Engineering Chemistry

BCHY101L

1
 Module 7

Industrial applications

Water purification methods - zeolites, ion-exchange resins and

reverse osmosis; Fuels and combustion -LCV, HCV, Bomb
calorimeter (numericals), anti-knocking agents); Protective
coatings for corrosion control: cathodic and anodic protection -
PVD technique; Chemical sensors for environmental monitoring -
gas sensors; Overview of computational methodologies: energy
minimization and conformational analysis.
Water purification methods

reverse osmosis

Protective coatings for corrosion control: cathodic

and anodic protection

PVD technique
 Fuels
 Fuel – a combustible substance, upon burning in air or O2
gives large amount of heat. Eg. wood, charcoal, kerosene,
petrol, LPG, biogas, etc.
 Combustion - a process in which a substance burn in air
or O2 with evolution of heat. A substance which is burnt is
called combustible substance.
 Fuels contain C and H as main constituent, during
combustion C and H combine with O2 and produce CO2
and H2O with simultaneous release of heat at rapid rate.
 CO2 and H2O has low energy than the compound from
which it is formed.
 Thus energy released during the combustion process is the
difference in the energy of the reactant and that of
products formed.
 Calorific Value (CV) of a fuel
 Efficiency of a fuel is judged 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 is generally expressed in Calories (cal), Kilo calories
(kcal), British Thermal Units (BTU), Centigrade Heat Unit (CHU)
 1 Calorie (cal) – quantity of heat required to raise the temp. of 1
g of H2O by 1 °C
1 cal = 4.185 Joules
1 Kilocalorie = 1000 cal.
1 British Thermal Unit (BTU) - quantity of heat required to
raise the temp. of 1 lb of H2O by 1 °F
1 BTU = 252 cal = 1054.6 Joules
1 Centigrade Heat Unit – amount of heat required to raise the
temperature of 1 lb of water through 1 °C
1 kg = 2.2 lb; 1 °C = 1.8 ° F
Unit of CV of solids and liquids
 Generally expressed in calories/gram (cal/g) or kilocalories/gram
(kcal/g) or BTU/lb or CHU/lb
Unit of CV of gas
 Expressed in kcal/m3 or cal/cm3 or BTU/ft3 at given T and P.
Heat quantity per unit volume of gas is CV of gaseous fuel.
 Since volume of gas varies with T and P. CV of gaseous fuel
includes T and P.
 CV of fuel generally expressed in two ways

Calorific Value
(CV)

Gross/High Calorific Net/Low Calorific

Value (GCV/HCV) Value (NCV/LCV)
Gross/High Calorific Value (GCV/HCV)
 Quantity of heat evolved by complete combustion of unit mass of
fuel in air or O2 and the products of combustion are brought
down to normal temperature.
 Hydrocarbon fuel is mostly used. During combustion, carbon is
oxidized to CO2 and hydrogen to steam. When products of
combustion are cooled to RT, latent heat of vaporization of steam
released is added to heat of combustion of fuel.
Net/Low Calorific Value (NCV/LCV)
 Quantity of heat evolved when unit mass of fuel is burnt
completely and the products are permitted to escape.
 In practice when fuel is burnt, the water vapor, and moisture are
not condensed and they escape along-with hot combustion gases.
Thus heat corresponds only to combustion and does not include
latent heat of condensation of steam. The quantity of heat so
measured is called net/low calorific value
GCV = Heat of combustion of fuel + latent heat of condensation of steam

