Prediction of Thermodynamic

Properties of Industrially Important

Polymers


Name: Rishikesh Awale
Roll No:10D020009
CL 445 Presentation
02/05/2014
Motivation
Developing Equation of state
Obtaining VLE data
Design of Separation processes


Polystyrene
Aromatic synthetic Vinyl Polymer made from
styrene by free radical polymerisation
Production Methods:
Bulk Polymerisation
Solution polymerisation
Suspension polymerisation
Emulsion polymerisation





Bulk and Solution Polymerisation
Free radical polymerisation

Chain Initiation : IR*+R*
R*+M RM*

Chain Propagation:



Chain Transfer:

Chain termination :
Styrene
Aromatic liquid hydrocarbon produced from
Ethyl benzene
Production Routes:
Catalytic dehydrogenation of ethyl benzene-
More than 90% global production
Ethyl benzene hydro peroxide process-
Less than 10% worldwide production

Catalytic dehydrogenation of ethyl benzene
Ethyl Benzene Hydro peroxide process
Ethyl benzene and styrene separation
Ethyl benzene and styrene are close boiling liquids
For high purity styrene distillation column demands
large number of trays and large reboiler duty
Addition of appropriate extracting agents can
increase value of relative volatility >1 for ethyl
benzene styrene VLE mixture.
Sulfolane raises relative volatility up to 2.2
Low vapour pressure exerting Ionic liquid 4-methyl-
N-butylpyridinium tetra fluoroborate ([4-mebupy]-
[BF4]) raises relative volatility up to 2.8



United Atom
United atoms Grouping of Carbon and all
attached hydrogen atoms to it together as an
interaction site located at carbon in
hydrocarbons
United atoms treated as pseudo atoms for
potential calculations
When only C and H atoms in Hydrocarbon
number of pseudo atoms is same as number
of carbon atoms
TRaPPE-UA
Transferrable potentials for phase equilibria United atom
Force field
Transferability-Same Potential energy parameters for united
atoms when present in different molecules
Fluid thermodynamic properties are depended on
Intermolecular interactions
Intermolecular interactions: Bonded Interactions & Non
Bonded Interactions
Bonded- Intramolecular interactions between pseudo atoms
within a molecule itself.
Non Bonded- Intermolecular interactions between pseudo
atoms present on different molecules and pseudo atoms
within a molecule separated by four or more chemical bonds.



Bonded Interactions








1-2 Bonded Interaction-Pseudo atoms at the two extremities of a bond of
fixed length.
1-3 Bonded Interaction-Also called harmonic bond bending potential.
Pseudo atoms separated by two chemicals bonds at the two ends of V
shaped network
1-4 Bonded Interaction- Dihedral interactions between pseudo atoms
separated by three Chemical bonds

Pseudo atom 1: sp
2
Carbon atom of
benzene ring
Pseudo atom 2, 3, 4, 5 &6: CH group in
benzene ring
Pseudo atom 7:CH group of substituted
alkene group
Pseudo atom 8: CH
2
group of substituted
alkene group

Non Bonded Interactions
Lenard Jones (6-12) potential describes Potential energy of
system

ij
-LJ well depth,
ij
-LJ diameter, r
ij
Distance between pseudo
atoms i and j

Potential energy for the pair of dissimilar pseudo atoms is
evaluated by using following Standard Lorentz Berthelot
Combining rule

Cut off radius Distance beyond which intermolecular
interactions between pseudo atoms is negligible.
GEMC
Gibbs ensemble Monte Carlo is computationally
most effective method of obtaining VLCC (Vapour
Liquid Co-existence)curves for pure component from
its simulation results.
Ensemble-Canonical (NVT)Ensemble Number of
particles N ,Volume of system V and Temperature T
are specified
Internal equilibrium within each phase
Equal pressure exerted by two phases
Equal chemical potential of pure component in both
vapour and liquid phases.




Schematic of GEMC
Perturbations/Trial Moves in Monte Carlo for
ascertaining equilibrium
Random displacement of a particle in one of the
boxes
Volume exchange by equal amount between two
boxes
Transfer of particle from one box to another

Partition function for the overall vapour liquid system

1

3
!

1=0

1
exp
1

1

2

2
exp
2

0

is the thermal de Broglie wavelength given as =
h
2mTk
b

=
1

,
1
and
2
are the scaled coordinates of the particles in vapour and
liquid phase respectively and U
1
(N
1
) and U
2
(N
2
) represent potential energy
of vapour and liquid phase
V
1
and N
1
are the volume and number of particles of vapour phase and
volume and number of particles of liquid phase are V-V
1
and N-N
1

respectively.
The probability of finding configuration of system with partition function
given as above is:
P (N
1
, V
1
; N, V, T)
!

