application of thermodynamics and molecular simulation in chemical engineering problems

8/18/2019 Application of Thermodynamics and Molecular Simulation in Chemical Engineering Problems

1/103

Application ofthermodynamics and

Molecular simulation in Green Separation processDr.R.Anantharaj

Department of Chemical Engineering

National Institute of Technology Tiruchirappalli

Tiruchirappalli-620015

Tamil NaduINDI!


2/103

My Home

GreenSolvent


3/103

Over view

Introduction "olecular #imulation Constituent

Ionic $i%uids

#eparation Techni%ues

!pplications

#ummary


4/103

What is thermodynamics?

Thermo = energy

Dynamics = motion

Thermodynamics = the motion of energy

Thermodynamics = the comparison of states to determine

their relative stability.


5/103

Denition of a “state” in terms ofenery

!"Σ#e$ i%epi&

'inetic enery

(otential enery

)nternal enery*


6/103

Why st+dy thermodynamics in ,hemical

-nineerin?

Thermodynamics is the basis for understanding a chemical response to changes in

temperature, pressure, and composition. Thus the critical link between processing

and microstructure requires a knowledge of the relevant thermodynamics principles.

(roperties

(rocessin

Str+ct+re

Atomic,rystal . Molec+lar

Grain str+ct+re(hase distri/+tion

DefectsMechanica

l,hemical-lectrical

Manetic0hermal

0emperat+re(ress+re . stress 1ol+me . strain

,hemical composition


7/103

Why Molec+lar sim+lation2? "olecular simulation is primarily a tool for

calculating the energy of a gi&en molecular

structure'

To define the chemical engineering pro(lem

)ell as one in&ol&ing a structure-energyrelationship'

Identifying correlations (et)een chemical

structures and properties #toring and searching for data on chemical

entities


8/103


9/103

Molec+lar Sim+lation2?


10/103

Di3erence 4etween MS 5 -6

"olecular #imulation E,perimentE,periment"olecular #imulation E,periment


11/103

Molec+lar Sim+lation,onstit+ent Molecular Mechanics (MM) a chemist3s

model It3s descri(es the energy of a molecule in terms

of a simple function which accounts for deformation from

“ideal” (ond distances and angles as )ell as and for

non(onded &an der 4aals and Coulom(ic interactions'

Quantum Mechanics (QM) a physicist3s

model It3s descri(es the energy of a molecule in terms

of interactions among nuclei and electrons as given by

the Schrödinger equation'


12/103

Schematic Diaram of MM

∑∑∑ ++=anglesdihedral

anglesbonds

twisting dihedral bending angle stretcing bond E 1

∑∑ +=atomsof

Pairsatomsof

Pairs

forceCoulombic forceWaalsder Van E 2

21 E E E += 21 E E E += 21 E E E +=

∑∑∑ ++=ang lesdihedral

anglesbonds


21 E E E +=

∑∑ +=atomsof

Pairsatomsof

Pairs


∑∑∑ ++=anglesdihedral

anglesbonds


21 E E E +=

∑∑ +=atomsof

Pairsatomsof

Pairs


∑∑∑ ++=ang lesdihedral

anglesbonds


21 E E E +=


13/103

Limitations of Molecular Mechanics

MM Description Basedon the Bonding

Pattern of Product

MM Description Basedon the Bonding

Pattern of Reactant

Correct description

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

A B C A B C

Reactant Product

A B C

Transition State

Progress of Reaction

nerg!


14/103

Quantum Mechanics

(QM)

The #chrdinger e%uation plays the role ofNe)tons la)s and conser&ation of energy inclassical mechanics

It is a )a&e e%uation in terms of the )a&e

function )hich predicts analytically andprecisely the pro(a(ility of e&ents oroutcome'

The #chrdinger e%uation gi&es the%uanti.ed energies of the system and gi&esthe form of the )a&e function so that otherproperties may (e calculated'


15/103

Schr7diner -8+ation

Computational Chemistry 5510

Spring 2006 Hai Lin


16/103

"uantum Mechanics

MacroscopicMicroscopic

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

Energy

Internuclear

DistanceO

H

H

!".#$ Correct Descri%tion

for Bond&brea'ing

and Bond&forming


17/103

Basis of "uantum Chemistr!