NCV = GCV – latent heat of steam

 Determination of Calorific Value
 CV of Non-volatile liquid fuel can be determined by Bomb
Calorimeter
 Strong cylindrical stainless steel bomb inside which the
combustion of fuel takes place.
 Bomb has a lid, which can be screwed to the body of bomb
to make a perfect gas-tight seal.
 The lid is provided with two stainless steal electrodes and
an oxygen inlet valve
 To one of the electrode a small ring is attached, which
supports a nickel or stainless steel crucible, where the fuel is
placed & burnt.
 Bomb is placed inside a copper calorimeter which is
surrounded by an air-jacket and water-jacket to prevent
heat loss due to radiation.
 Calorimeter provided with an electrically operated stirrer
and Beckmann’s thermometer, which can read accurately
temperature difference up to 1/100th of a degree
Working
 A known mass (0.5 to 1 g) of given fuel is taken in crucible.
 A fine Mg wire (0.75 mm) bent into loop and made to
touch the fuel sample, is then stretched across the
electrodes.
 Bomb lid is tightly screwed and bomb filled with O2 to 25
atm.
 Bomb is lowered into copper calorimeter, containing a
known mass of water.
 Calorimeter vessel is then placed in the insulating jacket.
 Stirrer is operated and initial temperature of the water is
noted
 Electrodes are connected to 6V battery to ignite the
sample. Sample burns and heat is liberated
 Heat liberated rises the temperature of water in the
calorimeter. Uniform stirring of water is continued and
maximum temp. attained is noted.
Heat Capacity
 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 for 1 °C rise.
 Heat capacity - amount of heat that W g of substance (which has
certain SHC) absorbed to bring about 1 °C rise in temperature.
 Heat capacity = W x SHC W = mass of water
Calculation
 Weight of the fuel sample taken = m g
 GCV of the fuel = θ cal/g
 Weight of the water taken in the calorimeter = W g
 Water equivalent of calorimeter, bomb, thermometer etc. = w g
 Initial temperature of water in calorimeter = t1
 Final temperature of water in calorimeter = t2
 Heat liberated by combustion of fuel = mθ
 Heat absorbed by water and calorimeter etc. = (W+w)(t2-t1)
 Heat liberated by fuel = Heat absorbed by water,
calorimeter etc.
mθ = (W+w) (t2-t1) x SHC
g. cal/g = g. °C. cal/g °C
 GCV of fuel (θ) = [(W+w) (t2-t1) x SHC of H2O]/m
 Note: Heat quantity calculated above is GCV because the
products of combustion remain inside the calorimeter and
brought down to ambient temperature.
 NCV can be calculated if the % of hydrogen in the fuel is
known. Let the % of hydrogen be H
 1 g of hydrogen produce 9 g of steam.
 So 1 g of fuel produce = 9H/100 g steam
 Latent heat of condensation of steam = 587 cal/g
 Heat liberated by condensation of 9H/100 g of steam =
9H/100 g x 587 cal/g
NCV = GCV – 0.09 x H x 587 cal
Corrections: For accurate results, the following correction applied.
 Fuse wire correction (t ): Heat liberated, as measured above, includes the
F
heat given out by ignition of the fuse wire used, which actually has to be
excluded from GCV.
 Acid correction (t ): Fuel containing S and N are oxidized to H SO
A 2 4 and
HNO3, under high pressure and temperature of ignition.
 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.
 For each ml of N/10 H SO formed, 3.6 cal. should be subtracted
2 4
 For each ml of N/10 HNO formed, 1.43 cal. should be subtracted
3
 Cooling correction (t ): Time taken to cool the water in calorimeter from
C
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.
GCV of fuel (θ) = (W+w) (t2-t1 + tC) x SHC of H2O – (tA + tF)
m cal/g (or kcal/kg)
 Water Equivalent in Bomb
Calorimeter (w)
 Water Equivalent - It is the amount of water which is
thermally equivalent to the given body.
 In other words, the water equivalent of a body is that mass
of water which has the same heat capacity that of the body
itself.
 Eg. Heat required to bring about 1 °C rise in temperature
of calorimeter is 570 cal. So, this same amount heat (570
cal) can bring about 1 °C rise in 570 g of water (we know
that specific heat capacity of water is 1 cal/g °C). Thus
calorimeter is thermally equivalent to 570 g of water or
simply its water equivalent is 570 g.
 Since water and bomb calorimeter are in thermal
equilibrium during the experiment, the temperature noted
in Beckmann’s thermometer is also the temperature of
bomb calorimeter.
 Numerical
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
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
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
4)On burning 0.75 x 10-3 kg of a solid fuel in a bomb calorimeter, the
temperature of 2.5 kg water is increased from 24 °C to 28 °C. The
water equivalent of calorimeter is 0.485 kg and the latent heat of steam
is 587 kcal/kg. If the fuel contains 2.5% hydrogen, calculate its GCV and
NCV.
Ans: GCV = 15920 kcal/kg ; NCV = 15787.9 kcal/kg
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
 Knocking
 Gasoline - a complex mixture of hydrocarbons (100 different
compounds) ranging from C5 to C9. Most of these are
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.
 Gasoline (petrol) is main source of fuel in motors. In the
internal combustion engine (ICE) of motors the following
occurs
 Compression of gasoline generates fine droplets of gasoline
vapor
 Gasoline vapor is mixed with air and transfer to ICE
 Petrol-air (fuel) mixture is compressed
 Mixture is ignited by spark from spark plug and burnt
 Gases produced by combustion reaction expands
 Normal combustion
spark plug

