Water Treatment

HARD WATER
Water that contains appreciable quantity
of dissolved minerals (like magnesium
and calcium ions) is called hard water.
Or
Water which does not produce lather
with soap solution

SOFT WATER
Treated water which does not contained
any dissolved minerals except sodium.
Or
Water which produce lather with
soap solution
 Why hard water do not produce lather with soap?

Soap is Na or K salts of long chain fatty acids, C 17H35COOH.

When water is hard (i.e. if it contains salts of magnesium and calcium),

the following reaction takes place when it is used with soap.

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

2C17H35COONa + MgSO4 → (C17H35COO)2Mg↓ + Na2SO4

Hardness of water is due to presence of Calcium and Magnesium salts

Test for Hardness- Eriochrome Black-T
test
1. Take Two conical flasks and Pure water Hard water
add 5 ml of ammonium buffer
solution and 2-3 drops of EBT
indicator
2. To one flask add 5 ml of RO
water (soft) and shake well
3. To another flask add 5 ml of
sea water (hard) and shake
well
4. Observe the colour in both Sodium salt of EBT
Estimation of Hardness by EDTA method
• Ca and Mg ions form complex with the chelating agent, ethylene diamine
tetraacetic acid (EDTA).
• When Eriochrome BlackT (EBT) is added to hard water in the presence of
ammonia- ammonium chloride buffer (pH 9-10) EBT forms a Meta stable
wine red coloured complex with the Ca& Mg ions
• On treating the wine red complex with EDTA, a more stable metal –EDTA
complex is formed setting the EBT free.
• This reaction proceeds with a colour change from wine red to steel blue.
 EDTA Sodium salt of EBT

Structure of Metal-EDTA
complex
(here M=Ca2+, Mg2+)

Dr.V.S.Gayathri
Hardness - expression
Hardness is expressed as equivalent amount (equivalents) of CaCO3

i. Molar mass of CaCO3 is exactly 100

ii. It is the most insoluble salt that can be precipitated in water treatment.

Equivalents of CaCO3 is calculated using the formula

Mass of hardness producing substance in mg/L x100
Molecular wt. of hardness producing substance

units – mg/L = ppm

parts of CaCO3 equivalents in hardness in 10 6 parts of water
Softening of hard water
 II. 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 Porous Structure of zeolite

 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink
 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 Ca 2+, 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 + 2NaHCO 3 Scale formation

Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO 3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na 2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na 2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained
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 HCO 3- and CO32- in the
softened water (then it may form NaHCO 3 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
 III. 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
In general the resins containing acidic functional groups (-COOH, -SO 3H 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-)
Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin

R = CH3
 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
 Process of softening

Reactions occurring at Cation exchange resin

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

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

Reactions occurring at Anion exchange resin

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

2 ROH- + Cl- (hard water) R 2Cl- + 2 OH-

At the end of the process

H+ + OH- H 2O
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
 IV. Softening of water by Mixed Bed deioniser

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 anioins 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 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

Demineralised
water
 Reverse osmosis

• Reverse osmosis filters have a pore size around

0.0001 micron
• 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
• Reverse osmosis removes monovalent ions,
which means that it desalinates the water
 Principle of osmosis and reverse
osmosis

• When two solutions of unequal concentrations are

separated by a semipermeable membrane, solvent
will flow from lower to higher solute concentration
• This phenomenon can be reversed (solvent flow
reversed) by applying hydrostatic pressure on the
concentrated side
 Osmosis Reverse Osmosis

Cellulose acetate
Hydrostatic pressure Polysulfone
in excess of osmotic Polysulfone
pressure is applied, amide
the solvent flow Polyamide
reverses Poly-acrylonitrile
Advantages:
Reverse OSMOSIS

1.Removes ionic, non-ionic, colloidal and high

molecular weight organic matter

2.Removes colloidal silica

3.Low Maintenance cost - Life time (~2 years)

