methyl tertiary butyl ether (MTBE).

MTBE is preferred over the others because it contains oxygen in the

form of ether and supplies oxygen during combustion thereby reducing
the extent of peroxy compound formation.

Major advantage of unleaded gasoline is that it permits the use of

catalytic converter attach to the exhaust in automobiles.
45
Cetane Number

46
 Cetane number
Working of diesel engine
Diesel is a mixture of hydrocarbons ranging from C10 to C18 and boiling
range is 250-320 °C

In diesel engine, air is only first compressed to about 30-50 kg/cm2, its
temp. raises to 500-600 °C.

At this stage diesel is injected in the form of spray in to the hot air. Diesel
vapourises, attains self-ignition temp.

Pressure is further increased to about 70 kg/cm2. Diesel oil starts burning.

47
 Cetane number
Whole process of combustion of fuel in diesel engine may be consider to
take place in the following steps .
Oil droplet shot into the very hot compressed air in the cylinder, it get
vaporized
Ignition of hot vapor occurs with consequent increase in temp. and
pressure.
Oil spray still entering burns like jet flame, supplying heat and hot
gaseous combustion products to keep up the push on the piston.

All these steps completed within small fraction of second.

48
 Cetane number
In high speed diesel engine (HSD) combustion takes place in about
1/500th of a second.
Fuel used must have self-ignition temp. at least 30 °C below the temp. of
the compressed air.

Usually there is time lag between vaporization and combustion called

Ignition lag or diesel lag.

Ignition lag should be as brief as possible for smooth working.

When there is long ignition lag there occurs diesel knock.

49
 Cetane number

Long ignition lag cause large portion of fuel to get injected and
accumulated into the cylinder in vapour state before ignition is initiated.

This result in diesel vapor and air to get ignited with explosion and
violent combustion and sudden increase in temp. and pressure causing
rough and bumpy run – diesel knock.

Longer the ignition lag – greater will be the diesel knock

Straight-chain paraffins give less diesel knock than aromatic and

branched hydrocarbons.
50
 Cetane number
Knocking characteristics of diesel oil are expressed in terms of ‘cetane
number’.
Cetane number indicates readiness with which a given diesel oil
undergoes compression ignition.

Cetane a straight-chain saturated hydrocarbon (n-hexadecane, C16H34)

is chosen as reference to express the knocking characteristics of diesel
oil because it has very short ignition lag, so knocking is almost nil so its
anti-knocking value is taken as 100 i.e cetane number 100.

51
 Cetane number
2-methyl naphthalene has very long ignition lag as compared to any
commercial diesel oil. So it has very bad knocking. Hence, its cetane number is
taken as 0

CN is just comparison of knocking characteristics of fuel under test with

knocking characteristics of cetane - 2-methyl naphthalene mixture %.

Cetane number (CN) - % by volume of cetane in a mixture of Cetane - 2-

methyl naphthalene which exactly matches in its knocking characteristics with
the oil under test.

CN of high speed, medium speed and low speed diesel engine should be at
least 45, 35 and 25 respectively. 52
 Cetane number
CN of an oil can be improved by adding substances (called dopes) like
EtNO2, EtNO3, isoamyl nitrite and acetone peroxide.

Dopes are added only in small amounts (2%) and they are not effective
on low CN fuels.

Knocking in petrol engine - due to sudden spontaneous ignition

Knocking in diesel engine - due to delayed ignition

An oil of high octane number has low CN and vice versa i.e
hydrocarbons which are poor gasoline fuel are good diesel fuels. 53
THANK YOU

54
Mod. 7: CORROSION AND COATINGS
The secret of effective engineering lies in controlling
rather than preventing corrosion, because its is
impossible to eliminate corrosion.
-Michael Henthorne
 Natural Abundance of Metals

In the form of oxides, carbonates, chlorides,

silicates etc.
 Rust formation in iron

4Fe + 3O2 + 6H2O → 4Fe(OH)3

• Corrosion is a natural process that converts a refined
metal into a more chemically stable form such as
oxide, hydroxide, or sulfide.

