MONTE CARLO CALCULATIONS FOR ALCOHOLS

ABSTRACT
Trappe-UA force-field for hydrocarbons has been extended to primary, secondary alcohols. Coupled-decoupled configurational bias Monte-Carlo Simulations in the Gibbs ensemble has been carried to calculate the 1 component vapor-liquid coexistence curves for Alcohols. Phase equilibria of the pure alcohols are accurately described by the Trappe-UA Force fields.

IMPORTANCE OF VLE
VLE gives the nature of intermolecular interactions present in the liquid and vapor phases. Useful in developing equations of state and corresponding state theories

Knowledge of critical points and VLE are key to achieving fundamental understanding of these fluids.

ALCOHOLS UNDER STUDY

Methanol

Ethanol
Propan-1-ol Propan-2-ol Butan-2-ol

Pentan-1-ol
Octan-1-ol

ALCOHOLS
They are amphiphilic molecules composed of a flexible, non-polar alkyl tail and a polar hydroxyl head that is capable of acting as hydrogen donor and acceptor Alcohols have desirable solvent characteristics due to their amphiphilic nature. They are readily available

NEED FOR MOLECULAR SIMULATION

Knowledge of fluid phase diagrams and related thermo-physical properties is essential in process design and process optimization. Reliable Experimental data are only available for relatively low molecular weight alcohols and only over a limited temperature range because of their thermal instability above 600K. Molecular simulation is an alternative approach to obtain the thermo-physical properties of alcohols Accuracy of the prediction depends largely on the quality of the force-field used and how well it describes the system.

TRAPPE MODEL
Trappe Model was developed to

Reproduce Thermo-Physical Properties over a wide range of physical Conditions

Keep the models as transferable as possible by minimizing the number of (Pseudo) atoms needed for any particular molecule and by using the same parameters for a given (Pseudo) atom in all types of molecules

TRAPPE MODEL
A Pseudo Atom mimics the interactions of its core electrons plus a share of the valence electron that make its bonds to the neighboring atoms. The Contribution of the valence electrons far outweighs the contribution of the core electrons towards molecular polarizability. Example: Pseudo atom for methyl group that is connected to another Carbon atom, accounts for 3 C-H bonds and a share of the C-C bond. The same Pseudo atom can be used for the methyl group in ethane, propane etc. However the pseudo atom for the methyl group connected by a single bond to an Oxygen atom is different due to the differences in the electronegativity between C and O atoms which leads to intramolecular charge transfer and requires the use of a partial charge

FORCE FIELD DEVELOPMENT

In Trappe-UA model, CHx groups are treated as pseudo atoms located at the sites of the carbon atoms whereas all other atoms(e.g O and H) are modeled explicitly. Non-bonded interactions are described by

Non-Bonded potentials of the above equation are used only for interactions of pseudoatoms belonging to different molecules or belonging to the same molecule but whose interactions are not accounted for by any of the intramolecular, bonded potentials.

FORCE-FIELD DEVELOPMENT
In TRAPPE-UA force-fields, all bond-lengths are fixed

A harmonic potential is used to control bond angle bending

Where , o and K are the measured bending angle, equilibrium bending angle and the force constant

The Torsional potentials used to restrict the dihedral rotations is as shown above

SIMULATION DETAILS
Combination of the Gibbs Ensemble Monte Carlo Method and the Configurational Bias Monte Carlo method was employed to calculate the Vapor-Liquid Coexistence curves Combined volume of the simulation boxes was adjusted to yield liquid-phase simulation boxes with linear dimension of 30 A and larger vapor-phase simulation box containing atleast 10 molecules For the LJ part of the potential, a cut-off distance of 14 A was set and analytic tail corrections were enforced. An Ewald sum with thin-foil boundary conditions was used for the long-range electrostatic interactions

SIMULATION DETAILS
5 different Monte-Carlo moves were used to sample phase space in the Gibbs ensemble simulations. The moves are Translational Rotational Conformational Volume Exchanges Particle Swaps between boxes Moves were selected randomly with fixed probabilities that were adjusted to yield about one volume exchange or particle swap move per 10 MC Cycles and the remainder of the moves were equally divided among the other moves

SIMULATION DETAILS
Coupled decoupled Configurational Bias Monte-Carlo algorithm was used for conformational and particle swap moves. Computational efficiency was increased by utilizing a Biased insertion Additional center of mass based cut-off which avoids computing unnecessary distances. Coupled-decoupled CBMC particle swap proceeds as follows (i) The hydroxyl O is inserted(using multiple insertions) (ii) The Hydroxyl H and -carbons are added as a consequence (iii) Then, the remainder of the alkyl tail is grown

RESULTS
Methanol(Dashed lines and Squares), Ethanol(Solid lines and circles)

Pentan-1-ol(dotted lines and diamonds),

octan-1-ol (dash-dotted lines and triangles up)

RESULTS
Propan-1-ol(solid lines and circles), Propan-2-ol ( dashed lines and squares)

Butan-2-ol (dash-dotted lines and triangles down)

RESULTS

RESULTS
Experimental Saturated liquid densities are very well reproduced with average deviations of about 1%. However, larger deviations were observed for the saturated vapor densities and pressures. Vapor pressures are overestimated at higher reduced temperatures but underestimated at lower reduced temperatures which is more pronounced for lower molecular weight alcohols. TRAPPE force-field predicted high saturated vapor-pressures for unsaturated alkanes too.

CRITICAL CONSTANTS

RESULTS
Agreement for the critical constants are satisfactory

Critical Temperatures of most alcohols are slightly underestimated with an average deviation of about 1.5%
Critical densities are overestimated on average by about 3% Critical Density disagreement can be due to Law of rectilinear diameters has a negative slope, an underestimation of the critical temperatures results in an overestimation of the critical densities Vapor densities at elevated temperatures are too high, which results in a shift of the mean saturated densities to higher values

OUR GCN AND NPT RESULTS

T (K)
470 500 510 515

p (MPa) 1.64303 3.017061 3.618617 3.948885

rVap (kg/m3) 34.44982 70.74142 91.18393 106.3667

rLiq (kg/m3) 591.996 521.8192 488.4794 468.5673

470 500 510 515

1.626919 3.02532 3.616337 3.923665

33.83991 74.36615 91.72798 105.7948

591.4571 515.2263 485.3918 472.4864

CONCLUSION
The performance of the TRAPPE-UA Force field for the prediction of thermo-physical properties is in general very satisfactory with mean errors of about 1% for the saturated liquid densities 1.5% for the critical temperature 3% for the critical density As observed for alkanes, alkenes, this force field tends to over-predict the saturated vapor densities.

REFERENCES
Bin chen,Jeffrey J. Potoff, and J. Iija Siepmann. Monte Carlo Calculations for Alcohols. Transferable Potentials for Phase equilibria. 5. United-Atom Description of Alcohols Frenkel D and Smit B. Understanding Molecular Simulations.

THANK YOU