MetalSHEelectrons.h

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/**
 * @file MetalSHEelectrons.h
 * Header file for the %MetalSHEElectrons class, which represents the
 * electrons in a metal that are consistent with the
 * SHE electrode (see \ref thermoprops and
 * class \link Cantera::MetalSHEelectrons MetalSHEelectrons\endlink)
 */

/*
 * Copyright (2005) Sandia Corporation. Under the terms of
 * Contract DE-AC04-94AL85000 with Sandia Corporation, the
 * U.S. Government retains certain rights in this software.
 */
#ifndef CT_METALSHEELECTRONS_H
#define CT_METALSHEELECTRONS_H

#include "mix_defs.h"
#include "SingleSpeciesTP.h"

namespace Cantera
{

//!  Class %MetalSHEelectrons represents electrons within
//!  a metal, adjacent to an aqueous electrolyte, that are consistent with the SHE reference electrode.
/*!
 *  The class is based on the electron having a chemical potential
 *  equal to one-half of the entropy of the H<SUP>2</SUP> gas at the system pressure
 *
 * <b> Specification of Species Standard %State Properties </b>
 *
 *  This class inherits from SingleSpeciesTP.
 *  It is assumed that the reference state thermodynamics may be
 *  obtained by a pointer to a populated species thermodynamic property
 *  manager class (see ThermoPhase::m_spthermo). How to relate pressure
 *  changes to the reference state thermodynamics is resolved at this level.
 *
 * The enthalpy function is given by the following relation.
 *
 *       \f[
 *            h^o_k(T,P) = h^{ref}_k(T)
 *       \f]
 *
 *  The standard state constant-pressure heat capacity is independent of pressure:
 *
 *       \f[
 *            Cp^o_k(T,P) = Cp^{ref}_k(T)
 *       \f]
 *
 *  The standard state entropy depends in the following fashion on pressure:
 *
 *       \f[
 *            S^o_k(T,P) = S^{ref}_k(T) -  R \ln(\frac{P}{P_{ref}})
 *       \f]
 *
 *  The standard state gibbs free energy is obtained from the enthalpy and entropy
 *  functions:
 *
 *       \f[
 *            \mu^o_k(T,P) =  h^o_k(T,P) - S^o_k(T,P) T
 *       \f]
 *
 *       \f[
 *            \mu^o_k(T,P) =  \mu^{ref}_k(T) + R T \ln( \frac{P}{P_{ref}})
 *       \f]
 *
 * where
 *       \f[
 *            \mu^{ref}_k(T) =   h^{ref}_k(T)   - T S^{ref}_k(T)
 *       \f]
 *
 *  The standard state internal energy is obtained from the enthalpy function also
 *
 *       \f[
 *            u^o_k(T,P) = h^o_k(T) - R T
 *       \f]
 *
 * <b> Specification of Solution Thermodynamic Properties </b>
 *
 *  All solution properties are obtained from the standard state
 *  species functions, since there is only one species in the phase.
 *
 * <b> %Application within %Kinetics Managers </b>
 *
 *  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 since the activity is
 *  always equal to one.
 *
 *  This is what is expected of electrons. The only effect that this class will
 *  have on reactions is in terms of the standard state chemical potential, which
 *  is equal to 1/2 of the H2 gas chemical potential, and the voltage assigned
 *  to the electron, which is the voltage of the metal.
 *
 * <b> Instantiation of the Class </b>
 *
 * The constructor for this phase is located in the default ThermoFactory
 * for %Cantera. A new %MetalSHEelectrons object may be created by
 * the following code snippets, where the file metalSHEelectrons.xml exists
 * in a local directory:
 *
 * @code
 *    MetalSHEelectrons *eMetal = new MetalSHEelectrons("metalSHEelectrons.xml", "");
 * @endcode
 *
 * or by the following call to importPhase():
 *
 * @code
 *    sprintf(file_ID,"%s#MetalSHEelectrons", iFile);
 *    XML_Node *xm = get_XML_NameID("phase", file_ID, 0);
 *    MetalSHEelectrons eMetal;
 *    importPhase(*xm, &eMetal);
 * @endcode
 *
 *  @code
 *  ThermoPhase *eMetal = newPhase("MetalSHEelectrons.xml", "MetalSHEelectrons");
 *  @endcode
 *
 *   Additionally, this phase may be created without including an xml file with
 *   the special command, where the default file is embedded into this object.
 *
 * @code
 *    MetalSHEelectrons *eMetal = new MetalSHEelectrons("MetalSHEelectrons_default.xml", "");
 * @endcode
 *
 *   <b> XML Example </b>
 *
 * The phase model name for this is called %MetalSHEelectrons. It must be supplied
 * as the model attribute of the thermo XML element entry.
 * Within the phase XML block,
 * the density of the phase must be specified though it's not used. An example of an XML file
 * this phase is given below.
 *
 * @code
 * <?xml version="1.0"?>
 * <ctml>
 *   <validate reactions="yes" species="yes"/>
 *
 *   <phase dim="3" id="MetalSHEelectrons">
 *     <elementArray datasrc="elements.xml">
 *         E
 *     </elementArray>
 *     <speciesArray datasrc="#species_Metal_SHEelectrons"> she_electron </speciesArray>
 *     <thermo model="metalSHEelectrons">
 *       <density units="g/cm3">2.165</density>
 *     </thermo>
 *     <transport model="None"/>
 *     <kinetics model="none"/>
 *   </phase>
 *
 *   <!-- species definitions     -->
 *   <speciesData id="species_Metal_SHEelectrons">
 *     <species name="she_electron">
 *       <atomArray> E:1  </atomArray>
 *       <charge> -1 </charge>
 *       <thermo>
 *         <NASA Tmax="1000.0" Tmin="200.0" P0="100000.0">
 *          <floatArray name="coeffs" size="7">
 *           1.172165560E+00,   3.990260375E-03,  -9.739075500E-06,  1.007860470E-08,
 *          -3.688058805E-12, -4.589675865E+02,  3.415051190E-01
 *          </floatArray>
 *         </NASA>
 *         <NASA Tmax="6000.0" Tmin="1000.0" P0="100000.0">
 *            <floatArray name="coeffs" size="7">
 *              1.466432895E+00,  4.133039835E-04, -7.320116750E-08, 7.705017950E-12,
 *             -3.444022160E-16, -4.065327985E+02, -5.121644350E-01
 *           </floatArray>
 *         </NASA>
 *       </thermo>
 *       <density units="g/cm3">2.165</density>
 *     </species>
 *   </speciesData>
 * </ctml>
 * @endcode
 *
 * The model attribute, "MetalSHEelectrons", on the thermo element
 * identifies the phase as being a %MetalSHEelectrons object.
 *
 * @ingroup thermoprops
 */
class MetalSHEelectrons : public SingleSpeciesTP
{
public:
    //! Default constructor for the MetalSHEelectrons class
    MetalSHEelectrons();