• It is the gradual destruction of materials by chemical

and/or electrochemical reaction with their
environment.

• Corrosion in other words is a natural-occurring “Anti-

metallurgy” where the metals, that are extracted and
refined from their mineral ores, slowly return to their
natural state.

• Corrosion can occur in plastics, polymers and

generally more common in metals.

Dr. Kiran Kumar Tadi Corrosion 02-August 2020

 Corrosion in Metals

Tarnishing of Silver In the case of silver tarnish,

the silver combines with sulfur and
forms silver sulfide ( Ag2S ) which is
black. The original silver surface can be
restored if the layer of silver sulfide is
removed

Blue-green patina of statue of liberty

Copper metal is oxidized to copper(I) oxide (Cu2O),
which is red, and then to copper(II) oxide, which is black
Coal, which was often high in sulfur, was burned
extensively in the early part of the last century. As a result, sulfur
trioxide, carbon dioxide, and water all reacted with the CuO.
Ancient Indian Technology

Iron Pillar of Delhi

 The iron pillar of Delhi is a structure 23 feet 8 inches (7.2 metres) high with 16
inches (40.64 cm) diameter that was constructed by Chandragupta II (reigned
c. 375-415 CE).
 The iron pillar in India was manufactured by the forge welding of pieces of
wrought iron.
 R. Balasubramaniam of the IIT Kanpur explains how the pillar's resistance to
corrosion is due to a passive protective film at the iron-rust interface.

 The presence of second-phase particles (slag and unreduced iron oxides) in the
microstructure of the iron, that of high amounts of phosphorus in the metal, and
the alternate wetting and drying existing under atmospheric conditions are the
three main factors in the three-stage formation of that protective passive film
Corrosion and It’s Classification

Any process of deterioration (or

destruction) and consequent loss of solid metallic
material, through an unwanted chemical or
electrochemical attack by its environment
Corrosion
(Oxidation)
Metal metallic compounds + Energy
Extraction of
Metals

Classification
• Dry or Chemical Corrosion

• Electrochemical Corrosion
 Protective coatings
oProtective coating provide a physical barrier between the metal
and the environment.
oThey not only give corrosion protection but also add to the
decorative value of the article.

oCoatings are broadly divided as:

a) Inorganic coatings : metallic and chemical conversion coatings

b) Organic coatings : paints, varnishes, enamels, lacquers

o Protective coatings are classified as:

i) metallic coatings
ii) chemical conversion coatings
iii) organic coatings and linings 9
Protective coatings
The most important step before protective coatings are applied to metals
is surface preparation.
o Surface preparation is a process to remove rust, oxide scales, oil,
grease, dust etc.
o If these materials are not removed, the protective coating will not be
smooth, uniform, cohesive and will not adhere to the metallic surface.
o Hence, mechanical and electrical methods are used to prepare the
surface of the metallic article to be coated clean and free of these
impurities.
o Mechanical cleaning, sandblasting, solvent cleaning, alkali cleaning,
acid pickling and etching are normal processes followed for surface
preparation of the article to be coated.

a) Mechanical cleaning:
o Useful for removing loose scales and rust.
o Hammering, wire brushing, grinding, pneumatic blasting, polishing are
the methods commonly used.
11
 SURFACE CLEANING
b) Sandblasting:
o Fine sand or abrasive material along with air stream at a pressure of
25-100 atm. is impinged on the metal surface.

o This will produce enough roughness for good adherence of the

protective coating.

o Though the method is expensive, it is quite fast and useful.

c) Solvent cleaning:
o Solvent cleaning is mainly used to remove oil, grease and rust from
the base metal.

o Alcohols, xylene, toluene, chlorinated hydrocarbons are used.

o Hot water cleaning is followed after solvent cleaning is done.

