Application of

thermodynamics and
Molecular simulation in
Green Separation process
Dr.R.Anantharaj

Department of Chemical Engineering

National Institute of Technology Tiruchirappalli
Tiruchirappalli-620015
Tamil Nadu,INDIA

My Home

Green
Solvent

Over view

Introduction

Molecular Simulation Constituent

Ionic Liquids

Separation Techniques

Applications

Summary

What is thermodynamics?
Thermo = energy
Dynamics = motion
Thermodynamics = the motion of energy
Thermodynamics =

the comparison of states to determine

their relative stability.

Definition of a state in terms of

energy
Kinetic energy
Internal energy:
U=(eki+epi)
Potential energy

Why study thermodynamics in Chemical

Engineering?
Processing

Atomic
Crystal / Molecular
Grain structure
Phase distribution
Defects
Structure

Temperature
Pressure / stress
Volume / strain
Chemical composition

Mechanica
l
Properties
Chemical
Electrical
Magnetic
Thermodynamics is the basis for understanding a chemical responseThermal
to changes in
temperature, pressure, and composition. Thus the critical link between processing
and microstructure requires a knowledge of the relevant thermodynamics principles .

Why Molecular simulation!?

Molecular simulation is primarily a tool for

calculating the energy of a given molecular
structure.

To define the chemical engineering problem

well as one involving a structure-energy
relationship.
Identifying correlations between chemical
structures and properties
Storing and searching for data on chemical
entities

To help in the efficient synthesis of ionic liquids

and organic/inorganic compounds.

To design molecules that interact in specific

ways with other molecules

For example: Simultaneous Desulphurization

and Denitrification of Diesel oil.
i.e. Ionic liquid(solvent) + aromatic/sulphur
/nitrogen based compounds (solute) + Diesel oil
(Resource)

Molecular Simulation!?

Difference Between MS & EX

Molecular Simulation

Experiment

Molecular Simulation
Constituent
Molecular
Mechanics (MM)

chemists

model:

Its describes the energy of a molecule in terms

of a simple function which accounts for deformation from
ideal bond distances and angles, as well as and for
nonbonded van der Waals and Coulombic interactions.

Quantum

model:

Mechanics

(QM)

physicists

Its describes the energy of a molecule in terms

of interactions among nuclei and electrons as given by
the Schrdinger equation.

Schematic Diagram of MM

E E1 E2

E1

dihedral
angles

angles

bonds

bond stretcing angle bending dihedral twisting

E2

Pairs
of atoms

Van der Waals

force

Pairs
of atoms

Coulombic force

Limitations of Molecular Mechanics

The bond-breaking and bond-forming cannot be described.
Energy

Transition State

C
MM Description Based
on the Bonding
Pattern of Product

MM Description Based
on the Bonding
Pattern of Reactant

Reactant

B
Product

Correct description
Progress of Reaction

Quantum Mechanics
The Schrdinger equation plays the
(QM)

role of
Newton's laws and conservation of energy in
classical mechanics
It is a wave equation in terms of the wave
function which predicts analytically and
precisely the probability of events or
outcome.
The Schrdinger equation gives the
quantized energies of the system and gives
the form of the wave function so that other
properties may be calculated.

Schrdinger Equation

Computational Chemistry 5510

Spring 2006

Hai Lin

Quantum Mechanics
Microscopic

Macroscopic

Quantum mechanics is the law governing the behavior of nuclei and electrons.
Energy

Internuclear
Distance

H
H

104.5

Correct Description
for Bond-breaking
and Bond-forming

Basis of Quantum Chemistry

Schrdinger equation:

H = E
Dirac (1929): The underlying physical
laws necessary for the mathematical
theory of a large part of physics and
the whole of chemistry are thus
completely known.

Erwin Schrdinger Paul A. M. Dirac

Nobel

in Physics
1933

Prize

"for the discovery of new

productive forms of
atomic theory"

However, it can be solved exactly only for one-electron systems (e.g., a

hydrogen atom) and numerically for any a system having more electrons.

Accurate Quantum Mechanical Methods

Accurate quantum mechanical computation is a powerful tool in study of
chemistry & chemical engineering .