    //! Construct and initialize a %MetalSHEelectrons %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.
     */
    MetalSHEelectrons(const std::string& infile, std::string id = "");

    //! Construct and initialize a MetalSHEelectrons ThermoPhase object
    //! directly from an XML database
    /*!
     *  @param phaseRef XML node pointing to a MetalSHEelectrons description
     *  @param id       Id of the phase.
     */
    MetalSHEelectrons(XML_Node& phaseRef, const std::string& id = "");

    //! Copy constructor
    /*!
     * @param right Object to be copied
     */
    MetalSHEelectrons(const MetalSHEelectrons&  right);

    //! Assignment operator
    /*!
     * @param right Object to be copied
     */
    MetalSHEelectrons& operator=(const MetalSHEelectrons& right);

    //! Destructor for the routine
    virtual ~MetalSHEelectrons();

    //! Duplication function
    /*!
     * This virtual function is used to create a duplicate of the
     * current phase. It's used to duplicate the phase when given
     * a ThermoPhase pointer to the phase.
     *
     * @return It returns a ThermoPhase pointer.
     */
    ThermoPhase* duplMyselfAsThermoPhase() const;

    /**
     * Equation of state flag.
     *
     * Returns the value cMetalSHEelectrons, defined in mix_defs.h.
     */
    virtual int eosType() const;

    //! @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);

    //! Returns  the isothermal compressibility. Units: 1/Pa.
    /*!
     * The isothermal compressibility is defined as
     * \f[
     * \kappa_T = -\frac{1}{v}\left(\frac{\partial v}{\partial P}\right)_T
     * \f]
     */
    virtual doublereal isothermalCompressibility() const;

    //! Return the volumetric thermal expansion coefficient. Units: 1/K.
    /*!
     * The thermal expansion coefficient is defined as
     * \f[
     * \beta = \frac{1}{v}\left(\frac{\partial v}{\partial T}\right)_P
     * \f]
     */
    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.
    //! @{

    //! This method returns an array of generalized concentrations
    /*!
     * \f$ C^a_k\f$ are defined such that \f$ a_k = C^a_k /
     * C^0_k, \f$ where \f$ C^0_k \f$ is a standard concentration
     * defined below and \f$ a_k \f$ are activities used in the
     * thermodynamic functions.  These activity (or generalized)
     * concentrations are used
     * by kinetics manager classes to compute the forward and
     * reverse rates of elementary reactions.
     *
     *  For a stoichiometric substance, there is
     *  only one species, and the generalized concentration is 1.0.
     *
     * @param c Output array of generalized concentrations. The
     *           units depend upon the implementation of the
     *           reaction rate expressions within the phase.
     */
    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;

