FixedChemPotSSTP.h

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/**
 * @file FixedChemPotSSTP.h
 * Header file for the FixedChemPotSSTP class, which represents a fixed-composition
 * incompressible substance with a constant chemical potential (see \ref thermoprops and
 * class \link Cantera::FixedChemPotSSTP FixedChemPotSSTP\endlink)
 */
 
// This file is part of Cantera. See License.txt in the top-level directory or
// at https://cantera.org/license.txt for license and copyright information.
 
#ifndef CT_FIXEDCHEMPOTSSTP_H
#define CT_FIXEDCHEMPOTSSTP_H
 
#include "SingleSpeciesTP.h"
 
namespace Cantera
{
 
//! Class FixedChemPotSSTP represents a stoichiometric (fixed composition)
//! incompressible substance.
/*!
 * This class internally changes the independent degree of freedom from density
 * to pressure. This is necessary because the phase is incompressible. It uses a
 * zero volume approximation.
 *
 * ## Specification of Species Standard State Properties
 *
 * This class inherits from SingleSpeciesTP. It uses a single value for the
 * chemical potential which is assumed to be constant with respect to
 * temperature and pressure.
 *
 * The reference state thermodynamics is inherited from SingleSpeciesTP.
 * However, it's only used to set the initial chemical potential to the value of
 * the chemical potential at the starting conditions. Thereafter, it is ignored.
 *
 * For a zero volume material, the internal energy and the enthalpy are equal to
 * the chemical potential. The entropy, the heat capacity, and the molar volume
 * are equal to zero.
 *
 * ## Specification of Solution Thermodynamic Properties
 *
 * All solution properties are obtained from the standard state species
 * functions, since there is only one species in the phase.
 *
 * ## Application within Kinetics Managers
 *
 * The standard concentration is equal to 1.0. This means that the kinetics
 * operator works on an (activities basis). Since this is a stoichiometric
 * substance, this means that the concentration of this phase drops out of
 * kinetics expressions.
 *
 * An example of a reaction using this is a sticking coefficient reaction of a
 * substance in an ideal gas phase on a surface with a bulk phase species in
 * this phase. In this case, the rate of progress for this reaction, \f$ R_s
 * \f$, may be expressed via the following equation:
 *   \f[
 *    R_s = k_s C_{gas}
 *   \f]
 * where the units for \f$ R_s \f$ are kmol m-2 s-1. \f$ C_{gas} \f$ has units
 * of kmol m-3. Therefore, the kinetic rate constant, \f$ k_s \f$, has units of
 * m s-1. Nowhere does the concentration of the bulk phase appear in the rate
 * constant expression, since it's a stoichiometric phase, and the activity is
 * always equal to 1.0.
 *
 * ## Instantiation of the Class
 *
 * This phase may be instantiated by calling the default ThermoFactory routine
 * for %Cantera. This new FixedChemPotSSTP object must then have a standalone
 * XML file description an example of which is given below.
 *
 * It may also be created by the following code snippets. The code includes the
 * special member function setChemicalPotential( chempot), which sets the
 * chemical potential to a specific value in J / kmol.
 *
 * @code
 *    XML_Node *xm = get_XML_NameID("phase", iFile + "#Li(Fixed)", 0);
 *    FixedChemPotSSTP *LiFixed = new FixedChemPotSSTP(*xm);
 *    // Set the chemical potential to -2.3E7 J/kmol
 *    LiFixed->setChemicalPotential(-2.3E7.)
 * @endcode
 *
 * or by the following call to importPhase():
 *
 * @code
 *    XML_Node *xm = get_XML_NameID("phase", iFile + "#NaCl(S)", 0);
 *    FixedChemPotSSTP solid;
 *    importPhase(*xm, &solid);
 * @endcode
 *
 * The phase may also be created by a special constructor so that element
 * potentials may be set. The constructor takes the name of the element and
 * the value of the element chemical potential. An example is given below.
 *
 * @code
 *     FixedChemPotSSTP *LiFixed = new FixedChemPotSSTP("Li", -2.3E7);
 * @endcode
 *
 * ## XML Example
 *
 * The phase model name for this is called FixedChemPot. It must be supplied
 * as the model attribute of the thermo XML element entry.
 *
 * @code
 * <?xml version="1.0"?>
 * <ctml>
 *   <validate reactions="yes" species="yes"/>
 *
 *   <!-- phase NaCl(S)    -->
 *   <phase dim="3" id="LiFixed">
 *     <elementArray datasrc="elements.xml">
 *       Li
 *     </elementArray>
 *     <speciesArray datasrc="#species_Li(Fixed)">
 *       LiFixed
 *     </speciesArray>
 *     <thermo model="FixedChemPot">
 *       <chemicalPotential units="J/kmol"> -2.3E7  </chemicalPotential>
 *     </thermo>
 *     <transport model="None"/>
 *     <kinetics model="none"/>
 *   </phase>
 *
 *   <!-- species definitions     -->
 *   <speciesData id="species_Li(Fixed)">
 *     <species name="LiFixed">
 *       <atomArray> Li:1 </atomArray>
 *       <thermo>
 *         <Shomate Pref="1 bar" Tmax="1075.0" Tmin="250.0">
 *           <floatArray size="7">
 *             50.72389, 6.672267, -2.517167,
 *             10.15934, -0.200675, -427.2115,
 *             130.3973
 *           </floatArray>
 *         </Shomate>
 *       </thermo>
 *     </species>
 *   </speciesData>
 * </ctml>
 * @endcode
 *
 * The model attribute, "FixedChemPot", on the thermo element
 * identifies the phase as being a FixedChemPotSSTP object.
 *
 * @ingroup thermoprops
 *
 * @deprecated To be removed after Cantera 2.5. Use the `fixed-stoichiometry`
 *     thermo model (class StoichSubstance) with a `constant-cp` species thermo
 *     model, `h0` set to the desired chemical potential, and `s0` set to 0.
 */
class FixedChemPotSSTP : public SingleSpeciesTP
{
public:
    //! Default constructor for the FixedChemPotSSTP class
    FixedChemPotSSTP();
 
