ChemCad Thermodynamic

Models
Andrew Poissant
Jonathan Jones
Erik Larmore
Marcus Benyamin
Thermodynamic models in Chemical Engineering
Importance
Thermodynamic models predict the equilibrium state of a system, and energy required
separation factors, heat duties, etc.
Choosing the right model
Depends on chemical species and operating conditions
Wrong model will give misleading results
Ex. separation of ethanol-water mixtures

Figure 1.
http://www.chemguide.co.uk/physical/phaseeqia/bpcompi4.gif Figure 2.
http://www.chemguide.co.uk/physical/phaseeqia/bpcompn1.gif
Phase Equilibrium Method Chart
Grayson-Streed Model (G-S)
What is it?

Semi-Empirical Model
Special emphasis placed on H2 during model design

When to Use

Up to three phase systems

Heavy hydrocarbon mixtures
T < 800C P < 200 Atm
N2, CO2, and H2S restricted to less than 5%
Grayson-Streed Model (G-S)
Calculations

Vapour fugacity coefficients calculated from Redlich-Kwong equations of

state

Liquid fugacity coefficients calculated via principle of corresponding states

Special fugacity calculations for N2, CO2, and H2S
H2O treated with steam tables and kerosene solubility chart
Peng-Robinson Model (P-R)
What is it?

Equations of State Model

Designed for natural gas processes
Parameters in terms of critical properties and acentric factor

When to use

Most accurate near the critical point

Peng-Robinson Model (P-R)
Calculations

Based on
Redlich-Kwong
equations of state
Calculates using
reduced temperature
and acentric factor
Redlich-Kwong-Soave Model (R-K-S)
Assumptions

Light hydrocarbons (C5 or lighter)

T<250 K
P<350 bar
Redlich-Kwong-Soave Model (R-K-S)
Calculations

Used to model non-idealities in the vapour phase

Used to relate T, P, and V of gases
More accurate than van der Waals for temperatures greater than critical
temperature
Benedict-Webb-Rubin Model (B-W-R)
Assumptions

T<250 K
Hydrocarbon C5 or lighter
No H2 present
Can only be used for systems that have a significant amount of
experimental data in a wide range of Ps and Ts
Can be used for hydrocarbon systems that include the common light
gases (N2, COs, etc.)
Benedict-Webb-Rubin Model (B-W-R)
Calculations

A0, B0, a, b, c, , characterize the individual properties of the gas. They are
determined from experimental data.
Braun - K10 Model
Developed for large hydrocarbons at low pressures (Hydrocarbon C6 or
larger, <1 bar)
K value is calculated at 10 psi to give K10, then adjusted using pressure
corrections to the system pressure
Cannot be used for systems containing small-molecules as gas (ex. H2)
Experimental Data: Wilson & NRTL
Both suitable for highly nonideal mixtures, and have free parameters that
must be fit
Both based on assumption that liquid composition is non-random
Wilsons: predicts azeotropes; cannot predict LLE
NRTL: can predict LLE (immiscible mixtures)

Disadvantage: experimental data is required to fit parameters

Non-experimental: UNIQUAC & UNIFAC
Both predict activity coefficients based on molecular structure of species
UNIQUAC: treats molecules as surfaces and makes predictions based on
surface fractions
UNIFAC: uses contributions of a molecules functional groups to
determine activity
Can be used to estimate parameters for Wilsons equation, NRTL and UNIQUAC

Advantage: Neither require experimental data, and both are suited to a wide
range of compounds

Disadvantage: UNIFAC requires low pressure (P < 4 bar) and Temperature (T (T

(T < 150 C)
Sour Water Option
Water containing CO2, H2S, and NH3
Combine with PR or SRK
Accounts for ionic effects on fugacity and enthalpy of solution
Extends valid T range beyond 20 C < T < 140 C
Selecting a Thermo Model in ChemCAD
References
Property Methods and Calculations. (n.d.). Retrieved February 2, 2017, from
http://people.clarkson.edu/~wwilcox/Design/HYSYSpropSelect.pdf

Property Package Descriptions. Retrieved Feb. 3, 2017, from

http://razifar.com/cariboost_files/Property_20Package_20Descriptions.pdf

Raoults Law and Ideal Mixtures of liquids. Retrieved February 3, 2017, from
http://www.chemguide.co.uk/physical/phaseeqia/bpcompi4.gif

Thermodynamic Property Models. (n.d.). Retrieved February 2, 2017, from

http://sites.poli.usp.br/d/pqi2408/physpropmodels.pdf