    //! Natural logarithm of the standard concentration of the kth species.
    /*!
     * @param k    index of the species (defaults to zero)
     */
    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 <I>T</I> and <I>P</I> 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;

    //! Returns the units of the standard and generalized concentrations.
    /*!
     * Note they have the same units, as their
     * ratio is defined to be equal to the activity of the kth
     * species in the solution, which is unitless.
     *
     * This routine is used in print out applications where the
     * units are needed. Usually, MKS units are assumed throughout
     * the program and in the XML input files.
     *
     * The base %ThermoPhase class assigns the default quantities
     * of (kmol/m3) for all species.
     * Inherited classes are responsible for overriding the default
     * values if necessary.
     *
     * @param uA Output vector containing the units
     *     uA[0] = kmol units - default  = 1
     *     uA[1] = m    units - default  = -nDim(), the number of spatial
     *                                   dimensions in the Phase class.
     *     uA[2] = kg   units - default  = 0;
     *     uA[3] = Pa(pressure) units - default = 0;
     *     uA[4] = Temperature units - default = 0;
     *     uA[5] = time units - default = 0
     * @param k species index. Defaults to 0.
     * @param sizeUA output int containing the size of the vector.
     *        Currently, this is equal to 6.
     * @deprecated
     */
    virtual void getUnitsStandardConc(doublereal* uA, int k = 0,
                                      int sizeUA = 6) const;

    //@}
    /// @name  Properties of the Standard State of the Species in the Solution
    //@{

    //! Get the nondimensional Enthalpy functions for the species
    //! at their standard states at the current <I>T</I> and <I>P</I> of the solution.
    /*!
     * @param hrt      Output vector of  nondimensional standard state enthalpies.
     *                 Length: m_kk.
     */
    virtual void getEnthalpy_RT(doublereal* hrt) const;

    //! Get the array of nondimensional Entropy functions for the
    //! standard state species at the current <I>T</I> and <I>P</I> of the solution.
    /*!
     * @param sr   Output vector of  nondimensional standard state entropies.
     *             Length: m_kk.
     */
    virtual void getEntropy_R(doublereal* sr) const;

    //! Get the nondimensional Gibbs functions for the species
    //! in their standard states at the current <I>T</I> and <I>P</I> of the solution.
    /*!
     * @param grt  Output vector of nondimensional standard state gibbs free energies
     *             Length: m_kk.
     */
    virtual void getGibbs_RT(doublereal* grt) const;

    //! Get the nondimensional Heat Capacities at constant
    //! pressure for the species standard states
    //! at the current <I>T</I> and <I>P</I> of the solution
    /*!
     * @param cpr   Output vector of nondimensional standard state heat capacities
     *              Length: m_kk.
     */
    virtual void getCp_R(doublereal* cpr) const;

    //!  Returns the vector of nondimensional Internal Energies  of the standard
    //!  state species at the current <I>T</I> and <I>P</I> 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;

    //@}
    /// @name Thermodynamic Values for the Species Reference States
    //@{

    //! Returns the vector of nondimensional
    //!  internal Energies of the reference state at the current temperature
    //!  of the solution and the reference pressure for each species.
    /*!
     * @param urt    Output vector of nondimensional reference state
     *               internal energies of the species.
     *               Length: m_kk
     */
    virtual void getIntEnergy_RT_ref(doublereal* urt) const;
    // @}

    /*
     * @internal Initialize. This method is provided to allow
     * subclasses to perform any initialization required after all
     * species have been added. For example, it might be used to
     * resize internal work arrays that must have an entry for
     * each species.  The base class implementation does nothing,
     * and subclasses that do not require initialization do not
     * need to overload this method.  When importing a CTML phase
     * description, this method is called just prior to returning
     * from function importPhase.setParameters
     *
     * @see importCTML.cpp
     */
    virtual void initThermo();

    virtual void initThermoXML(XML_Node& phaseNode, const std::string& id);

    //! Make the default XML tree
    /*!
     *   @return Returns a malloced XML tree containing the
     *           default info.
     */
    static XML_Node* makeDefaultXMLTree();

    //! Set the equation of state parameters
    /*!
     * @internal
     *
     * @param n number of parameters
     * @param c array of \a n coefficients
     *        c[0] = density of phase [ kg/m3 ]
     * @deprecated Use setDensity()
     */
    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 ]
     * @deprecated Use density()
     */
    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() in
     * file importCTML.cpp 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 density of the phase is specified in this block.
     *
     * @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="StoichSubstance">
     *     <density units="g/cm3">3.52</density>
     *   </thermo>
     * </phase>
     * @endcode
     */
    virtual void setParametersFromXML(const XML_Node& eosdata);

protected:
    XML_Node* xdef_;
};

}
#endif