THERMODYNAMIC MODELS

&
PHYSICAL PROPERTIES
Books and journals
– DECHEMA, Fluid Phase Eq., J.Che.Eng.D.,
JANAF tables, Int’l Critical. Tables,
Data companies
– AIChE\DIPPR, DECHEMA/DETHERM,
Knovel.com, PPDS
Pure component properties
Important to ensure properties of pure components
and mixtures estimated appropriately. Carefully
consider choice of methods to estimate the different
properties.
e.g. density, viscosity, surface tension
Physico-chemical Properties and Generation of
Pxy/Txy Diagrams from ChemCad
Accessing the component databank
From Thermophysical command on main menu
select Databank. Gives access to the CHEMCAD
component databank.
Select the View/Edit command from the Databank
Menu, select a component from the database. Then
View/Edit Component Data Menu will appear.
Phase equilibria
Select a model or method for calculating vapor-liquid
(or vapor-liquid-liquid) phase equilibrium (called the
K-value option¸ Ki=yi/xi) and selecting a method or
model for calculating the heat balance (called the
enthalpy option). Mathematical models which
describe the composition of the vapour and/or liquid
phases of a mixture
Models can be based on physical effects,
thermodynamic constraints, or fit to empirical data
No [precise and accurate] universal model exists.
Different systems have different dominating effects.
Two basic models i) Equations of State and
ii) Activity coefficient methods : Correlated or
Predictive
Equations of State
Peng-Robinson, Grayson Streed, SRK, API SRK,
TSRK, MSRK, PSRK, BWRS
Activity Coefficient Models
UNIFAC (LLE, VLE), UNIFAC (Polymers),
UNIQUAC, NRTL, Van Laar, Wilson, Wilson Salt,
T.K. Wilson, Margules, Hiranuma, GMAC, Regular
Solution
To select model use ThermoPhysical command
located on the menu bar.
CHEMCAD library has about 50 K-value models, and
about twelve enthalpy models. The issues involved
and the proper techniques for selection are described
in the Thermodynamics section of the on-line
manual.
CHEMCAD can assist user using feature called
Thermo Wizard (described in the Thermodynamics
section of the on-line manual). K-Value Wizard aids
thermodynamic model selection.
Selection based on component list and operating
temperature and pressure ranges. The Wizard decides
which model to use between EOS, activity coefficient,
empirical and special.

Validating a model selection

Generate Pxy, Txy and xy data/diagrams for the given
chemical system using variety of K-value/enthalpy
models (ideal vapour pressure/latent heat for Raoult’s
law; other activity coefficient models for the liquid
phase, or an equation of state for both liquid and
vapour phases).
Compare ChemCad generated data for each model
against each other and with experimental data