4.Easy membrane replacement

5.Low operating cost, high reliability

 Module VI
FUELS & COMBUSTION
INTRODUCTION AND SOLID FUELS
FUELS
Fuel is a combustible substance which when burnt in
oxygen or air, produces significant amount of heat which
can be economically used for domestic and industrial
purposes for generating power.
In the process of combustion, the chemical energy of
fuel is converted into heat energy.
• Fuel + Air/oxidizer  Products of combustion + Energy
Calorific value of fuels

• The most important property of fuel to be taken into

account is its calorific value or the capacity to supply
heat. The calorific value of a fuel can be defined as
"the total quantity of heat liberated when a unit mass
or volume of the fuel is burnt completely".
• Units are Calorie/ Kilocalorie - Calorie is the
amount of heat required to raise the temperature of
one gram of water through one degree centigrade.
Determination of Calorific Value
Bomb calorimeter
Calculation

m = mass of fuel pellet (g)

W = mass of water in the calorimeter (g)
w = water equivalent of calorimeter (g)
t1 = initial temperature of calorimeter.
t2 = final temperature of calorimeter.
HCV = gross calorific value of fuel.
Higher or Gross Calorific Value (HCV or GCV)

• Usually, all fuels contain some hydrogen and when the

calorific value of hydrogen containing fuel is determined
experimentally, the hydrogen is converted to steam.
• If the products of combustion are condensed to room
temperature (15C or 60F), the latent heat of condensation of
steam also gets included in the measured heat, which is then
called "higher or gross calorific value".
• So gross or higher calorific value may be defined as "the total
amount of heat produced when one unit mass/volume of the
fuel has been burnt completely and the products of combustion
have been cooled to room temperature".
 Lower or Net Calorific Value

• In actual use of fuel, the water vapour and moisture etc are not
condensed and escapes as such along with hot combustion gases.
Hence a lesser amount of heat is available. So, net or lower calorific
value may be defined as "the net heat produced when unit mass /
volume of the fuel is burnt completely and the products are permitted
to escape".
• Net or lower calorific value can be found from GCV value
NCV = GCV - Latent heat of water vapour formed
= GCV - Mass of hydrogen x 9 x latent heat of steam
• 1 part by mass of hydrogen produces 9 parts by mass of water. The
latent heat of steam is 587 k cal / kg or 1060 B. Th. U. / lb of water
vapour formed at room temperature. (ie 15 C).
 Water Equivalent of the calorimeter is
determined by burning a fuel of known calorific
value (benzoic acid (HCV = 6,325 kcal/kg) and
naphthalene (HCV = 9,688 kcal/kg)
If H is the percentage of hydrogen in fuel,
the mass of water produced from 1 g of fuel =
(9/100)×H
= 0.09 H
Heat taken by water in forming steam = 0.09 H× 587 cal
(latent heat of steam = 587 cal/kg)

LCV = HCV – Latent heat of water formed

1. 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
2. On burning 0.83 of a solid fuel in a bomb calorimeter , the
temperature of 3,500g of water increased from 26.5oC to 29.2oC.
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
1. Fuse wire correction
2. Acid correction
3. Cooling correction
 Corrections

Fuse wire correction:

Heat liberated during sparking should be subtracted
from calorific value
Acid correction:
Fuels containing Sulphur and Nitrogen if oxidized, the heats of formation of H 2SO4 and
HNO3 should be subtracted (as the acid formations are exothermic reactions)
Cooling correction:
The rate of cooling of the calorimeter from maximum temperature to room temperature
is noted. From this rate of cooling (i.e., dt°/min) and the actual time taken for cooling (X
min) then correction (dt × X) is called cooling correction and is added to the (t2 . t1)
term.
 (W+w) (t2-t1+Cooling Correction) – (Acid + Fuse Correction)
GCV =

Mass of the fuel (x)

3. A sample of coal contains C =93%; H =6% and ash = 1%. The following data were
obtained when the above coal was tested in bomb calorimeter.
Wt. of coal burnt =0.92g
Wt. of water taken =550g
Water equivalent of calorimeter =2,200g
Rise in temperature =2.42 oC
Fuse wire correction =10.0 cal
Acid correction =50.0 cal
Calculate gross and net calorific value of the coal, assuming the latent heat of
condensation of steam as 580 cal/g.