Nobel Prize in
Chemistry 1998
Walter Kohn
for his development of the
density-functional theory

John A. Pople
for his development of
computational methods in
quantum chemistry

Schrdinger Equation
H = Tn + Te + Vnn + Vee + Vne
Nn

1 2
Tn
a
a 2M a
Ne

Te
i

1
i2
2me

e1
Kinetic energy of nuclei
n1

e2

n2

Kinetic energy of electrons

Nn Nn

Z a Zb
Vnn
a b a rab
Ne

Ne

1
Vee
i i j rij
Nn Ne

Za
Vne
a
i rai

Coulombic energy between nuclei

Coulombic energy between electrons
Coulombic energy between nuclei and electrons

Approximations
To solve the Schrdinger equation approximately, assumptions
are made to simplify the equation:
Born-Oppenheimer approximation allows separate
treatment of nuclei and electrons. (ma >> me)
Hartree-Fock independent electron approximation
allows each electron to be considered as being affected by
the sum (field) of all other electrons.
LCAO Approximation represents molecular orbitals as
linear combinations of atomic orbitals (basis functions).

Born-Oppenheimer Approximation
Nuclei are much heavier than electrons (ma / me 1836) and
move much slower.
Effectively, electrons adjust themselves instantaneously to
nuclear configurations.
Electron and nuclear motions are uncoupled, thus the energies
of the two are separable.
Energy

1. For
a
given
nuclear
configuration,
one
calculates
electronic
energy.
2. As
nuclei
move
continuously, the points of
electronic energy joint to
form a potential energy
surface on which nuclei
move.

Internuclea
r Distance

Many-electron Wave function

Hartree product: All electrons are independent, each in its
HP(x1, x2, , xN ) = i(x1) own
k(xN)
j(x2) orbital.

Pauli principle: Two electrons can not have all

e1
quantum number equal.

e2

This requires that the total (many-electron) wave functionei

is anti-symmetric whenever one exchanges two electrons

coordinates.
(x1, x2, , xN ) =(x2, x1, , xN )
eN
Slater determinant satisfies the Pauli principle.
i(x1) j(x1) k(x1)
(x1, x2, , xN ) = (1/N!) i(x2) j(x2) k(x2)

i(xN) j(xN) k(xN)

Many-electron Wave function (2)

Example: A two-electron system.
Hartree product: Both electrons are
HP(x1, xindependent.
2) = i(x1) j(x2)
Slater determinant satisfies the Pauli principle.
i(x1) j(x1)
(x1, x2) = (1/2) (x ) (x )
j 2
i 2

e1

(x1, x2) = (1/2) [i(x1) j(x2) i(x2) j(x1)]

(x2, x1) = (1/2) [i(x2) j(x1) i(x1) j(x2)] = (x1, x2)

The total (many-electron) wavefuntion is anti-symmetric when one
exchanges two electrons coordinates x1 and x2.

e2

Hartree-Fock Approximation
Each electron feels all the other electrons as a whole (field
of charge), .i.e., an electron moves in a mean-field generated
by all the other electrons.
A Fock operator F is introduced for a given electron in the i-th orbital:

Fi i = i i

e1
e2
ei

eN

potential
kinetic energy
Fi = term of the
energy term
due to fixed
given electron
nuclei
averaged
potential
energy term
i is the i-th molecular
dueorbital,
to theand i is the corresponding orbital energy.
other electrons
Note: The total energy is NOT the sum of orbital energies. If you sum them
up, you count the electron-electron interactions twice.

The Fock Operator

N

Fi h i ( J j K j )
j

Core-Hamiltonian
operator
Kinetic energy term
and nuclear attraction
for the given electron

Coulomb
operator
Coulombic energy
term for the given
electron due to
another electron

Exchange
operator
Exchange energy due
to another electron
(A
pure
quantum
mechanical term due to
the Pauli principle, no
classical interpretation)

Self-consistency
Each electron feels all the other electrons as a whole (field of
charge), .i.e., an electron moves in a mean-field generated by
all the other electrons.
The Fock equation for an electron in
the i-th orbital contains information of
all the other electrons (in an averaged
fashion), i.e., the Fock equations for all
electrons are coupled with each other.
All equations must be solved together
(iteratively until self-consistency is obtained).
Self-consistent field (SCF) method.

ek

ej
ei

Refresh Your Mind:

Eigenvalue & Eigenvector
Generally, one can construct a matrix for an operator, e.g., the
Hamiltonian H, using a set of basis functions {i}.