Schr#dinger e$uation%

HHψ ψ "" E Eψ ψ

Erwin (chr)dinger *aul A. +. Dirac

Nobel Prize in Physics1933

"or the !iscovery o ne#ro!uctive orms o

atomic theory"

Dirac &'()(*% +The underl!ing ph!sical

la,s necessar! for the mathematical

theor! of a large part of ph!sics and

the ,hole of chemistr! are thus

completel! kno,n.

o,e/er0 it can be sol/ed e1actl! onl! for one-electron s!stems &e.g.0 a

h!drogen atom* and numericall! for an! a s!stem ha/ing more electrons.


18/103

2ccurate "uantum Mechanical Methods

2ccurate $uantum mechanical computation is a po,erful tool in stud! ofchemistr! 3 chemical engineering .

,obel *ri-e inChemistry /

4alter 5ohn 6ohn 2. Pople

+for his de/elopment of the

densit!-functional theor!

+for his de/elopment of

computational methods in

$uantum chemistr!


19/103

Schr#dinger $uation

2

n

n

2

1a

N

a a M ∇−= ∑T

∑∇−=

e N

i

i

m

2

e

e

2

1T

Kinetic energy of nuclei

Kinetic energy of electrons

Coulombic energy between nuclei

Coulombic energy between electrons

Coulombic energy between nuclei and electrons

H Tn ! Te ! Vnn ! Vee ! Vne

n9 n:

e9 e:

∑∑>

=n n

nn

N

a

N

ab ab

ba

r

Z Z V

∑∑>=e e 1

ee

N

i

N

ji ijr V

∑∑=n e

ne

N

a

N

i ai

a

r

Z V


20/103

2ppro1imations

To solve the "chr#dinger equation appro$imately, assumptionsare made to simplify the equation%

&Born-Oppenheimer approximation allows separate

treatment of nuclei and electrons. 'ma (( me)

&Hartree-o!" in#epen#ent ele!tron approximation

allows each electron to be considered as being affected by

the sum 'field) of all other electrons.

&LC$O $pproximation represents molecular orbitals as

linear combinations of atomic orbitals 'basis functions).


21/103

Born-7ppenheimer 2ppro1imation

& *uclei are much heavier than electrons 'ma + me ≥ 1-) andmove much slower.

&/ffectively, electrons ad0ust themselves instantaneously to

nuclear configurations.

&/lectron and nuclear motions are uncoupled, thus the energies

of the two are separable.

Energy

Internuclea

r Distance

9; oint toform a potential enery

s+rface on which n+cleimove;


22/103

Man!-electron 4a/e function

%

e9

e:

e N

ei

Pauli #rinci#le& 0wo electrons can not have all8+ant+m n+m/er e8+al;

This requires that the total 'manyelectron) wave function

is antisymmetric whenever one e$changes two electrons

coordinates.

φ i' x 1) φ j' x 1) 3 φ k ' x 1)

φ i' x 2) φ j' x 2) 3 φ k ' x 2)

φ i' x N ) φ j' x N ) 3 φ k ' x N )

Ψ' x 1, x 2, 3, x N ) '1+ N 4)5

Hartree #ro!uct& All electrons are independent= each in itsown or/ital;Ψ67' x 1, x 2, 3, x N ) φ i' x 1) φ j' x 2)3

φ k ' x N )

Ψ' x 1, x 2, 3, x N ) − Ψ' x 2, x 1, 3, x N )

Slater !eterminant satises the (a+li principle;


23/103

Man!-electron 4a/e function &)*

e9e:

The total 'manyelectron) wavefuntion is antisymmetric when one

e$changes two electrons coordinates x 1 and x 2.