Solution: Wt. of coal sample (x) = 0.92 g; wt. of water (W) =550 g;
water equivalent of calorimeter (w) = 2,200g;
temperature rise (t2-t1) = 2.42 oC;
acid correction = 50.0cal;
fuse wire correction = 10.0 cal;
latent heat of steam = 580 cal/g;
percentage of H =6%
GCV = (W + w) (t1 - t2) –[acid+fuse corrections]
x
= (550+2,200) × 2.42 – [50+10] cal
0.92g
= 7,168.5 cal/g.

NCV = [GCV – 0.09 H × latent heat steam]

= (7168.5 – 0.09 × 6 × 580) cal/g
= 6855.3 cal/g
 Knocking
• In an internal combustion engine, a mixture of gasoline vapour and air
is used as a fuel.

• After the initiation of the combustion reaction by spark in the cylinder,

the flame should spread rapidly and smoothly through the gaseous
mixture, thereby the expanding gas drives the piston down the cylinder.

• The ratio of the gaseous volume in the cylinder at the end of the
suction-stroke to the volume at the end of compression-stroke of the
piston is known as the 'compression ratio'.

• The efficiency of an internal combustion engine increases with the

compression ratio.
• Compression ratio (CR) is defined as the ratio of the cylinder volume
(V1) at the end of the suction stroke to the volume (V2) at the end of
the compression stroke of the piston.

• V1 being greater than V2, the CR is >1.

• The CR indicates the extent of compression of the fuel-air-mixture by

the piston.

• However, successful high compression ratio is dependent on the nature

of the constituents present in the gasoline used.

• In certain circumstances, due to the presence of some constituents in

the gasoline used, the rate of oxidation becomes so great that the last
portion of the fuel-air mixture gets ignited instantaneously producing
an explosive violence, known as 'knocking'.

• The knocking results in loss of efficiency, since this ultimately

decreases the compression ratio.
 Chemical structure and knocking

• The tendency of fuel constituents to knock is in the

following order. Straight - chain paraffins > branched - chain
paraffins (isoparaffin) > olefins > cyclo paraffins (naphthenes)
> aromatics.

Octane number
• The most common way of expressing the knocking
characteristics of a combustion engine fuel is by 'octane
number', introduced by Edger. It has been found that n-
heptance, knocks very badly and hence, its anti-knock value
has arbitrarily been given zero.
 Octane number
• Octane number is equal to the percentage by volume of iso-octane (2,2,4-
trimethyl pentane) in a mixture of n-heptane and iso-octane having the same
knocking tendency compared to the sample of gasoline being tested;

• Iso-octane has the best antiknocking properties and assigned an octane

number of 100 whereas n-heptane has poor antiknocking property and
assigned an octane number of zero.

• The hydrocarbons present influence the knocking properties of gasoline

which vary according to the series:

straight chain paraffin > branched chain paraffin > olefin > cycloparaffin >
aromatics.

• The fuel which has same knocking tendency with the mixture having 80%
iso-octance has octane number 80.
 H H H H H H H

H C C C C C C C H

H H H H H H H

n-heptane

CH 3

CH 3 C CH 2 CH CH 3

CH 3 CH 3

Isooctane
 Improvement of anti-knock characteristics of a fuel
• The octane number of many otherwise poor fuels can be raised by
the addition of tetra ethyl lead (C2H5)4Pb or TEL and diethyl
telluride (C2H5)2Te. In motor spirit (Motor fuel) about 0.5ml and in
aviation fuel 1.0 - 1.5ml of TEL is added per litre of petrol.

• TEL is converted into a cloud of finely divided lead and lead oxide
particles in the cylinder and these particles react with any
hydrocarbon peroxide molecules formed, thereby slowing down
the chain oxidation reaction and thus decreasing the chances of any
early detonation.

• However deposit of lead oxide is harmful to the engine life. In

order to help the simultaneous elimination of lead oxide formed
from the engine, a small amount of ethylene dibromide (or
ethylene dichloride) is also added to petrol.