H11 H12 ...

H H ...
21
22

H1n
H2n

Where Hij = i | H |
=

i*(x) H(x) j (x) dx

Hn1 Hn2 ... Hnn

After diagonalization, one obtains eigenvalues (energy levels)
and eigenvectors (wavefunctions).

Linear Combination of Atomic Orbitals

Each one-electron molecular orbital is approximated by a linear combination
of atomic orbitals (basis functions).

= c 1 1 + c 2 2 + c 3 3 +
where is the molecular orbital wavefunction, i represents atomic orbital
wavefunction, and ci is the corresponding expansion coefficients.
The resulting Fock equations are called Roothaan-Hall equations.

This reduces the problem of finding the best functional form for the
molecular orbitals to the much simpler one of optimizing a set of coefficients
y
(cn) in a linear equation.

Variational Principle
Based on the LCAO approximation, each one-electron molecular
orbital is approximated as a linear combination of atomic orbitals.

= c1 1 + c2 2 + c3 3 +
The energy calculated from any approximated wave function is
higher than the true energy.
The better the wave function, the lower the energy.
One can vary the coefficients to minimize the calculated energy.
At the energy minimum, E = 0, and one has the best
approximation of the true energy that is what we want.

H i E i

where :
H is the hamiltonian operator

E is the total energy (kinetic energy potential energy )

i is the wave function

Quantum :

Classical :

Erwin
Schrdinger,
1927

p2 1 2
1 2 1 2
kx
Conservation of energy mv kx Conservation of energy
2m 2
2
2

Newtons law; F ma kx
p
i x
n
2 2 1 2
Schrodinger Equation; H
kx
i C i
2m x 2 2

Quantum Harmonic Oscillator:

Wave function

Quantum Chemical Map

CHEMICAL
ENGINEER
DECIDES

Starting
molecular
geometry

Basis set & Basis

function

COMPUTER CALCULATES

Type of
Calculation

Properties to be
calculated

O
H

AO

LCAO

MO

Basis Function & Basis Set

Types:
-

Minimal (GTOs): Describes only the most basic

aspect of the orbitals.
Extended (STOs): Describes the orbitals in great
detail.

GTOs means Gaussian type orbitals

2 r 2
GTOs 0.75 e

where
is the orbital exp onential term
r is the radius

3 r
STOs 0.5 e

The
The no
no of
of
Gaussian
Gaussian
function
function
summed
summed to
to
describe
describe the
the
inner
inner shell
shell
orbital
orbital

The
The no
no of
of
Gaussian
Gaussian
function
function
Comprise
Comprise the
the
first
first STO
STO of
of
the
the double
double
zeta
zeta

The
The no
no of
of
Gaussian
Gaussian
function
function
summed
summed in
in the
the
second
second STO
STO

HF / 6 31G *

Hartree fock
scheme

Gaussian type
orbital function
(GTOs)

Taking
Taking into
into
account
account
polarization
polarization

Software Packages Required

Exceed - Gate way

MOLDEN -To draw the molecular structure

Gaussian:1.To optimize the molecular structure

2.To find the partial charges of the atom in
the molecules
3.To generate the COSMO file

Ionic Liquids

Ionic liquids(ILs) are organic salts with wide liquid range and low
melting

point

(<1000C):consists

of

organic

cation

and

organic/inorganic anion

ILs also known as designer solvents due to their ability to vary

the ions (i.e cation and anion) and thereby modifying and optimizing
the ILs properties.

ILs are referred to as green solvents due to negligible vapour

pressure which can reduce the technical exposure & solvent loss to
the environment.

ILs having high density than organic, inorganic and water

molecules, in which it may exist as a separate phase when in contact
with aromatic sulphur/nitrogen compounds.