12
 SURFACE CLEANING
d) Alkali cleaning:

o Cleaning of the base metal with sodium hydroxide,

trisodium phosphate, sodium silicate, soda ash etc., is
carried out to remove old paint coatings soluble in alkaline
medium.
o After alkali cleaning, washing is done with 1% chromic acid
solution.

e) Acid pickling and etching:

o Base metal is dipped inside the acid solution at higher

temperature for long periods of time.
o This treatment ensures cleaning of the base metal surface
free from all kinds of impurities including oils, greases, rust etc.,
o H2SO4, HCl, HF, H3PO4, HNO3 are the acids commonly
used for pickling and etching.
14
 Protective coatings
Metallic coatings:

a) Anodic coatings

b) Cathodic coatings

5a) Anodic coatings:

o Anodic coatings are given on cathodic metals using metals which are
more anodic.
o Zinc, aluminium, cadmium coatings on iron are anodic coatings.
o If the coating breaks, then a galvanic couple is set up and corrosion rate
gets enhanced.
o During this process, the anodic coating gets disintegrated but it protects
the cathodic base metal.
o Hence, the anodic metal sacrifices itself to protect the base metal.
o This type of coating is known as galvanisation.

15
 Protective coatings
5b) Cathodic coatings:

o Cathodic coatings are given on anodic metals using metals which are
more cathodic.
o Coating of tin, chromium, nickel on iron surface are cathodic coatings.
o If there is a discontinuity in the coating, then galvanic couple will form
with base metal as anode and the coated metal as cathode.
o Then the process of corrosion will start by the base metal ions going
into solution and the metal deteriorating.
o To avoid this, the article is checked and re-plated periodically so that
there is no discontinuity in the coating.

16
 Anodic vs. Cathodic Coating
Anodic Coating Cathodic Coating

Protects the underlying base metal ‘sacrificially’ Protects the underlying base metal, due to its noble
character and high corrosion-resistance

Electrode potential of coating metal is lower than that of Electrode potential of coating metal is higher than that of
the base metal the base metal

If pores, breaks or discontinuities occur in such coating, If pores, breaks or discontinuities occur in such a coating,
the base metal is not corroded till all the coating metal is the corrosion of the base metal is speeded up
consumed

Coating of Zn on Iron is an example Coating of Sn on Iron is an example

Protective coatings
Methods of metallic coatings:

a) Hot dipping
b) Physical Vapor Deposition
a) Thermal Vapor Depsosition
b) Sputtering
c) Ion-Implantation
c) CVD

a) Hot dipping:

Two types of hot dipping techniques are known:

i) Galvanizing: Dipping the base metal iron in molten zinc metal solution

ii) Tinning : Dipping the base metal iron in molten tin metal solution.

18
Galvanising and Tinning
Hot dipping is also a technique of metallic coating
Two types of hot dipping techniques are known

i) Galvanizing: Dipping the base metal iron in molten zinc

metal solution.

Eg. Galvanised iron pipes used for water lines

i) Tinning : Dipping the base metal iron in molten tin metal

solution.

Eg. Tin coated steel containers for storage of food stuff such
as Fruit pulp etc.
Illustrations for Metallic Coatings
Tinned Cans
 Physical Vapour Deposition
o This is a process of depositing some material by atom by atom or
molecule by molecule or ion by ion.

Applications:
1. This process is widely used to produce decorative coatings on plastic
parts those are resembling shiny metal.

2. Many automobile parts are plastic with a PVD coating of aluminium.

3. A lacquer coating is applied over the decorative coating to provide

corrosion protection.

