thermodynamics and
Molecular simulation in
Green Separation process
Dr.R.Anantharaj
My Home
Green
Solvent
Over view
Introduction
Ionic Liquids
Separation Techniques
Applications
Summary
What is thermodynamics?
Thermo = energy
Dynamics = motion
Thermodynamics = the motion of energy
Thermodynamics =
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 .
Molecular Simulation!?
Molecular Simulation
Experiment
Molecular Simulation
Constituent
Molecular
Mechanics (MM)
chemists
model:
Quantum
model:
Mechanics
(QM)
physicists
Schematic Diagram of MM
E E1 E2
E1
dihedral
angles
angles
bonds
Pairs
of atoms
force
Pairs
of atoms
Coulombic force
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
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
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.
Nobel
in Physics
1933
Prize
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
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
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
e2
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)
e1
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.
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
H1n
H2n
Where Hij = i | H |
=
= 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
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
Starting
molecular
geometry
COMPUTER CALCULATES
Type of
Calculation
Properties to be
calculated
O
H
AO
LCAO
MO
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
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
CH3
N
1-Alkyl-3-methylimidazolium
anion
X-
1-Butyl-3-methylimidaozlium
hexafluorophosphate
[BMIM]
[PF6]
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
40
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)
S (Sulphur)
Undesirable.
Undesirable.
Catalyst deactivation .
Catalyst deactivation .
ozone
Ozone(O3 )
HDS
e.g.:pyrrole,indoline,pyridine,q
uinoline.
e.g.: thiophene,benzothiophene.
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+
Methods of operation
Stage 1
Stage 2
Cross flow
Counter-current flow
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
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
>1
Properties:
Density: A density difference is required between
the two phases.
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
Dispersion energy
: DE = IEMP2-IE HF
of the
Orbital Definitions-Scalar
Properties
Properties name
Electronegativity ()
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
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 of
IL(BMPYRO-BF4)
Partial Charges of IL
+Thiophene
LUMO-HOMO Energies
Predictions
Interaction Energies
Predictions
COSMO-RS model
Powerful tool to find potential ILs from 1018 of cation & anion
combination.
A.Klamt.J.Phy.Chem.99 (1995)2224.
Solute Molecule
Solvent
Accessible Area
(SAS)
Molecule Placed
In a conductor
+_
+
__
+
+
__+
'
+
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
Hydrogen bonding
aeff
2
misfit constant
Non-Polar
Region
Hydrogen Bonding
Donor Capacity
Hydrogen
Atom on
Water
Hydrogen Bonding
Acceptor Capacity
Oxygen
Atom on
Water
Activity Coefficient
ln S ( ) ln
E ( , )
E ( , )
kT
pS ( ) S ( ) exp
ln i / S ni pi ( )[ln S ( ) i ( )] ln iSG
/S
Where
ni
Ai
aeff
Sij,max =S
ij
IL phase
Diesel phase
IL phase
1
C
12
86
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]
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
Acknowledgements
Dr.Tamal Banerjee,IITGuwahati
Dr.G.Pugazhenthi,IITGuwahati
Dr. Aloke Kumar Ghoshal,IITGuwahati
Dr.T.K.Radhakrishnan,NITTiruchy
Dr.N.Anantharaman,NITTiruchy