 To run the engine smoothly combustion of fuel-air

mixture inside ICE should proceed in a controlled fashion.
Normal combustion flame front

 After ignition flame spread rapidly and smoothly piston

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.
Abnormal combustion
 Last unburned 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
 Knocking causes 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.
 Octane number
 Octane number is equal to the percentage by H H H H H H H
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 H C C C C C C C H
sample of gasoline being tested
H H H H H H H
 Iso-octane has the best antiknocking properties
and assigned an octane number of 100 whereas
n-heptane has poor antiknocking property and
n-heptane

assigned an octane number of zero.

 The hydrocarbons present influence the knocking

properties of gasoline which vary according to CH3
the series
CH3 C CH2 CH CH3
Straight chain paraffin > branched chain
paraffin > olefin > cycloparaffin > aromatics.
CH3 CH3
 The fuel which has same knocking tendency with Isooctane
the mixture having 80% iso-octance has octane
number 80.
 Knocking tendency of gasoline

 Hydrocarbons with branched-chains are more resistant to knocking than

the corresponding straight-chain paraffins.
 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
 Knocking tendency decrease with presence double bonds and cyclic
structure.
 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.
 Anti-knocking agents
 Substances added to control knocking are 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 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.

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.
 C H Br
2 4 removes PbO as volatile PbBr2 with the exhaust gases. These
2
lead halides are poisonous to human beings and animals.
 Also leaded gasoline cannot be used in automobiles equipped with
catalytic convertor -Pb present in exhaust gas poisons the catalyst.
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.
 Chemical sensors for environmental
monitoring - gas sensors
Introduction

• Chemical sensors are measurement devices that convert a chemical

or physical property of a specific analyte into a measurable signal,
whose magnitude is normally proportional to the concentration of
the analyte.

• A chemical sensor typically contains two main components: a

receptor and a transducer. The receptor transforms chemical
information about a sample into a form of energy. The transducer
then transforms the energy into some form of analytical signal.

• The chemical sensor is an analyser that responds to a particular

analyte in a selective and reversible way and transforms input
chemical quantity, ranging from the concentration of a specific
sample component to a total composition analysis, into an
analytically electrical signal.
How it works?
Classification of Chemical Sensors
 Gas sensors
▪ Gas sensor is a subclass of chemical sensors.
▪ Gas sensor measures the concentration of gas in its vicinity.
▪ Gas sensor interacts with a gas to measure its concentration.
▪ Each gas has a unique breakdown voltage i.e. the electric
field at which it is ionized. Sensor identifies gases by
measuring these voltages.
▪ The concentration of the gas can be determined by
measuring the current discharge in the device.
▪ Types of gas sensors:
▪ Electrochemical gas sensor
▪ Contact combustion gas sensor
▪ Optical gas sensor
▪ Polymer gas sensor
▪ Semiconductor gas sensor
 IR absorption type CO2 gas sensor