φ i' x 1) φ j' x 1)

φ i' x 2) φ j' x 2)Ψ' x 1, x 2) '1+2)5

Hartree #ro!uct& 4oth electrons areindependent;Ψ67' x 1, x 2) φ i' x 1) φ j' x 2)

Ψ' x 2, x 1) '1+2)5 8φ i' x 2) φ j' x 1) − φ i' x 1) φ j' x 2)9 − Ψ' x 1, x 2)

Slater !eterminant satises the (a+li principle;

-@ample* A twoelectron system;

Ψ' x 1, x 2) '1+2)5 8φ i' x 1) φ j' x 2) − φ i' x 2) φ j' x 1)9


24/103

artree-8ock 2ppro1imation

%

&: ;ock operator is introduced for a given electron in the ith orbital%

i

φ i

ε i

φ i

$inetic eneryterm of the

iven electron

potentialenery termd+e to @ed

n+cleiaveraed

potentialenery termd+e to the

other electrons

i %

φ i is the ith molecular orbital, and ε i is the corresponding orbital energy.

*ote% The total energy is *feels? all the other electrons as a whole 'field

of charge), .i.e., an electron moves in a meanfield generated by all the other electrons.


25/103

The 8ock 7perator

Kinetic energy term

and nuclear attraction

for the given electron

∑ −+= N

j

j jii )' % &h

,oreHamiltonian

operator

,o+lom/

operator

-@chane

operator

Coulombic energy

term for the given

electron due to

another electron

/$change energy due

to another electron

': pure quantum

mechanical term due tothe 7auli principle, no

classical interpretation)


26/103

Self-consistenc!

&The ;ock equation for an electron in

the ith orbital contains information ofall the other electrons 'in an averaged

fashion), i.e., the ;ock equations for all

electrons are coupled with each other.

e jek

ei

&/ach electron >feels? all the other electrons as a whole 'field of

charge), .i.e., an electron moves in a meanfield generated byall the other electrons.

&:ll equations must be solved together

'iteratively until selfconsistency is obtained).

@ "elfconsistent field '"C;) method.


27/103

Refresh 9our Mind%

igen/alue 3 igen/ectorAenerally, one can construct a matri$ for an operator, e.g., the6amiltonian H' using a set of basis functions Bφ i.

φ 1 φ 2 ... φ nφ 1φ 2... φ n

H 99 H 9: ;;; H 9n

H :9 H :: ;;; H :n

H n9 H n: ;;; H nn:fter diagonaliDation, one obtains eigenvalues 'energy levels)

and eigenvectors 'wavefunctions).

Where H ij " 〈φ i B H B φ j〉

" ∫ φ i*# x & H# x & φ j # x & d x


28/103

Linear Combination of 2tomic 7rbitals

&/ach oneelectron molecular orbital is appro$imated by a linear combination

of atomic orbitals 'basis functions).

φ c1 χ1 ! c2 χ2 ! c- χ- ! 3

where φ is the molecular orbital wavefunction, χi represents atomic orbitalwavefunction, and ci is the corresponding e$pansion coefficients.

&The resulting ;ock equations are called Eoothaan6all equations.

&This reduces the problem of finding the best functional form for the

molecular orbitals to the much simpler one of optimiDing a set of coefficients

'cn) in a linear equation.

x

y


29/103

:ariational Principle

Fased on the GC:< appro$imation, each oneelectron molecular

orbital is appro$imated as a linear combination of atomic orbitals.

φ c1 χ1 ! c2 χ2 ! c- χ- ! 3

&The energy calculated from any appro$imated wave function ishigher than the true energy.

&The better the wave function, the lower the energy.