STRUCTURE OF IONIC LIQUID

+
R

CH3
N

1-Alkyl-3-methylimidazolium
anion

X-

1-Butyl-3-methylimidaozlium
hexafluorophosphate

[BMIM]
[PF6]

TYPICAL CATIONS AND ANIONS IN IONIC

LIQUIDS
CATIONS
R1

R2

N
R5

N R3
R4

ANIONS

R5
R4

R6

P+

R3

R1

R4

Pyridinium

R1

R4

R3

HN

N
R2

quaternary ammonium

R3

phosphonium

R2

Imidazolium

R2

R1

R1

R2

pyrrolidinium

NH3+
NH2

Cl-/AlCl3
Cl-,Br-,INO3-,SO3[CF3COO]-, [ CF3SO2 ]
[BF4] [PF6]

[(CF3SO2)2N]-

Guanadinium

The combination of cation and anion leads to 1018

possible ionic liquids !!!

Chemical systems of ILs

Pure ionic liquids
cation + anion = ILs
Binary mixture containing ILs
ILs + Molecular Compounds
Molecular compounds: aliphatic alkanes,
cyclohydrocarbons, aromatic hydrocarbons,etc...
Examples: solubility of O2 and CO2 in 1-Butyl-3Methylimidazolium Tetrafluoroborate
Ternary mixture containing ILs
ILs + Molecular compound + Molecular compound
(or)
ILs + ILs + Molecular compound

April 12, 2016

State of the art Seminar

40

Application of ionic liquid in the future

Typical Sulphur & Nitrogen

compounds
S

Thiophene (TS)

Benzothiophene (BTS)

Dibenzothiophene (DBTS)
H
N

NH
N
H

N
H

Pyrrole (PYR)

Indole (IND)

Indoline (INDO)

Carbazole (CA)

N
N
N

Pyridine (PY)

Quinoline (QU)

Benzoquinoline (BQU)

How S & N compound can affect!?

Disadvantages of nitrogen and sulphur in

Diesel oil
N (Nitrogen)

S (Sulphur)

Undesirable.

Undesirable.

Catalyst deactivation .

Catalyst deactivation .

Leading to coke formation.

Leading to coke formation.

Highly inhibiting effect on

HDS.

Highly inhibiting effect on

active catalyst.

Potentially affect diesel

stability during storage.

Potentially affect diesel

stability during storage.

To produce NOX (x=1,2,3..n).

To produce SOX (x=1,2,3..n).

Potentially damaging human

health.
e.g: Lung damage, empysema,
bronchitis and heart disease.

Potentially damaging human

health.
e.g: Respiratory illness and
trouble breathing

Originator to ozone formation Originator to

:
formation:
NOX VOC
UV Ozone(O3 )
SOX VOC
UV

ozone

Ozone(O3 )

Precursors to acid rain:

Precursors to acid rain:
2 NO2 g H 2O l HNO2 aq HNO3 aq
SO3 g H 2O l H 2 SO4 aq

HDN & HDS Limitations

HDN

HDS

Consume high energy

Consume high energy

Severe operating conditions

T=300-500C & P =7-10 MPa

Severe operating conditions

T=300-400C & P =>4 MPa

Lower space velocity

Lower space velocity

Additives are needed to

improve fuel properties and
performance

Additives are needed to

improve fuel properties and
performance

Less efficiency for refractory

nitrogen.

Less efficiency for refractory

sulphur.

e.g.:pyrrole,indoline,pyridine,q
uinoline.

e.g.: thiophene,benzothiophene.

Simulated Diesel composition

n-Paraffins
(CnH2n+2)
Isoparaffins
(CnH2n+2)
Aromatics
(CnH2n-6)
Naphthenes
(CnH2n)
Olefins
(CnH2n)

Until C5

C6

C8

C9

C10

wt %

wt %

6.7

1.32

0.41

2.5

wt
%
0.06

10.9

5.62

1.81

17

1.3

0.3

0.32

36.7

0.3

0.3

0.6

0.4

0.4

1.62

1
1.1

1.2

6.7

1.62

0.51

0.1

0.2

wt % wt % wt %

C11+

Separation processes general

Mechanical separations e.g. filtration of a

solid from a suspension in a liquid,
centrifugation, screening etc
Mass transfer operations e.g. distillation,
extraction etc