4. This process is also used to apply relatively thick (1mm) coatings of

heat resistant materials on jet engine parts, A special alloy of
chromium, aluminium and yttrium is used for this type of coating. 24
 PVD: – 1. Thermal Evaporation Method

Al and Au are quite usable in thermal evaporation system with heated

crucible, for they can be melt in crucible and generate enough quantity of
vapours.
However, W and Ti are not suitable for their low vapour pressure.
Typical deposition rates in industry is around 0.5 µm/min (~8 nm/s, for Al)25
 PVD: 2 – Sputtering Method
Sputtering :
A popular method for adhering thin films onto a substrate.
Sputtering is done by bombarding a target material with a charged gas (typically
argon) which releases atoms in the target that coats the nearby substrate.
It all takes place inside a magnetron vacuum chamber under low pressure.
1. High technology coatings such as ceramics, metal alloys and organic and inorganic
compounds are applied by sputtering.
2. The substance to be coated is connected to a high voltage DC power supply.
3. When the vacuum chamber has been pumped down, a controlled amount of argon or
another gas is introduced to establish a pressure of about 10-2 to 10-3 torr.
4. On energizing current supply, plasma is established between the work and the
material to
be coated.
5. The sputtering gas is often an inert gas such as argon. For efficient momentum
transfer, the
atomic weight of the sputtering gas should be close to the atomic weight of the
target, so for sputtering light elements neon is preferable, while for heavy elements
krypton or xenon are used. Reactive gases can also be used to sputter compounds.
27
 PVD: 2 – Sputtering Method
Sputtering is a process whereby particles are ejected from a solid target material due to
bombardment of the target by energetic particles.

Sputtering is done either using DC voltage (DC sputtering) for metals or using AC voltage
(RF sputtering) for dielectric materials and polymers.
The gas atoms are ionized and they
bombard the material to be coated.

The energy of imposing ions cause

atoms of the target material to be
sputtered off and they are transported
through the plasma to form a coating.

Direct current sputtering is used when

the target is electrically conductive.

Radio-frequency sputtering, which uses

a RF power supply is used when the
target is a non conductor such as
polymer. Figure : PVD by sputtering process
28
 PVD: 2 – Sputtering Method
Plasma is a “state of matter similar to gas in which a certain portion of the particles are
ionized”
• The main principle is to build a vaccum chamber and fill with Argon

• By adding a high voltage, the argon will arc to plasma state

• The argon ion (Ar+) will move toward to cathode with high speed and sputter the
target material (use target as cathode).

• The target atom or molecular will be hit to substrate surface and condense as a
film.

• Instead of heat melting in evaporation method, the plasma Ar+ ion hit and sputter
the target is the main mechanism in plasma sputtering method.

• The target atom is knocked out by Ar+ ion, the knock force is so big and can
accelerate target atom a high speed. With such velocity, the target atom can hit
and attach to substrate surface deeply.

• The film density is good compared to thermal evaporation.

 PVD: 2 – Sputtering Method
Applications of Sputtering method:

o This method is used in VLSI fabrication

(Very-large-scale
integration (VLSI) is the process of creating an integrated circuit (IC) by
combining hundreds of thousands of transistors or devices into a single chip)

o Sputtering is used extensively in the semiconductor industry to deposit thin films of

various materials in integrated circuit processing.
o Thin antireflection coatings (MgF2 and Fluoropolymers; mesoporous silica materials;
titanium nitride and niobium nitride) on glass for optical applications are also
deposited by sputtering.
o An important advantage of sputter deposition is that even materials with very high
melting points are easily sputtered while evaporation of these materials in a resistance
evaporator or Knudsen cell is problematic or impossible. Sputter deposited films have
a composition close to that of the source material.

31
Sputtering offers the following advantages over other PVD methods used in
VLSI fabrication:
1) Sputtering can be achieved from large-size targets, simplifying the deposition of
thins with unifrom thickness over large wafers;
2) Film thickness is easily controlled by fixing the operating parameters and simply
adjusting the deposition time;
3) Control of the alloy composition, as well as other film properties such as step
coverage and grain structure, is more easily accomplished than by deposition
through evaporation;
4) Sputter-cleaning of the substrate in vacuum prior to film deposition can be
done;
5) Device damage from X-rays generated by electron beam evaporation is
avoided.

