Thermodynamic Models CHBE 446 Group 6 Alex Dinh

Thermodynamic Models CHBE 446 Group 6 Alex Dinh, Josh Fernandes, Maira Iqbal, Jesse Matthews, Vy Pham

Thermodynamic Model Review ● Allow for estimation of non -idealities in systems ○ ○ ○ Fugacity coefficients for gaseous mixtures Activity coefficients for liquid mixtures Activity coefficients for aqueous solutions with ions Sandler, S. Chemical, Biochemical, and Engineering Thermodynamics , 5 th ed. ; John Wiley & Sons, 2017.

Thermodynamic Model Applications ● Prediction of state variables (enthalpy, Gibbs’ free energy) for each component as a function of temperature, pressure, composition ● Prediction of solubility of components in a solvent ● Prediction of phase equilibria ● Essential to improve process performance and product quality Sandler, S. Chemical, Biochemical, and Engineering Thermodynamics , 5 th ed. ; John Wiley & Sons, 2017.

Modeling Proteins and Other Biopolymers ● Large proteins can be approximated as dipeptides of their constituent amino acids ○ Protein composition should be analyzed to select most common residues (~5) ● Biopolymers can be approximated by their repeat unit ● Literature values for physical properties of dipeptides are available Gomez-Rios, D. ; Navarro, G. ; Monsolva, P. ; Barrera-Zapata, R. ; Rios-Estapa, R. Aspen Plus Simulation Strategies Applied to the Study of Chitin Bioextraction from Shrimp Waste. Food Technol Biotechnol. 2019. 57, 238 -248.

Selection of Thermodynamic Models ● Non-idealities of a gas phase system are modeled by cubic equation of states Redlich-Kwong equation of state (RK) Peng-Robinson equation of state (PR) ● System with liquid phase non-idealities must be modeled using activity coefficient methods. NRTL, UNIQUAC and Wilson when sufficient data is available ( >50%) UNIFAC when data is incomplete (<50%) Edwards, J. Process Modeling Selection of Thermodynamic Methods. P&I Design Ltd. 2001.

Appropriate Thermodynamic Models To predict the solubility of solids (different pharmaceuticals and chemicals) in pure or mixed solvents, non-correlative thermodynamic models can be utilized. 2 categories: ● UNIQUAC - need experimental data of various temperatures, pressures, compositions. x ● NRTL segment activity coefficient (NRTL-SAC) and UNIFAC - need very few experimental data and some fundamental properties of the chemical molecules. ✓ Sheikholeslamzadeh, E. ; Rohani, S. Prediction of Solubility of Active Pharmaceutical Ingredients in Single Solvents and Their Mixtures — Solvent Screening. In Recent Advances in Thermo and Fluid Dynamics; Gorji-Bandpy, M. , Ed. ; Intech. Open, 2015.

Comparison of Thermodynamic Models UNIFAC ● ● ● Non-electrolytic and non-ideal behaviors systems Identify molecules by functional groups Good for prediction of systems containing light alcohols and water NRTL-SAC ● ● ● Non-electrolytic, non-ideal behaviors and organic electrolyte systems Identify molecules by dividing the surface into four segments (e. g. , hydrophobic segment (X), hydrophilic (Z), and polar segments (Y-, Y+)) Good for prediction of almost all other systems Sheikholeslamzadeh, E. ; Rohani, S. Prediction of Solubility of Active Pharmaceutical Ingredients in Single Solvents and Their Mixtures — Solvent Screening. In Recent Advances in Thermo and Fluid Dynamics; Gorji-Bandpy, M. , Ed. ; Intech. Open, 2015.

Txy diagrams of different systems via UNIFAC and NRTL-SAC at 1 atm Sheikholeslamzadeh, E. ; Rohani, S. Prediction of Solubility of Active Pharmaceutical Ingredients in Single Solvents and Their Mixtures — Solvent Screening. In Recent Advances in Thermo and Fluid Dynamics; Gorji-Bandpy, M. , Ed. ; Intech. Open, 2015.

Vapor phase mole fractions prediction from UNIFAC and NRTLSAC Sheikholeslamzadeh, E. ; Rohani, S. Prediction of Solubility of Active Pharmaceutical Ingredients in Single Solvents and Their Mixtures — Solvent Screening. In Recent Advances in Thermo and Fluid Dynamics; Gorji-Bandpy, M. , Ed. ; Intech. Open, 2015.

Aspen Demonstration

References [1]https: //www. researchgate. net/publication/229120400_Thermodynamics_of_pharmaceuticals_Prediction_of_solubility_in_pure_and_mixed_ solvents_with_PC-SAFT (accessed Feb 1, 2021). [2]https: //www. intechopen. com/books/recent-advances-in-thermo-and-fluid-dynamics/prediction-of-solubility-of-active-pharmaceuticalingredients-in-single-solvents-and-their-mixtures (accessed Feb 1, 2021) [3]https: //www. chemicalprocessing. com/assets/Media. Manager/thermo. pdf (accessed Feb 1, 2021). [4]https: //core. ac. uk/download/pdf/12043408. pdf (accessed Feb 1, 2021). [5]Sandler, S. Chemical, Biochemical, and Engineering Thermodynamics , 5 th ed. ; John Wiley & Sons, 2017.