    //! Construct and initialize a FixedChemPotSSTP ThermoPhase object
    //! directly from an ASCII input file
    /*!
     * @param infile name of the input file
     * @param id     name of the phase id in the file.
     *               If this is blank, the first phase in the file is used.
     */
    FixedChemPotSSTP(const std::string& infile, const std::string& id = "");
 
    //! Construct and initialize a FixedChemPotSSTP ThermoPhase object
    //! directly from an XML database
    /*!
     *  @param phaseRef XML node pointing to a FixedChemPotSSTP description
     *  @param id       Id of the phase.
     */
    FixedChemPotSSTP(XML_Node& phaseRef, const std::string& id = "");
 
    //! Special constructor for the FixecChemPotSSTP class setting an element
    //! chemical potential directly
    /*!
     *  This will create a FixedChemPotSSTP consisting of a single species with the
     *  stoichiometry of one of the specified atom. It will have a chemical potential
     *  that is given by the second argument.
     *
     *  @param Ename String name of the element
     *  @param chemPot  Value of the chemical potential of that element (J/kmol)
     */
    FixedChemPotSSTP(const std::string& Ename, doublereal chemPot);
 
    virtual std::string type() const {
        return "FixedChemPot";
    }
 
    virtual bool isCompressible() const {
        return false;
    }
 
    //! @}
    //! @name Mechanical Equation of State
    //! @{
 
    //! Report the Pressure. Units: Pa.
    /*!
     * For an incompressible substance, the density is independent of pressure.
     * This method simply returns the stored pressure value.
     */
    virtual doublereal pressure() const;
 
    //! Set the pressure at constant temperature. Units: Pa.
    /*!
     * For an incompressible substance, the density is independent of pressure.
     * Therefore, this method only stores the specified pressure value. It does
     * not modify the density.
     *
     * @param p Pressure (units - Pa)
     */
    virtual void setPressure(doublereal p);
 
    virtual doublereal isothermalCompressibility() const;
    virtual doublereal thermalExpansionCoeff() const;
 
    /**
     * @}
     * @name Activities, Standard States, and Activity Concentrations
     *
     *  This section is largely handled by parent classes, since there
     *  is only one species. Therefore, the activity is equal to one.
     * @{
     */
 
    virtual Units standardConcentrationUnits() const;
 
    //! @copydoc ThermoPhase::getActivityConcentrations
    /*!
     * For a stoichiometric substance, there is only one species, and the
     * generalized concentration is 1.0.
     */
    virtual void getActivityConcentrations(doublereal* c) const;
 
    //! Return the standard concentration for the kth species
    /*!
     * The standard concentration \f$ C^0_k \f$ used to normalize the activity
     * (i.e., generalized) concentration. This phase assumes that the kinetics
     * operator works on an dimensionless basis. Thus, the standard
     * concentration is equal to 1.0.
     *
     * @param k Optional parameter indicating the species. The default is to
     *         assume this refers to species 0.
     * @return
     *   Returns The standard Concentration as 1.0
     */
    virtual doublereal standardConcentration(size_t k=0) const;
    virtual doublereal logStandardConc(size_t k=0) const;
 