Sputtering, however, has the following disadvantages too:

1) High capital expenses are required;

2) The rates of deposition of some materials (such as SiO2) are relatively low;
3) Some materials such as organic solids are easily degraded by ionic
bombardment;
4) Sputtering has a greater tendency to introduce impurities in the substrate than
deposition by evaporation because the former operates under a lesser vacuum range
than the latter.
 PVD – 3 - Ion Implantation Method
1. A third variation of the PVD process is ion implantation method

2. Metal is evaporated thermally and plasma is established to ionize

the evaporating species

3. Evaporant ions bombard the substrate with energy

4. They physically implant into the substrate to produce an

extremely strong coating bond.

5. Sputter and ion plated coatings are used in design for very thin
films for electrical, optical and wear-resistant applications.

6. The wear properties of tools are widely enhanced by hard thin

film coatings.
33
34
35
Applications of PVD

36
 Applications
1. This process is widely used to produce decorative coatings on
plastic parts those are resembling shiny metal.

2. Many automobile parts are plastic with a PVD coating of

aluminium.

3. A polish coating is applied over the decorative coating to provide

corrosion protection.

4. This process is also used to apply relatively thick (1mm) coatings

of heat resistant materials on jet engine parts;

- A special alloy of chromium, aluminium and yttrium is used for

this type of coating.
Computational chemistry is the use of computers to
solve the equations of a theory or model for the
properties of a chemical system.

1
Three “Pillars” of Scientific Investigation
⮚ Experiment
⮚ Theory (analytical equations)
⮚ Computational Simulation
⮚ (“theoretical experiments”)

2
⮚Simulation is becoming a third pillar of science, along
with theory and experiment.

⮚Using theory, we develop models: simplified

representations of physical systems.

⮚We test the accuracy of these models in experiment,

and use simulation to help refine this feedback loop.

⮚Anything that can be measured can be simulated,

including properties related to energetics, structures,
and spectra of chemical systems.
3
 The Nobel Prize in Chemistry 1998

John A. Pople Walter

Kohn
The Nobel Prize in Chemistry 1998 was divided equally
between Walter Kohn "for his development of the density-
functional theory" and John A. Pople "for his development of
computational methods in quantum chemistry".
4
 2013 Nobel Prize In Chemistry

"for the development of multiscale models for complex chemical systems”

• Martin Karplus, Université de Strasbourg, France, and Harvard University,
Cambridge, MA, USA

• Michael Levitt, Stanford University, Los Angeles, CA, USA

• Arieh Warshel, University of Southern California (USC), CA, USA 5

 Computational Chemistry
WHY
do theoretical calculations?

WHAT
do we calculate?

HOW
are the calculations carried out?

6
 Advantages of Computational Studies
 Performing “in silico” experiments that would be too
dangerous or too expensive (or simply impossible for
practical reasons)
 Optimization of different parameters to identify promising
setups for experiments. It saves time and money.
 Rationalizing the experimental conditions
 Docking of ligand in receptor active sites and exact
measurement of geometric and energetic favor ability of
such interactions. Eg. Virus protein binding to cell
7
receptor
 Theoretical/Computational
Chemistry

Classical Mechanics Quantum

Mechanics
Sir Isaac Newton Erwin Schrödinger
(1642 - 1727) (1887 - 1961)

9
 Overview of computational methodologies

Quantum Mechanics (QM) Classical Mechanics (CM)

Molecular Mechanics (MM)

Molecular Dynamics (MD)
Ab initio methods Semi-empirical
methods

Density functional theory (DFT)

 Schrödinger Equation

• H is the quantum mechanical Hamiltonian for the

system (an operator containing derivatives)
• E is the energy of the system
• Ψ is the wave function (contains everything we are
allowed to know about the system)
• |Ψ|2 is the probability distribution of the particles
Ab-initio methods
o The term "Ab Initio" is Latin for "from the beginning".
Computations of this type are derived directly from theoretical
principles, with no inclusion of experimental data.
o Mathematical approximations are usually a simple functional form
for a an approximate solution to A wave function! (The Shrödinger
Equation).
o These methods try to compute an accurate as possible many
electron wavefunction which then automatically leads to an
accurate total energy.
o Accuracy can be systematically improved.