1
!
2
!
exp(N
1
lnV
1
+N
2
lnV
2
- U
1
(N
1
)-U
2
(N
2
))


Particle transfer within a box
Potential energy of vapour phase corresponding to initial configuration U
1i
Potential energy of vapour phase corresponding to initial configuration U
1f
Potential energy of liquid phase remains unchanged
Probability distribution of initial configuration is:
P
i

1
!
2
!
exp(N
1
lnV
1
+N
2
lnV
2
- U
1i
(N
1
)-U
2i
(N
2
)) (1)
Probability distribution of final configuration is:
P
f

1
!
2
!
exp(N
1
lnV
1
+N
2
lnV
2
- U
1f
(N
1
)-U
2i
(N
2
)) . (2)
Relative probability for transition from initial configuration to final configuration

= [exp(-(U
1f
(N
1
)- U
1f
(N
1
))]

= [exp(-(U)]
U>0 then move accepted if a random number generated in [0,1] is less than
exp(-U) otherwise not accepted.
U <0 the probability of transition of particle to new location is 1
Volume exchange among the two boxes
Initial and final volumes of vapour phase are V
i
and V
f
respectively then
the change in volume is V= V
f
-

V
i
.Let total potential energy of the vapour
phase before and after volume change is E
i
and E
f
then change in potential
energy of vapour phase is U= U
f
-U
i

Probability density corresponding to initial configuration where volume of
vapour phase is V
i
and energy E
i
is:
P
i

1
!
2
!
exp (N
1
lnV
1
+N
2
lnV
2
- U
1i
(N
1
)-U
2i
(N
2
)) [U
1i
(N
1
) + U
2i
(N
2
) =U
i
]
Similarly for final configuration where volume of vapour phase is V
f
and
total energy E
f
probability density is:
P
f

!

1
!
2
!
exp (N
1
lnV
1
+N
2
lnV
2
- U
1f
(N
1
)-U
2f
(N
2
)) [U
1f
(N
1
) + U
2f
(N
2
)=U
f
]
Relative probability for transition from initial configuration to final
configuration as:

= [

]
N1
[

]
N-N1
exp[-(E
f
-E
i
)]

Particle exchange between two boxes
For transfer of particle from vapour phase to liquid phase the
relative probability for occurrence of this event is:

1
!
1
!
1

1
1
(
1
)
(
1
1)
(
1
1)! (
1
1 )!
1

1
(
1
)

1
exp[-(E
f
-E
i
)]
Probability that particle from vapour phase will go to liquid phase

1
(
1
)
(
1
+1)
1
exp[-(E
f
-E
i
)]
Probability for transfer of particle from liquid to vapour phase

(
1
)(
1
)
(
1
+1)(
1
)
exp[-(E
f
-E
i
)]
References
[1] http://inventors.about.com/od/pstartinventions/a/styrofoam.htm
[2] http://www.nature.com/srep/2013/130826/srep02502/fig_tab/srep02502_F1.html
[3] Polystyrene: Synthesis Production and Application by J.R. Winsch
[4] http://www.boedeker.com/polyst_p.htm
[5] http://webbook.nist.gov/chemistry/
[6] http://www.styrenemonomer.org/2.2.html &
http://www.chemicalbook.com/ChemicalProductProperty_EN_CB3415111.htm
[7] Ullmann's Encyclopedia of Industrial Chemistry
[8] Arno Behr, Styrene Production from Ethylbenzene. Universitat Dortmund
[9] http://www.sbioinformatics.com/design_thesis/Styrene/Styrene_Methods-2520of-
2520Production.pdf
[10] Chemical process technology 2
nd
edition Jacob A Moulin et al
[11] Journal of chemical and engineering data Mark T. G. Jongmans et al
[12] Journal of chemical and engineering data Isobaric Low-Pressure VaporLiquid Equilibrium
Data for Ethylbenzene + Styrene + Sulfolane and the Three Constituent Binary Systems By
Mark T. G. Jongmans et al
[13] Styrene: 2013 World Market Outlook and Forecast up to 2017, merchant research
and consulting ltd.
[14] ASTM, Designation: D2827 13 Standard Specifications for Styrene Monomer
[15] Introduction to Molecular Simulation and Statistical Thermodynamics by Berend Smit
Daan Frenkel.
[16] https://www.chem.umn.edu/groups/siepmann/trappe/united_atom.php