Mass transfer operations

nature of interface between

Gas-liquid contact e.g. absorption,

phases

evaporation, distillation etc

Liquid-liquid contact e.g. extraction
Liquid-solid contact e.g. crystallisation,
adsorption
Gas-solid contact e.g. adsorption, drying etc

Mass transfer operations

controlling transport

Mass transfer controlling e.g.distillation,

phenomenon

absorption, extraction, adsorption etc

Mass transfer and heat transfer controlling
e.g. drying, crystallisation
Heat transfer controlling e.g. evaporation

Methods of operation

Non steady state concentration changes

with time e.g. batch processes
Steady state
Stage
Differential contact

When both phases are

Co-current contact
flowing:

Stage 1

Stage 2

Cross flow

Counter-current flow

Choice of separation process

Factors to be considered:
Feasibility
Product value
Cost
Product quality
selectivity

Liquid-liquid extraction
principles
Feed phase contains a component, i, which is
to be removed. Addition of a second phase
(solvent phase) which is immiscible with feed
phase but component i is soluble in both
phases. Some of component i (solute) is
transferred from the feed phase to the solvent
phase. After extraction the feed and solvent
phases are called the raffinate (R) and
extract (E) phases respectively.

Extractants
The efficiency of a liquid liquid extraction can
be enhanced by adding one or more
extractants to the solvent phase. The
extractant interacts with component i
increasing the capacity of the solvent for i.To
recover the solute from the extract phase the
extractant-solute complex has to be
degraded.

Distribution coefficient
K = mass fraction solute in E phase
mass fraction solute in R phase
K = y/x
Large values are desirable since less solvent is
required for a given degree of extraction

Immiscible liquids
e.g. water chloroform
Consider a feed of water/acetone(solute).
K = mass fraction acetone in chloroform phase
mass fraction acetone in water phase
K = kg acetone/kg chloroform = y/x
kg acetone/kg water

K = 1.72
i.e. acetone is preferentially soluble in the chloroform phase

Partially miscible liquids

E.g. water MIBK
Consider a solute acetone.
Need to use a triangular phase diagram to show
equilibrium compositions of MIBK-acetonewater mixtures.
Characteristics are single phase and two phase
regions, tie lines connecting equilibrium phase
compositions in two phase region.

Choice of solvent
Factors to be considered:
Selectivity
Distribution coefficient
Insolubility of solvent
Recoverability of solute from solvent
Density difference between liquid phases
Interfacial tension
Chemical reactivity
Cost
Viscosity, vapour pressure
Flammability, toxicity

Selectivity

= (mass fraction B in E)/(mass fraction A in E)

(mass fraction B in R)/(mass fraction A in R)

>1

Recoverability of solvent and

solute

No azeotrope formed between solvent and

solute
Mixtures should have a high relative volatility
Solvent should have a small latent heat of
vapourisation

Properties:
Density: A density difference is required between
the two phases.

Interfacial tension : The larger the interfacial

tension between the two phases the more
readily coalescence of emulsions will occur to
give two distinct liquid phases but the more
difficult will be the dispersion of one liquid in the
other to give efficient solute extraction.
Chemical reactivity: Solvent should be stable and
inert.

Physical properties
For material handling:
Low viscosity
Low vapour pressure
Non-flammable (high flash point)
Non-toxic

Separation Techniques

Liquid-Liquid Extraction
1.Process is applicable at ambient conditions
2.Special equipment requirements
3.Energy consumption is negligible
4.No hydrogen consumption
5.Handling is easy
6.The process does not change the chemical
structure of the components.

Application of Molecular
To predict the LUMO and HOMO energy
Simulation

molecules and their thermodynamic properties

To find the scalar properties :

Chemical potential ()
Electronegativity ()
Global hardness ()
Global softness (S)
Electrophilicity index ()

Electrostatic interaction: IE=EILS (EC+EA)

Dispersion energy

: DE = IEMP2-IE HF

of the

Orbital Definitions-Scalar
Properties
Properties name

Electronegativity ()

Global Softness (S)

1 2 E

2 N 2
s

index( )

1
2 E
N 2

V (r )

V (r )

IP EA

HOMO LUMO

IP EA

HOMO LUMO

IP EA

HOMO LUMO

v(r )