▪ CO2 absorbs infrared light therefore CO2 sensor

consists of a tube containing an infrared source
at one end and an infrared detector at the other
end.
▪ The infrared detector detects the infrared light
which is not absorbed by CO2 between source and
detector.
▪ Infrared radiation which is not being absorbed by
CO2 produces heat so the temperature will
increase.
▪ The infrared detector measures the temperature.
▪ A voltage is produced due to the temperature
increase in the infrared sensor.
▪ We can read amplified voltage into the data
logger.
 Solid electrolyte-type CO2 sensors
• Low-cost, high-sensitivity, high-selectivity and simple-element
structure.
• NASICON is the active element. Formula Na1+xZr2SixP3-xO12 (1.8 < x <
2.4)
• A commercial NASICON with a nominal-composition is Na3Zr2Si2PO12
• Binary carbonate systems such as Na2CO3-BaCO3, Na2CO3-CaCO3,
Li2CO3-BaCO3, and Li2CO3-CaCO3 are also used as active elements (as
auxiliary constituents).
• The NASICON layer was screen-printed with a paste on the alumina
substrate. The Pt electrodes were also screen-printed on the
designated regions before and after the deposition of the NASICON
layer.
• The assembly was sintered at 900°C, 1000°C, and 1100°C for 4
hours in air, respectively. After this, a series of auxiliary phases
(Na2CO3-CaCO3) was screen-printed on the Pt sensing electrode.
• The EMF response to CO2 content as a function of the CO2
concentration is calculated. Greater the CO2 concentration greater the
EMF recorded.
Solid electrolyte-type CO2 sensors
 Hydrogen gas sensor
▪ Mostly palladium is used to detect hydrogen
because palladium selectively absorbs
hydrogen gas and forms the chemical
palladium hydride.
▪ Types of hydrogen gas sensor:
▪ Electrochemical
▪ Thin film sensor
▪ Thick film sensor
▪ Chemochromic hydrogen sensors
▪ Diode based Schottky sensor
▪ Optical fiber hydrogen sensors
▪ Nanoparticle-based hydrogen micro sensors
 NOx gas sensor – Metal oxide type
• WO3 is known as the most promising NOx gas-
sensing material
• Other materials: ZnO, SnO2, In2O3, TiO2, etc.
• These sensing materials are oxygen-deficient
nonstoichiometric compounds
• The conductivity of these n-type semiconductors,
such as WO3 and In2O3, is estimated based on the
electron created by the surplus metal.
• When sensing materials are exposed to oxidizing
gases at temperature ranging from 200ºC to 300ºC,
the concentration of electrons is decreased due to
the reaction between the electron and the gas.
• Consequently, the conductivity decreases and the
resistance increases.
• As NOx is also an oxidizing gas, the concentration of
electrons is decreased due to the reaction between
the electrons in the sensing materials and NOx gas,
as shown in the following equations:
 Carbon monoxide gas sensor

• CO is a colourless, tasteless and odourless gas

produced by incomplete combustion of carbon-
containing materials. It is often referred to as the
"silent killer" because it is virtually undetectable by
humans.
• Types of CO sensors:

▪ Semiconductor sensor
▪ Electrochemical sensor
▪ Biomimetic type
▪ Opto-chemical type (Widely used)
 Opto-chemical type CO sensor
• The detector consists of a pad of a coloured chemical
which changes colour upon reaction with carbon
monoxide. They only provide a qualitative warning of the
gas however. The main advantage of these detectors is
that they are the lowest cost, but the downside is that
they also offer the lowest level of protection.
• One reaction used for carbon monoxide detection is
potassium disulphitopalladate (II) catalytic oxidation.
CO + K2Pd(SO3)2 ⟶ Pd + CO2 + SO2 + K2SO3
• As reaction progresses, atomic palladium release causes
the color to change from yellow to brown to black.
 Biomimetic and electrochemical type
CO sensor
• A biomimetic sensor works in a fashion similar to haemoglobin which
darkens in the presence of CO proportional to the amount of carbon
monoxide in the surrounding environment.
• It uses cyclodextrins, a chromophore, and a number of metal salts.
This can either be seen directly or connected to an infrared source of
photons such as an IR LED and then monitored using a photodiode.
• The electrochemical detector uses the principle of a fuel cell to
generate an electrical current when the gas to be detected undergoes
a chemical reaction.
• The generated current is precisely related to the amount of carbon
monoxide in the immediate environment close to the sensor.
• Essentially, the electrochemical cell consists of a container, two
electrodes, connection wires and an electrolyte, typically sulfuric acid.
Carbon monoxide is oxidized at one electrode to carbon dioxide while
oxygen is consumed at the other electrode.
• Advantages of electrochemical cell over other technologies: highly
accurate and linear output to carbon monoxide concentration,
requires minimal power as it is operated at room temperature, and
has a long lifetime.
 Overview of computational
methodologies: energy minimization and
conformational analysis.
Computational chemistry is the use of computers to solve the
equations of a theory or model for the properties of a chemical
system.

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Three “Pillars” of Scientific Investigation

⮚ Experiment
⮚ Theory (analytical equations)
⮚ Computational Simulation
⮚ (“theoretical experiments”)

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⮚ 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.

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 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".
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 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 40

 Computational Chemistry
WHY
do theoretical calculations?

WHAT
do we calculate?

HOW
are the calculations carried out?

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 Theoretical/Computational
Chemistry

Classical Mechanics Quantum

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

43
 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.
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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.)

47
Doing Chemistry with Computers

48
49
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 50
 Computer Performance

1990 2000 2021

Years
51
• 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.

52
• 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

54
Potential Energy Surfaces and Mechanism

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 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.
minimum
Global

Local minima

56
Local minimum Local minimum

Global minimum

57
Ethane Conformations

58
59
60
61
 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.

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 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

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 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)