&


30/103

functionwaetheis

energy !otential energykineticenergytotal theis E

o!erator nhamiltoniatheis "

where

i −

+−

−

ψ

)'

%

2

2

22

22

2

1

26/quationIdinger"chr

2

1

2

%

kx xm

o

xi

!

kxm

!energyof onConserati

#uantum

+∂∂−

=∂

∂=

+=

functionwaetheis



where

i −

+−

−

ψ

)'

%ii E " ψ ψ =

functionwaetheis



where

i −

+−

−

ψ

)'

%

µ

µ

µ φ ψ ∑=

=n

ii C 1

ii E " ψ ψ =

functionwaetheis



where

i −

+−

−

ψ

)'

%

2

2

22

22

2

1


2

1

2

%

kx xm

o

xi

!

kxm


#uantum

+∂∂−

=∂

∂=

+=

µ

µ

µ φ ψ ∑=

=n

ii C 1

2

2

22

22

2

1


2

1

2

%

kx xm

o

xi

!

kxm


#uantum

+∂∂−

=∂

∂=

+=

functionwaetheis



where

i −

+−

−

ψ

)'

%

µ

µ

µ φ ψ ∑=

=n

ii C 1

2

2

22

22

2

1


2

1

2

%

kx xm

o

xi

!

kxm


#uantum

+∂∂−

=∂

∂=

+=

kxma $ law Newtons

kxmenergyof onConserati

Classical

−==

+=

I

2

1

2

1

%

22

ii E " ψ ψ =

ErwinSchrödinger,

1927

2

2

22

22

2

1


2

1

2

%

kx xm

o

xi

!

kxm


#uantum

+∂∂−

=∂

∂=

+=

kxma $ law Newtons


Classical

−==

+=

I

2

1

2

1

%

22

µ

µ

µ φ ψ ∑=

=n

ii C 1

2

2

22

22

2

1


2

1

2

%

kx xm

o

xi

!

kxm


#uantum

+∂∂−

=∂

∂=

+=

kxma $ law Newtons


Classical

−==

+=

I

2

1

2

1

%

22

functionwaetheis



where

i −

+−

−

ψ

)'

%

µ

µ

µ φ ψ ∑=

=n

ii C 1

2

2

22

22

2

1


2

1

2

%

kx xm

o

xi

!

kxm


#uantum

+∂∂−

=∂

∂=

+=

kxma $ law Newtons


Classical

−==

+=

I

2

1

2

1

%

22


31/103

C+ant+m Harmonic Oscillator*Wave f+nction


32/103


33/103

C+ant+m ,hemical Map

7

8 8 8 8

7

M% &% 'C&% →

CHEMICAL

ENGINEERDECIDES

COMPUTER CALCULATES

#tartingmoleculargeometry

9asis set : 9asisfunction

Type of

Calculation

;roperties to (ecalculated

7

8 8 8 8

7

M% &% 'C&% →

7

8 8 8 8

7

M% &% 'C&% → M% &% 'C&% →

7

8 8 8 8

7

M% &% 'C&% →


34/103

4asis


35/103

L+ -1 "$ (−

The no of


36/103

Software (ac$aes e8+ired

E,ceed -


37/103

)onic Ei8+ids Ionic li%uids/I$s are organic salts )ith )ide li%uid range and lo)

melting point /?1000Cconsists of organic cation and

organic*inorganic anion

I$s also =no)n as @deigner o!"entA due to their a(ility to &ary

the ions /i'e cation and anion and there(y modifying and optimi.ing

the I$s properties'

I$s are referred to as @green o!"entA due to negligi(le &apour

pressure )hich can reduce the technical e,posure : sol&ent loss to

the en&ironment'

I$s ha&ing high denit# than organic inorganic and )ater

molecules in )hich it may e,ist as a separate phase )hen in contact

)ith aromatic sulphur*nitrogen compounds'


38/103

S'*'+ ,- .,N.* /.Q.0

NN

CH3)

*-

+

12lyl3methylimi!azoliumanion 14utyl3methylimi!aozlium

he5a6uoro#hos#hate

F4M)MF(


39/103

'7P.*2/ *2'.,NS 2N0 2N.,NS .N .,N.*/.Q.0S

*

*

E -

E 1

E K

E M

E 2

*

E .