1
2

1

2 N

Orbital Definition

v(r )

E
= -
N

Electrophilicity

expression

Chemical potential ( )

Global Hardness ( )

Operational

Empirical expression

v(r )

IP EA

HOMO LUMO

v(r )

IP EA

HOMO LUMO

MOLDEN Software

GAUSSIAN03 Software
File Edit
% Section
Route
section
Title section
Charge and
multiplicity

additional
No need
#HF/6-31G* opt freq
Geometry optimization
01

Molecular specification
For example: Thiophene values from MOLDEN out file
s
c 1 cs2
c 2 cc3
1 ccs3
c 3 cc4
2 ccc4
1 dih4
c 4 cc5
3 ccc5
2 dih5
h 5 hc6
4 hcc6
1 dih6
h 4 hc7
5 hcc7
3 dih7
h 3 hc8
4 hcc8
2 dih8
h 2 hc9
3 hcc9
1 dih9
cs2
cc3
ccs3
cc4
ccc4
dih4
cc5
ccc5
dih5
hc6
hcc6
dih6
Etc..

1.710000
1.450000
109.471
1.450000
109.471
0.000
1.450000
109.471
0.000
1.089000
109.471
180.000

0
Run
Ok

Partial Charges Predictions

File Edit
% section

additional
% mem=100MW

Route section

#P B3LYP/6-311+G* opt=gdiis
SCF(CONVER=7,MAXCYCLE=128) pop(npa,chelpg)
geom=distance
Partial charges
01

Title section
Charge and multiplicity
Molecular specification
For example; Thiophene optimized values from MOLDEN out file(after 2ND step)
s
c 1 cs2
c 2 cc3
1 ccs3
c 3 cc4
2 ccc4
1 dih4
c 4 cc5
3 ccc5
2 dih5
h 5 hc6
4 hcc6
1 dih6
h 4 hc7
5 hcc7
3 dih7
h 3 hc8
4 hcc8
2 dih8
h 2 hc9
3 hcc9
1 dih9
cs2
1.710000
cc3
1.450000
ccs3
109.471
cc4
1.450000
ccc4
109.471
dih4
0.000
cc5
1.450000
ccc5
109.471
dih5
0.000
hc6
1.089000
hcc6
109.471
dih6
180.000
hc7
1.089000
hcc7
109.471
dih7
180.000

R
u
n
O
k

Partial Charges For

Thiophene

Partial Charges For Anion

(BF4)

Partial Charges of Cation

(BMPYRO)

Partial Charges of
IL(BMPYRO-BF4)

Partial Charges of IL
+Thiophene

LUMO-HOMO Energies
Predictions

Interaction Energies
Predictions

COSMO-RS model

COSMO-RS consist of:

- Quantum theory
- Surface interactions
- Statistical thermodynamics
- Dielectric continuum models

Gives results in terms of activity coefficient at infinite dilution.

Excellent model for solubility's study, especially in non-ideal

liquid mixture.

Powerful tool to find potential ILs from 1018 of cation & anion
combination.

A.Klamt.J.Phy.Chem.99 (1995)2224.

COSMO : COnductor Like

Screening MOdel
Element Specific
Molecular Cavities
Created

Solute Molecule

Solvent
Accessible Area
(SAS)
Molecule Placed
In a conductor

Surface Charge Distribution : SIGMA PROFILE

Total 0 solute Aq*

SAS divided into small segments

each having a screening charge
density

Molecule Pulls Charges

From the conductor
To the interface

Possible Contact Interactions

(PCI)
<<
' 0

+_
+
__
+
+
__+
'
+

Hydrogen Bonding
Interaction
Misfit Energy
Interaction
Ideal
Electrostati
c
Contact

The energy difference between the real situation of such contact and
the ideally screened situation has to be defined as a local electrostatic
interaction energy, which results from the contact of the molecules.