    //! Get the array of chemical potentials at unit activity for the species at
    //! their standard states at the current *T* and *P* of the solution.
    /*!
     * For a stoichiometric substance, there is no activity term in the chemical
     * potential expression, and therefore the standard chemical potential and
     * the chemical potential are both equal to the molar Gibbs function.
     *
     * These are the standard state chemical potentials \f$ \mu^0_k(T,P) \f$.
     * The values are evaluated at the current temperature and pressure of the
     * solution
     *
     * @param mu0     Output vector of chemical potentials. Length: m_kk.
     */
    virtual void getStandardChemPotentials(doublereal* mu0) const;
 
    //@}
    /// @name Partial Molar Properties of the Solution
    /// These properties are handled by the parent class, SingleSpeciesTP
    //@{
 
    //! Get the species partial molar volumes. Units: m^3/kmol.
    /*!
     * This is the phase molar volume.  \f$ V(T,P) = V_o(T,P) \f$.
     *
     * set to zero.
     *
     *  @param vbar On return, contains the molar volume of the single species
     *              and the phase. Units are m^3 / kmol. Length = 1
     */
    virtual void getPartialMolarVolumes(doublereal* vbar) const;
 
    //@}
    /// @name  Properties of the Standard State of the Species in the Solution
    //@{
 
    virtual void getEnthalpy_RT(doublereal* hrt) const;
    virtual void getEntropy_R(doublereal* sr) const;
    virtual void getGibbs_RT(doublereal* grt) const;
    virtual void getCp_R(doublereal* cpr) const;
 
    //! Returns the vector of nondimensional Internal Energies of the standard
    //! state species at the current *T* and *P* of the solution
    /*!
     * For an incompressible, stoichiometric substance, the molar internal
     * energy is independent of pressure. Since the thermodynamic properties are
     * specified by giving the standard-state enthalpy, the term \f$ P_{ref}
     * \hat v\f$ is subtracted from the specified reference molar enthalpy to
     * compute the standard state molar internal energy.
     *
     * @param urt  output vector of nondimensional standard state
     *             internal energies of the species. Length: m_kk.
     */
    virtual void getIntEnergy_RT(doublereal* urt) const;
 
    //! Get the molar volumes of each species in their standard states at the
    //! current *T* and *P* of the solution.
    /*
     * units = m^3 / kmol
     *
     * We set this to zero
     *
     * @param vbar On output this contains the standard volume of the species
     *             and phase (m^3/kmol). Vector of length 1
     */
    virtual void getStandardVolumes(doublereal* vbar) const;
 
    //@}
    /// @name Thermodynamic Values for the Species Reference States
    //@{
 
    virtual void getIntEnergy_RT_ref(doublereal* urt) const;
    virtual void getEnthalpy_RT_ref(doublereal* hrt) const;
    virtual void getGibbs_RT_ref(doublereal* grt) const;
    virtual void getGibbs_ref(doublereal* g) const;
    virtual void getEntropy_R_ref(doublereal* er) const;
    virtual void getCp_R_ref(doublereal* cprt) const;
 
    //@}
 
    virtual void initThermoXML(XML_Node& phaseNode, const std::string& id);
 
    virtual void initThermo();
 
    //! Set the equation of state parameters
    /*!
     * @internal
     * @param n number of parameters = 1
     * @param c array of \a n coefficients
     *        c[0] = density of phase [ kg/m3 ]
     */
    virtual void setParameters(int n, doublereal* const c);
 
    //! Get the equation of state parameters in a vector
    /*!
     * @internal
     *
     * @param n number of parameters
     * @param c array of \a n coefficients
     *
     *  For this phase:
     *       -  n = 1
     *       -  c[0] = density of phase [ kg/m3 ]
     */
    virtual void getParameters(int& n, doublereal* const c) const;
 
    //! Set equation of state parameter values from XML entries.
    /*!
     * This method is called by function importPhase() when processing a phase
     * definition in an input file. It should be overloaded in subclasses to set
     * any parameters that are specific to that particular phase model. Note,
     * this method is called before the phase is initialized with elements
     * and/or species.
     *
     * For this phase, the chemical potential is set.
     *
     * @param eosdata An XML_Node object corresponding to
     *                the "thermo" entry for this phase in the input file.
     *
     * eosdata points to the thermo block, and looks like this:
     *
     * @code
     *   <phase id="stoichsolid" >
     *     <thermo model="FixedChemPot">
     *       <chemicalPotential units="J/kmol"> -2.7E7 </chemicalPotential>
     *     </thermo>
     *   </phase>
     * @endcode
     */
    virtual void setParametersFromXML(const XML_Node& eosdata);
 
    //! Function to set the chemical potential directly
    /*!
     *  @param chemPot  Value of the chemical potential (units J/kmol)
     */
    void setChemicalPotential(doublereal chemPot);
 
protected:
    //!  Value of the chemical potential of the bath species
    /*!
     *  units are J/kmol
     */
    doublereal chemPot_;
};
 
}
 
#endif