E -

E M

E 1

E 2

E K

*

E 1

E 2

E -

E M

C$T,O-S $-,O-S

8F;M9

87;.9

Cl+:lCl-

Cl,Fr ,=

*


40/103

Chemical systems of IL’s

April 9:= :I9 State of the art Seminar JI

;ure ionic li%uids

cation anion B I$3s 9inary mi,ture containing I$3s

I$3s "olecular Compounds

Molecular compouns: aliphatic al=anes

cyclohydrocar(ons aromatic hydrocar(onsetc'''!"amples: solu(ility of 72 and C72 in 1-9utyl->-

"ethylimida.olium Tetrafluoro(orate

Ternary mi,ture containing I$3s

I$3s "olecular compound "olecular compound

/or

I$3s I$3s "olecular compound


41/103

Application of ionic li8+id in the f+t+re


42/103

0ypical S+lph+r 5 Kitroencompo+nds#

#

#

NH

NH

NH

HN

N

N

N

Thiophene TS3 Ben4othiophene BTS3 i(en4othiophene BTS3

yrrole 7) 3 ,n#ole ,3 ,n#oline ,O3Car(a4ole C$3

yri#ine 73 8uinoline 893 Ben4ouinoline B893

# #

#

NH

NH

NH

HN

N

N

N

Thiophene TS3 Ben4othiophene BTS3 i(en4othiophene BTS3



i(en4othiophene BTS3

# #

#

NH

NH

NH

HN

N

N

N

Thiophene TS3 Ben4othiophene BTS3




43/103

Ho$ S % N co&'ound can a((ect)*

Di d t f it d l h i


44/103

Disadvantages of nitrogen and sulphur in

Diesel oil

itrogen3 S Sulphur3

Nndesirable. Nndesirable.

Catalyst deactivation . Catalyst deactivation .

Geading to coke formation. Geading to coke formation.

6ighly inhibiting effect on6O".

6ighly inhibiting effect onactive catalyst.

7otentially affect dieselstability during storage.

7otentially affect dieselstability during storage.


45/103

To produce *


46/103

HDN & HDS Limitations

H HS

Consume high energy Consume high energy

"evere operating conditionsT-HHHHQC R 7 J1H S7a

"evere operating conditionsT-HHMHHQC R 7 (M S7a

Gower space velocity Gower space velocity

:dditives are needed toimprove fuel properties and

performance

:dditives are needed toimprove fuel properties and

performance

Gess efficiency for refractorynitrogen. Gess efficiency for refractorysulphur.

e.g.%pyrrole,indoline,pyridine,quinoline.

e.g.% thiophene,benDothiophene.

Si l t d Di l iti


47/103

Simulated Diesel composition

#nti! C$

wt %

C&

wt %

C'

wt %

C9

wt %

C1(

wt %

C11)

wt

%

n*+arans

-Cn.2n)2/

&07 102 (01 20$ * * (0(&

4soparans-Cn.2n)2/

1(09 $0&2 10'1 17 10 * (0

5romatics

-Cn.2n*&/

* (02 &07

1

(0 (0 (0& (0

6aphthenes-Cn.2n/

(0 10&2 101 102 * * *

O!ens

-Cn.2n/

&07 10&2 (0$1 (01 (02 * *


48/103

Separation processes eneral "echanical separations e'g' filtration of a

solid from a suspension in a li%uid

centrifugation screening etc

"ass transfer operations e'g' distillatione,traction etc


49/103

Mass transfer operations Lnat+re of interface /etween

phases


50/103

Mass transfer operations Lcontrollin transport

phenomenon "ass transfer controlling e'g'distillationa(sorption e,traction adsorption etc

"ass transfer and heat transfer controlling

e'g' drying crystallisation 8eat transfer controlling e'g' e&aporation


51/103

Methods of operation

Non steady state concentration changes

)ith time e'g' (atch processes

#teady state

#tage

Differential contact


52/103

When /oth phases areowin* Co-current contact

Cross flo)