Interaction Energy
Misfit interaction
Calculations

Emisfit ( , ) aeff emisfit ( , )

Hydrogen bonding

aeff

2

Ehb ( , ) aeff ehb ( , )

misfit constant

Effective Contact Surface Area

of a segment

aeff chb min{0, min(0, don hb ) max(0, acc hb )}

Hydrogen Bonding coefficient

threshold for Hydrogen

Bonding

Model Sigma profiles

Cut-off surface charge
Density = +0.0084

Cut-off surface charge

Density = - 0.0084

Non-Polar
Region
Hydrogen Bonding
Donor Capacity

Hydrogen
Atom on
Water

Hydrogen Bonding
Acceptor Capacity
Oxygen
Atom on
Water

Activity Coefficient

Activity Coefficient of the Segment

ln S ( ) ln

E ( , )

E ( , )

kT

pS ( ) S ( ) exp

( ) 2 chb min{0, min(0, don hb ) max(0, acc hb )}

2

Activity Coefficient of Component in Mixture

ln i / S ni pi ( )[ln S ( ) i ( )] ln iSG
/S
Where

ni

Ai
aeff

i.e The contribution of molecule i to the surface segments

Once Activity Coefficients

i/S
Equilibria (LLE)

is known we can predict Liquid Liquid

Generation of COSMO File

Step:1: Geometry Optimization in Gas Phase
Level of Theory:

PBV86 (Density Functional Theory)

Basis Set: TZVP (Triple Zeta Valence Polarized ) with

DGA1 (Density Gradient Approximation)
Step 2: COSMO File Generation
Level of Theory:

PBV86 (Density Functional Theory)

Basis Set: TZVP (Triple Zeta Valence Polarized ) / DGA1

SCRF Calculation is done with SCRF=COSMORS keyword in
GAUSSIAN03

Modified Rashford Rice algorithm

for COSMO-RS model.

Selectivity & Capacity

The selectivity is defined as the ratio of the composition of

(nitrogen/sulphur compounds) species in IL rich phase (extract)
and its composition in model diesel rich (raffinate) phase.
[Mukhopadhyay,1979]

Sij,max =S

ij

IL phase

Diesel phase

IL phase

The inverse of the activity coefficient of the species

(nitrogen/sulphur compounds)at infinite dilution in solvent rich
(extract) phase. [Mukhopadhyay & Rao,1987]

1
C

12

86

Separation of aromatic nitrogen

& sulphur compounds

Ternary Diagram
Benzothiophene
0
10

100
Experimental
COSMO-RS Predictions

90

20

80

30

70

40

60

50

50

60

40

70

30

80

20

90

10

100

Hexane

0
10

20

30

40

50

60

70

80

90

100

[EMIM][EtSO4]

RMSD for Quaternary systems

S.No

Name of the systems

NRTL model

UNIQUAC
model

COSMO-RS
model

[EMIM][OAc]+Thiophene
+Pyridine+Pentane

0.73

1.69

4.62

[EMIM][EtSO4]+Thiophene
+Pyridine+Pentane

0.12

0.19

5.3

[EMIM][MeSO3]+Thiophene
+Pyridine+Pentane

1.49

1.60

6.7

[EMIM][OAc]+Thiophene
+Pyridine+Cyclohexane

1.03

1.69

7.85

[EMIM][EtSO4]+Thiophene
+Pyridine+Cyclohexane

1.25

1.90

5.93

[EMIM][MeSO3]+Thiophene
+Pyridine+Cyclohexane

1.09

2.47

5.35

[EMIM][OAc]+Thiophene
+Pyridine+Toluene

0.928

1.54

8.41

[EMIM][EtSO4]+Thiophene
+Pyridine+Toluene

1.23

1.54

8.74

[EMIM][MeSO3]+Thiophene
+Pyridine+Toluene

09.37

2.34

6.53

Summary

Global scalar properties have great significance in

solubility of solute in solvent
Interaction energies and partial charges can give clear
information about the simultaneous separation using a
potential solvent
Molecular rearrangement in the mixture strongly
depends on hydrogen bond formation between the
molecules
Potential solvent selected for LLE experiment
LLE data were predicted via COSMO-RS with a RMSD
of ~4%

Acknowledgements

Dr.Tamal Banerjee,IITGuwahati
Dr.G.Pugazhenthi,IITGuwahati
Dr. Aloke Kumar Ghoshal,IITGuwahati
Dr.T.K.Radhakrishnan,NITTiruchy
Dr.N.Anantharaman,NITTiruchy

Thanks, and Ill see you next time.