• The added ethylene dibromide removes lead oxide as volatile lead

bromide along with the exhaust gases. The presence of sulphur
compounds in petrol reduces the effectiveness of the TEL. TEL is
more effective on saturated hydrocarbons than on unsaturated ones.
 Other additives

• Oxidation inhibitors - 2,4 - ditertiary butyl - 4 - methyl phenol.

• Rust inhibitors - Organic compounds of phosphorus or

antimony.

• Ignition control additives - tricresyl phosphate which suppresses

pre-ignition of the fuel due to glowing deposits on spark plug or
a hot spot on the cylinder wall.
 Diesel Engine Fuels

Characteristics of an ideal diesel oil

• It should have low spontaneous ignition

temperature.
• It should have very little sulphur, aromatic and ash
content.
• The ignition lag should be as short as possible.
 Knocking in Diesel Engines

• In a diesel engine, the fuel is exploded not by a spark, but by the

application of heat and pressure. In the cycle of operations of a diesel
engine, air is first drawn into the cylinder and compressed.
• Towards the end of the compression stroke, the fuel (diesel oil) is
injected as a finely-divided spray into air in the cylinder heated to about
500C by compression.
• The oil absorbs the heat from the air and if it attains its ignition
temperature the oil ignites spontaneously. The pressure of the gases is
further increased by the heat accompanying the ignition of the oil.
• The piston is pushed by the expanding gases and this constitutes the
power stroke.
• Fuel feed and ignition continue during this down stroke. The fuel
injection stops at the exhaust stroke.
• Diesel engine fuels consist of longer chain hydrocarbons than internal combustion
engine fuels.

• The main characteristic of diesel engine fuel is that it should easily ignite below
compression temperature.

• There should be as short an induction lag as possible. This means that it is essential
that the hydrocarbon molecules in a diesel fuel should be as far as possible the
straight-chain ones with a minimum admixture of aromatic and side-chain
hydrocarbon molecules.

• The suitability of a diesel fuel is determined by its cetane value, which is the
percentage of hexadecane in a mixture of hexadecane and 2-methyl naphthalene,
which has the same ignition characteristics as the diesel fuel sample, under the same
set of conditions.

• The cetane number of a diesel fuel can be raised by the addition of small quantity of
certain "pre-ignition dopes" like alkyl nitrites such as ethyl nitrite, iso-amyl nitrite,
acetone peroxide.
 H H H

H C C C H
14
H H H
n-Hexadecane (Cetane No. = 100)

CH3

2-Methyl naphthalene (Cetane No. = 0)

 Ignition quality decreases among
hydrocarbons is as follows

• n-alkanes > naphthalenes > alkenes > branches

alkanes > aromatics

•Cetane number decreases

•Ignition quality decreases
•Ignition delay increases
CORROSION
CONTROL
 Spontaneity of Corrosion
Metal has natural tendency to go to Thermodynamically stable
state
Metals (thermodynamically unstable) are usually extracted from
ores (thermodynamically stable) through the application of a
considerable amount of energy
Corrosion (oxidation)
Metal Ore (metallic compd) Energy
(T.D.Unstable) T.D.Stable
Metallurgy (reduction)
The energy required to convert ore to metallic state is returned
when the metal corrodes to form the original compound.
The tendency of metal to release this energy by corrosion, is
reflected by the relative positions of pure metals in the
electrochemical series.
 Rust formation in iron

4Fe + 3O2 + 6H2O → 4Fe(OH)3

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
 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.
 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)
 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.
High technology coatings such as ceramics, metal alloys and organic and inorganic
compounds are applied by sputtering.
The substance to be coated is connected to a high voltage DC power supply.
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.
On energizing current supply, plasma is established between the work and the material to
be coated.

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

 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.
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;

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.
Computational chemistry is the use of computers to
solve the equations of a theory or model for the
properties of a chemical system.
⮚ 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.
 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".
 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

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
• 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.
Potential energy for nuclear motion in a diatomic molecule
Potential Energy Surfaces and Mechanism
 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.
⮚ 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
Local minimum Local minimum

Global minimum
Ethane Conformations