Counter-current flo)

Stae 9 Stae :

9 :

9 :


53/103

,hoice of separation process

+actors to (e considered

+easi(ility

;roduct &alue

Cost

;roduct %uality

selecti&ity


54/103

Ei8+idli8+id e@tractionprinciples+eed phase contains a component i )hich is

to (e remo&ed' !ddition of a second phase/sol&ent phase )hich is immisci(le )ith feed

phase (ut component i is solu(le in (othphases' #ome of component i /solute istransferred from the feed phase to the sol&entphase' !fter e,traction the feed and sol&ent

phases are called the raffinate / ande,tract /E phases respecti&ely'


55/103

-@tractants

The efficiency of a li%uid li%uid e,traction can

(e enhanced (y adding one or more

e,tractants to the sol&ent phase' The

e,tractant interacts )ith component iincreasing the capacity of the sol&ent for i'To

reco&er the solute from the e,tract phase the

e,tractant-solute comple, has to (e

degraded'

/ 3


56/103

Distri/+tion coe3icient

B mass fraction solute in E phase

mass fraction solute in phase

B y*,

$arge &alues are desira(le since less sol&ent is

re%uired for a gi&en degree of e,traction

) i i/l li id


57/103

)mmisci/le li8+ids

e'g' )ater chloroform

Consider a feed of )ater*acetone/solute'

B mass fraction acetone in chloroform phase mass fraction acetone in )ater phase

B =g acetone*=g chloroform B y*,

=g acetone*=g )ater

B 1'2i'e' acetone is preferentially solu(le in the chloroform phase


58/103

( i ll i i/l li id


59/103

(artially misci/le li8+idsE'g' )ater "I9

Consider a solute acetone'

Need to use a triangular phase diagram to sho)

e%uili(rium compositions of "I9-acetone-)ater mi,tures'

Characteristics are single phase and t)o phaseregions tie lines connecting e%uili(rium phasecompositions in t)o phase region'

,h i f l t


60/103

,hoice of solvent+actors to (e considered

#electi&ity Distri(ution coefficient

Insolu(ility of sol&ent

eco&era(ility of solute from sol&ent

Density difference (et)een li%uid phases

Interfacial tension

Chemical reacti&ity

Cost Fiscosity &apour pressure

+lamma(ility to,icity

S l ti it


61/103

Selectivity

G B /mass fraction 9 in E*/mass fraction ! in E

/mass fraction 9 in */mass fraction ! in

G H 1


62/103

( ti


63/103

(roperties*Density: ! density difference is re%uired (et)een

the t)o phases'

$nter%acial tension : The larger the interfacialtension (et)een the t)o phases the more

readily coalescence of emulsions )ill occur togi&e t)o distinct li%uid phases (ut the more

difficult )ill (e the dispersion of one li%uid in the

other to gi&e efficient solute e,traction'

Chemical reacti&ity: #ol&ent should (e sta(le andinert'

(h i l ti


64/103

(hysical properties

+or material handling

$o) &iscosity

$o) &apour pressure

Non-flamma(le /high flash point

Non-to,ic

S ti 0 h i


65/103

Separation 0echni8+es

$i%uid-$i%uid E,traction1';rocess is applica(le at am(ient conditions

2'#pecial e%uipment re%uirements

>'Energy consumption is negligi(le

'No hydrogen consumption

5'8andling is easy

6'The process does not change the chemical

structure of the components'

A li ti f M l l


66/103

Application of Molec+larSim+lation To predict the $J"7 and 87"7 energy of the

molecules and their thermodynamic properties

To find the scalar properties

Chemical potential /K

Electronegati&ity /L


67/103

roperties name :mpiri!al expressionOperational

expressionOr(ital e.inition

Chemical potential ' )

/lectronegativity 'U)

Alobal 6ardness 'V )

Alobal "oftness '")

/lectrophilicity

inde$'W )

