### Abstract

Shannon entropy expressed by variables that characterize discrete states of individual

molecules in terms of their interacting neighbors in a mixture. To apply

this method to condensed-phase lattice fluids, this paper further develops

an approach proposed by Vinograd which features discrete Markov-chains for

the sequential lattice construction and rigorous use of Shannon information as

thermodynamic entropy, providing an in-depth discussion of the modeling

concept evolved. The development comprises (1) improved accuracy compared

to Monte Carlo data and (2) an extension from a two-dimensional to a

three-dimensional simple lattice. The resulting model outperforms the quasichemical

approximation proposed by Guggenheim, a frequently used reference

model for the simple case of spherical molecules with uniform energetic surface

properties. To illustrate its potential as a starting point for developing gE-models

in chemical engineering applications, the proposed modeling methodology is

extended, using the example of a simple approach for dicelike lattice molecules with multiple interaction sites on their surfaces, to

address more realistic substances. A comparison with Monte Carlo simulations shows the model’s capability to distinguish between

isomeric configurations, which is a promising basis for future gE-model development in view of activity coefficients for liquid mixtures.

Original language | English |
---|---|

Pages (from-to) | 1294−1306 |

Journal | Industrial & engineering chemistry research |

Volume | 57 |

Publication status | Published - 26 Dec 2017 |

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### Fields of Expertise

- Mobility & Production

### Cite this

**Discrete Modeling Approach as a Basis of Excess Gibbs-Energy Models for Chemical Engineering Applications.** / Wallek, Thomas; Mayer, Christoph; Andreas, Pfennig.

Research output: Contribution to journal › Article › Research › peer-review

*Industrial & engineering chemistry research*, vol. 57, pp. 1294−1306.

}

TY - JOUR

T1 - Discrete Modeling Approach as a Basis of Excess Gibbs-Energy Models for Chemical Engineering Applications

AU - Wallek, Thomas

AU - Mayer, Christoph

AU - Andreas, Pfennig

PY - 2017/12/26

Y1 - 2017/12/26

N2 - Discrete modeling is a concept to establish thermodynamics onShannon entropy expressed by variables that characterize discrete states of individualmolecules in terms of their interacting neighbors in a mixture. To applythis method to condensed-phase lattice fluids, this paper further developsan approach proposed by Vinograd which features discrete Markov-chains forthe sequential lattice construction and rigorous use of Shannon information asthermodynamic entropy, providing an in-depth discussion of the modelingconcept evolved. The development comprises (1) improved accuracy comparedto Monte Carlo data and (2) an extension from a two-dimensional to athree-dimensional simple lattice. The resulting model outperforms the quasichemicalapproximation proposed by Guggenheim, a frequently used referencemodel for the simple case of spherical molecules with uniform energetic surfaceproperties. To illustrate its potential as a starting point for developing gE-modelsin chemical engineering applications, the proposed modeling methodology isextended, using the example of a simple approach for dicelike lattice molecules with multiple interaction sites on their surfaces, toaddress more realistic substances. A comparison with Monte Carlo simulations shows the model’s capability to distinguish betweenisomeric configurations, which is a promising basis for future gE-model development in view of activity coefficients for liquid mixtures.

AB - Discrete modeling is a concept to establish thermodynamics onShannon entropy expressed by variables that characterize discrete states of individualmolecules in terms of their interacting neighbors in a mixture. To applythis method to condensed-phase lattice fluids, this paper further developsan approach proposed by Vinograd which features discrete Markov-chains forthe sequential lattice construction and rigorous use of Shannon information asthermodynamic entropy, providing an in-depth discussion of the modelingconcept evolved. The development comprises (1) improved accuracy comparedto Monte Carlo data and (2) an extension from a two-dimensional to athree-dimensional simple lattice. The resulting model outperforms the quasichemicalapproximation proposed by Guggenheim, a frequently used referencemodel for the simple case of spherical molecules with uniform energetic surfaceproperties. To illustrate its potential as a starting point for developing gE-modelsin chemical engineering applications, the proposed modeling methodology isextended, using the example of a simple approach for dicelike lattice molecules with multiple interaction sites on their surfaces, toaddress more realistic substances. A comparison with Monte Carlo simulations shows the model’s capability to distinguish betweenisomeric configurations, which is a promising basis for future gE-model development in view of activity coefficients for liquid mixtures.

M3 - Article

VL - 57

SP - 1294−1306

JO - Industrial & engineering chemistry research

JF - Industrial & engineering chemistry research

SN - 0888-5885

ER -