ThermoSolver

An Integrated Educational
Thermodynamics Software Program
Connelly Barnes

What is ThermoSolver?
Programmed by Connelly Barnes.
Software program used to teach Chemical
Engineering (ChE) thermodynamics.
Available for free from Web (Google it).
Allows students to "explore"
thermodynamics make nontrivial
calculations, and compare different
thermodynamic models.

Motivation
Thermodynamic equations can become
complicated, must be solved by lookup
tables or computer algorithms.
Tables are available for a limited set of
pure species.

Motivation (continued)
Computer solutions: spreadsheets,
scripts, Computer Algebra System
worksheets can be used, but it's hard to
let the student use different number of
species, thermodynamic models, etc.
We would like students to not have the
burden of programming every solution,
especially for routine calculations.

Objectives
Standalone educational software program.
Easy to use interface reduce all
"barriers" to using the software.
Research and develop algorithms needed
to solve equations.
Integrate with chapter problems in
Engineering and Chemical
Thermodynamics by Milo Koretsky.

Use at Universities
At OSU, ThermoSolver used in ChE thermo
course, graduate reactors course, plant
design.
In plant design, ThermoSolver not specifically
named, but 10/39 students used it.
Don't track usage by other Universities, but
Web search reveals it has been used at Univ.
Notre Dame, Indiana and Univ. of Colorado
at Boulder.

Features

Database, 350+ chemical compounds.

Calculate saturation pressure, temp.
Solve equations of state (LK and PR).
Find pure, mixed fugacity coefficients.
Fit excess Gibbs energy models to
experimental data.
Bubble point and dew point calculations.
Plot phase diagrams for binary systems.

Features (continued)

Calculate Keq for single chemical reaction.

Multiple chemical reaction equilibria.
Plotting.
HTML docs provided, numerical methods
and equations described.

Tour of Program:

Saturation Pressure Calculator

Solve for saturation pressure or saturation
temperature.
Saturation pressure/temp determines
where liquid/vapor phase transition
occurs.
Example problem: Find saturation
pressure of 1,4-dioxane (C4H8O2) at 50 oC.

Tour of Program:

Equation of State Solver

Finds one of the state properties pressure,
molar volume, or temperature given the
other two, using the LK or PR equations of
state.
Example problem: Find molar volume of
propane at 35 bar and 50 oC. Compare w/
ideal gas: 0.77 L/mol.

Tour of Program:

Fugacity Coefficient Solver

Finds the pure fugacity coefficient i or the
fugacity coefficient i of a species in a
mixture, using the LK or PR equation of
state.

Tour of Program:

Fugacity Coefficient Solver

i

Tour of Program:

Models for excess Gibbs energy

Fits activity coefficient models to
experimental data for binary Vapor-Liquid
Equilibrium (VLE) systems.
Objective function.

Example: Chloroform-heptane.

Tour of Program:

Bubble point / Dew Point Calculator

Dew point: gaseous system, when first drop
of liquid forms achieved by decreasing
temperature or increasing pressure.
Bubble point: liquid system, when first bubble
forms.
Solver finds temp./pressure where first bubble
or dewdrop forms, and composition of
chemicals in bubble or dew-drop.

Tour of Program:

Bubble point / Dew Point Calculator

Tour of Program:

Binary Phase Diagrams

Make plots of phase transitions in binary
vapor-liquid systems.

Example: Plot pressure vs. liquid mole

fraction for methylcyclohexane-benzene
system at 50 oC.

Tour of Program:

Equilibrium Constant Solver

Finds KT at a single temperature, for a
single chemical reaction.
Plots KT vs T.

Tour of Program:

Equilibrium Constant Solver

Tour of Program:

Multiple Chemical Reaction Equilibria

Gas-solid equilibrium.
Found by minimizing excess Gibbs energy.

Tour of Program:

Multiple Chemical Reaction Equilibria

Tour of Program:

Multiple Chemical Reaction Equilibria

Numerical Algorithms
Newton root finder with backtracking.
Downhill simplex method for minimization.
Iterative substitution.

Multidimensional Newton Method

Vector-valued function F: Rn -> Rn.
F1
x
1
DF
Fn
x1

F1

xn

Fn

xn

(
D
F
)
F( x i )
Newton step
xi
Iterate x i 1 x i

Newton Backtracking
Use full Newton step if norm ||F||2 is less
than its value at xi, otherwise try /2, /4,
/8, ... until ||F||2 is less than its value at xi.
This is guaranteed to happen, as is a
descent direction for ||F||2.

Simplex Method
J.A. Nelder and R. Mead, "A simplex
method for function minimization,"
Computer Journal 7 (1965) 308-313.
Simple, derivative free method for finding
minimum of function of form F: Rn -> R.
Does not use derivatives, so constrained
minimization possible by setting F to
infinity.

Algorithms
Equation of state solver: Newton method.
Excess Gibbs energy model fitting: Simplex.
Bubble point / dew point: Custom iterative
methods based on those of Smith, Van Ness,
and Abbott.
Multiple chemical reaction equilibria: Newton
and simplex. Typically converges, however
Dr. Koretsky found a problem where this
method does not converge.

Conclusion
Objectives met?
User interface is straightforward to use.
Numerical methods converge with one
known exception.
A practical tool integrated with problems in
a textbook.

Acknowledgements
Milo Koretsky, Mentor.
Rubin Landau, Computational Physics.