Or/ital DenitionsScalar(roperties

' ) r

E

N µ

∂ = ∂ 2

/P E&+ − ÷ 2

"%M% '+M%ξ ξ + ÷

' ) r

E

N χ µ ∂ = ∂

; -

2

/P E&+ ÷ 2

"%M% '+M%ξ ξ + ÷

2

2' ) ' )

1 1

2 2V r r

E

N N

µ η

∂ ∂ = = ∂ ∂ 2 /P E&−

÷ 2

"%M% '+M%ξ ξ − +

÷

2

2' ) ' )

1 1 1

2 2V r r

s E

N N

µ η = = =∂ ∂ ∂ ∂

2 /P E&

÷− 2

"%M% '+M%ξ ξ

÷− +

2

2

µ ω

η = M

/P E&+ ÷ M

"%M% '+M%ξ ξ − +

÷

MOED-K S ft


68/103

MOED-K Software


69/103

(artial ,hares (redictions


70/103

(artial ,hares (redictions'ile !it aitional

section mem=-M> un

Route section ? @35?*+,3--B/ opt=2iis#C'(C4N!R=9MAECC5!=-6) pop(npachelp2)2eom=istance

7=

Title section ?artial char2es

Char2e an multiplicity -

Molecular speci%ication

'or e"ampleF Thiophene optimi1e &alues %rom M45D!N out %ile(a%ter 6ND step)s c - cs6c 6 cc3 - ccs3c 3 cc7 6 ccc7 - ih7

c 7 cc8 3 ccc8 6 ih8h 8 hc+ 7 hcc+ - ih+h 7 hc9 8 hcc9 3 ih9h 3 hc 7 hcc 6 ihh 6 hc; 3 hcc; - ih;cs6 -.9-cc3 -.78ccs3 -;.79-cc7 -.78ccc7 -;.79-ih7 .

cc8 -.78ccc8 -;.79-ih8 .hc+ -.;hcc+ -;.79-ih+ -.hc9 -.;hcc9 -;.79-ih9 -.

(artial ,hares


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(artial ,hares


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(artial ,hares


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(artial ,hares of ,ation#4M(O&

(artial ,hares of


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(artial ,hares of)E#4M(O4


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(artial ,hares of )E%0hiophene

E!MO HOMO -neries


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E!MOHOMO -neries(redictions

)nteraction -neries


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)nteraction -neries(redictions

COSMO RS model


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COSMO-RS model C7#"7-# consist of

- Puantum theory- #urface interactions

- #tatistical thermodynamics

- Dielectric continuum models


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*,SM, & *,n!uctor /ieScreenin8 M,!el

Element #pecific

"olecular Ca&itiesCreated #ol&ent !ccessi(le !rea

/#!#

"olecule ;laced

In a conductor #olute "olecule

"olecule ;ulls Charges

+rom the conductor

To the interface

":" divided into small segments

each having a screening charge

density X

LH :q)otal soluteΦ Φ = = +

#urface Charge Distri(ution #I


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The energy difference (et)een the real situation of such contact and

the ideally screened situation has to (e defined as a local electrostatic

interaction energy )hich results from the contact of the molecules'

PCI!

))))))

σY

σ

σ>> 0σYZZ H 8ydrogen 9onding

Interaction

"isfit Energy

Interaction

IdealElectrostati

c

Contact

I t ti "


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Interaction "ner#yCalculations "isfit interaction

6ydrogen bonding ( )2

' , ) ' , )

2

misfit eff misfit

eff

E a e

a

σ σ σ σ

α σ σ

′ ′=

′′= +

' , ) ' , )

minBH,min'H, )ma$'H, )C

hb eff hb

eff hb don hb acc hb

E a e

a c

σ σ σ σ

σ σ σ σ

′ ′=

= + −

mist constant

.8drogen :onding coecientthresho!d for .8drogen:onding

E;ecti


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$cti%ity Coe&icient


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$cti%ity Coe&icient

!cti&ity Coefficient of the #egment

!cti&ity Coefficient of Component in "i,ture

' , )ln ' ) ln ' ) ' )e$p

* * *

E !

k) σ

σ σ σ σ σ

′

′ − Γ = − Γ ∑

2' , ) ' ) minBH, min'H, ) ma$'H, )C

2 hb don hb acc hb

E cα

σ σ σ σ σ σ σ σ ′

′ ′= + + + −

+ +ln ' )8ln ' ) ' )9 ln *(

i * i i * i i * n !

