Computing Thermodynamic Properties

Demonstration of how to use Cantera to compute thermodynamic properties of a phase

Class ThermoPhase

Cantera can be used to compute thermodynamic properties of pure substances, solutions, and mixtures of various types, including ones containing multiple phases. The first step is to create an object that represents each phase. A simple, complete program that creates an object representing a gas mixture and prints its temperature is shown below:

#include "cantera/core.h"
#include <iostream>

int main(int argc, char** argv)
{
    // Create a new Solution object
    auto sol = Cantera::newSolution("h2o2.yaml");
    auto gas = sol->thermo();

    std::cout << gas->temperature() << std::endl;
    return 0;
}

Here, newSolution imports all information held by a YAML input file into a Cantera Solution object, which is accessed by the pointer sol. The thermodynamic information is accessible via sol->thermo(), which itself returns a pointer to a ThermoPhase object.

Class ThermoPhase is the base class for Cantera classes that represent phases of matter. It defines the public interface for all classes that represent phases. For example, it specifies that they all have a method temperature that returns the current temperature, a method setTemperature(double T) that sets the temperature, a method getChemPotentials(double* mu) that writes the species chemical potentials into array mu, and so on.

Class ThermoPhase can be used to represent the intensive state of any single-phase solution of multiple species. The phase may be a bulk, three-dimensional phase (a gas, a liquid, or a solid), or it may be a two-dimensional surface phase, or even a one-dimensional "edge" phase. The specific attributes of each type of phase are specified by deriving a class from ThermoPhase and providing implementations for its virtual methods.

Cantera has a wide variety of models for bulk phases currently. Special attention (in terms of the speed of execution) has been paid to an ideal gas phase implementation, where the species thermodynamic polynomial representations adhere to either the NASA polynomial form or the Shomate polynomial form. This is widely used in combustion applications, the original application that Cantera was designed for. Recently, a lot of effort has been placed into constructing non-ideal liquid phase thermodynamics models that are used in electrochemistry and battery applications. These models include a Pitzer implementation for brines solutions and a Margules excess Gibbs free energy implementation for molten salts.

The Intensive Thermodynamic State

Class ThermoPhase and classes derived from it work only with the intensive thermodynamic state. That is, all extensive properties (enthalpy, entropy, internal energy, volume, etc.) are computed for a unit quantity (on a mass or mole basis). For example, there is a method enthalpy_mole() that returns the molar enthalpy (J/kmol), and a method enthalpy_mass() that returns the specific enthalpy (J/kg), but no method enthalpy() that would return the total enthalpy (J). This is because class ThermoPhase does not store the total amount (mass or mole) of the phase.

The intensive state of a single-component phase in equilibrium is fully specified by the values of any \(r+1\) independent thermodynamic properties, where \(r\) is the number of reversible work modes. If the only reversible work mode is compression (a "simple compressible substance"), then two properties suffice to specify the intensive state. Class ThermoPhase stores internally the values of the temperature, the mass density, and the mass fractions of all species. These values are sufficient to fix the intensive thermodynamic state of the phase, and to compute any other intensive properties. This choice is arbitrary, and for most purposes you can't tell which properties are stored and which are computed.

Derived Classes

Many of the methods of ThermoPhase are declared virtual, and are meant to be overloaded in classes derived from ThermoPhase. For example, class IdealGasPhase derives from ThermoPhase, and represents ideal gas mixtures.

Although class ThermoPhase defines the interface for all classes representing phases, it only provides implementations for a few of the methods. This is because ThermoPhase does not actually know the equation of state of any phase—this information is provided by classes that derive from ThermoPhase. The methods implemented by ThermoPhase are ones that apply to all phases, independent of the equation of state. For example, it implements methods temperature() and setTemperature(), since the temperature value is stored internally.

Example Program

In the program below, a gas mixture object is created, and a few thermodynamic properties are computed and printed out:

#include "cantera/core.h"
#include <iostream>

using namespace Cantera;

void thermo_demo(const std::string& file, const std::string& phase)
{
    // Create a new Solution object
    auto sol = newSolution(file, phase);
    auto gas = sol->thermo();

    gas->setState_TPX(1500.0, 2.0*OneAtm, "O2:1.0, H2:3.0, AR:1.0");

    // temperature, pressure, and density
    std::cout << gas->temperature() << std::endl;
    std::cout << gas->pressure() << std::endl;
    std::cout << gas->density() << std::endl;

    // molar thermodynamic properties
    std::cout << gas->enthalpy_mole() << std::endl;
    std::cout << gas->entropy_mole() << std::endl;

    // specific (per unit mass) thermodynamic properties
    std::cout << gas->enthalpy_mass() << std::endl;
    std::cout << gas->entropy_mass() << std::endl;

    // chemical potentials of the species
    size_t numSpecies = gas->nSpecies();
    vector_fp mu(numSpecies);
    gas->getChemPotentials(mu.data());
    for (size_t n = 0; n < numSpecies; n++) {
        std::cout << gas->speciesName(n) << " " << mu[n] << std::endl;
    }
}

int main(int argc, char** argv)
{
    try {
        thermo_demo("h2o2.yaml", "ohmech");
    } catch (CanteraError& err) {
        std::cout << err.what() << std::endl;
        return 1;
    }
    return 0;
}

Note that the methods that compute the properties take no input parameters. The properties are computed for the state that has been previously set and stored internally within the object.

Naming Conventions

  • methods that return molar properties have names that end in _mole.

  • methods that return properties per unit mass have names that end in _mass.

  • methods that write an array of values into a supplied output array have names that begin with get. For example, the method getChemPotentials(double* mu) writes the species chemical potentials into the output array mu.

The thermodynamic property methods are declared in class ThermoPhase, which is the base class from which all classes that represent any type of phase of matter derive.

See ThermoPhase for the full list of available thermodynamic properties.

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