Semi-empirical methods
o It uses approximations from empirical (experimental) data to
provide the input into the quantum chemical models.
o Accuracy depends on parameterization.
12
o DFT allows getting information about the energy, the structure and
the molecular properties of molecules at lower costs. It goes with
electron density instead of wave function. Accuracy varies with
functionals, however, there is no systematical way to improve the
accuracy.

o Molecular mechanics uses classical physics and empirical or semi-

empirical (predetermined) force fields to explain and interpret the
behavior of atoms and molecules. Generally not very accurate.

o Molecular dynamics is a computer simulation technique that allows one

to predict the time evolution of a system of interacting particles (atoms,
molecules, etc.)

13
Doing Chemistry with Computers

14
15
Using computational chemistry software you can in particular perform:

o Electronic structure predictions

o Geometry optimizations or energy minimizations
o Conformational analysis and potential energy surfaces (PES)
o Frequency calculations
o Finding transition structures and reaction paths
o Molecular docking: Protein – Protein and Protein-Ligand interactions
o Electron and charge distributions calculations
o Calculations of rate constants for chemical reactions: Chemical
kinetics
o Thermochemistry - heat of reactions, energy of activation, etc.
o Calculation of many other molecular and physical and chemical
properties
o Orbital energy levels and electron density
o Electronic excitation energy 16
 Computer Performance

1990 2000 2021

Years
17
• Structure of a molecule in general is how atoms are arranged
in the molecule in the three dimensional space.

• Potential energy surface (PES) is a plot of energy with respect

to various internal coordinates of a molecule such as bond
length, bond angle etc.

18
• The PES is the energy of a molecule as a function of the positions
(coordinates).

• This energy of a system of two atoms depends on the distance

between them.

• At large distances the energy is zero, meaning “no interaction”.

• The attractive and repulsive effects are balanced at the minimum

point in the curve
Potential energy for nuclear motion in a diatomic molecule

20
Potential Energy Surfaces and Mechanism

21
 Conformational Analysis

⮚Identification of all possible minimum energy structures

(conformations) of a molecule is called conformational analysis.

⮚Conformational analysis is an important step in computational

chemistry studies as it is necessary to reduce time spent in the
screening of compounds for properties and activities.

22
⮚The identified conformation could be the local minimum,
global minimum, or any transition state between the
minima.

⮚Out of the several local minima on the potential energy

surface of a molecule, the lowest energy conformation is
known as the global minimum.
Global minimum

Local minima

23
Local minimum Local minimum

Global minimum

24
Ethane Conformations

25
26
27
28
 Ramachandran plot: Peptide and Protein systems
• In a polypeptide, the main chain N-C and C-C bonds relatively are free to rotate. These
rotations are represented by the torsion angles phi and psi, respectively.

• G N Ramachandran used computer models of small polypeptides to systematically vary

phi and psi with the objective of finding stable conformations.

29
 Geometry optimization
Or
Energy Minimization

To Find

• Minimum energy geometry

• Lowest energy structure
• Most stable conformation
• Many problems in computational chemistry (and scientific
computing in general!) are optimization problems

• Finding the “stationary points” in multidimensional

system – Difficult Job

Why do we need the stable geometry?

 Geometry optimization

⮚ The most stable geometry is the one which yields

minimum energy

⮚ Objective of geometry optimization is to find an atomic

arrangement(geometry) which makes the molecule most
stable

32
 Methods of Optimization
Energy only:
• Simple methods

Energy and first derivatives (forces)

• Steepest descents (poor convergence)
• Conjugate gradients (retains information)
• Approximate Hessian update

Energy, first and second derivatives

• Newton-Raphson
• Broyden (BFGS) updating of Hessian (reduces
inversions)
• Rational Function Optimization (for transition states)