σ

γ σ σ σ γ = Γ − Γ +∑i

i

eff

&n

a==here

i0e The contri(ution of molecule Ri’ to the surface segment

( )+γ i S 7nce !cti&ity Coefficients is =no)n )e can predict $i%uid $i%uidE%uili(ria /$$E

'eneration of COSMO (ile


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'eneration of COSMO (ile

#tep:-: eometry 4ptimi1ation in as ?hase

5e&el o% Theory ;9FQ6 /Density +unctional Theory

@asis #et TSF; /Triple Seta Falence ;olari.ed )ith

D

#tep 6: C4#M4 'ile eneration

5e&el o% Theory ;9FQ6 /Density +unctional Theory

@asis #et TSF; /Triple Seta Falence ;olari.ed * D

#C+ Calculation is done )ith SCRF=COSORS =ey)ord in


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"odified ashford ice algorithm

for C7#"7-# model'

Selectivity 5 ,apacity


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Selectivity 5 ,apacity

The selecti&ity is defined as the ratio of the composition of/nitrogen*sulphur compounds species in I$ rich phase /e,tract

and its composition in model diesel rich /raffinate phase'

"u=hopadhyay1UUV

The in&erse of the acti&ity coefficient of the species

/nitrogen*sulphur compoundsat infinite dilution in sol&ent rich

/e,tract phase' "u=hopadhyay : ao1UQV

86

2 1 2

1 2 1

/' !hase 0iesel !hase /' !hase

ij1max ij* 2* γ γ γ

γ γ γ

∞ ∞ ∞∞

∞ ∞ ∞

= ≈ ÷ ÷ ÷

12

1

1C

γ ∞

∞

= ÷

Separation of aromatic nitroen


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Separation of aromatic nitroen5 s+lph+r compo+nds

0ernary Diaram


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0ernary Diaram

TE"I"VTEt#7V0 10 20 >0 0 50 60 0 Q0 U0 100

9en.othiophene

0

10

20

>0

0

50

60

0

Q0

U0

100

8e,ane

0

10

20

>0

0

50

60

0

Q0

U0

100

E,perimental

C7#"7-# ;redictions

RMSD for Quaternary systems


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yy#'No Name of the systems NT$ model JNIPJ!C

modelC7#"7-#model

1 !M$MI4AcIBThiophene

;yridine?entane

0'> 1'6U '62

2 E"I"VEt#7VThiophene

;yridine?entane

0'12 0'1U 5'>

> !M$MIMe#43IBThiophene

;yridine?entane

1'U 1'60 6'

!M$MI4AcIBThiophene

;yridineCyclohe"ane

1'0> 1'6U 'Q5

5 !M$MI!t#47IBThiophene

;yridineCyclohe"ane

1'25 1'U0 5'U>

6 !M$MIMe#43IBThiophene

;yridineCyclohe"ane

1'0U 2' 5'>5

!M$MI4AcIBThiophene

;yridineToluene

0'U2Q 1'5 Q'1

Q !M$MI!t#47IBThiophene

;yridineToluene

1'2> 1'5 Q'

U !M$MIMe#43IBThiophene

;yridineToluene

0U'> 2'> 6'5>

S+mmary


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S+mmary


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Ac$nowledements


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c o ede e ts

Dr'Tamal 9anerYeeIIT


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Than>s, and 4?!! see 8ou ne@t time0

application of thermodynamics and molecular simulation in chemical engineering problems

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