VPStandardStateTP.h

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/**
 *  @file VPStandardStateTP.h
 *    Header file for a derived class of ThermoPhase that handles
 *    variable pressure standard state methods for calculating
 *    thermodynamic properties (see \ref thermoprops and
 *    class \link Cantera::VPStandardStateTP VPStandardStateTP\endlink).
 *
 *    These include most of the
 *    methods for calculating liquid electrolyte thermodynamics.
 */
/*
 * 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_VPSTANDARDSTATETP_H
#define CT_VPSTANDARDSTATETP_H

#include "ThermoPhase.h"
#include "VPSSMgr.h"

namespace Cantera
{

class XML_Node;
class PDSS;

/**
 * @ingroup thermoprops
 *
 *  This is a filter class for ThermoPhase that implements some prepatory
 *  steps for efficiently handling
 *  a variable pressure standard state for species.
 *
 *  Several concepts are introduced. The first concept is there are temporary
 *  variables for holding the species standard state values
 *  of Cp, H, S, G, and V at the
 *  last temperature and pressure called. These functions are not recalculated
 *  if a new call is made using the previous temperature and pressure. Currently,
 *  these variables and the calculation method are handled by the VPSSMgr class,
 *  for which VPStandardStateTP owns a pointer to.
 *
 *  To support the above functionality, pressure and temperature variables,
 *  m_Plast_ss and m_Tlast_ss, are kept which store the last pressure and temperature
 *  used in the evaluation of standard state properties.
 *
 *  This class is usually used for nearly incompressible phases. For those phases, it
 *  makes sense to change the equation of state independent variable from
 *  density to pressure. The variable m_Pcurrent contains the current value of the
 *  pressure within the phase.
 *
 * @todo
 *   Put some teeth into this level by overloading the setDensity() function. It should
 *   now throw an exception. Instead, setPressure routines should calculate the
 *   solution density and then call State:setDensity() directly.
 *
 *  @nosubgrouping
 */
class VPStandardStateTP : public ThermoPhase
{

public:
    //! @name Constructors and Duplicators for %VPStandardStateTP

    /// Constructor.
    VPStandardStateTP();

    //! Copy Constructor.
    /*!
     *  @param b   Object to be copied
     */
    VPStandardStateTP(const VPStandardStateTP& b);

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

    //! Destructor.
    virtual ~VPStandardStateTP();

    //! Duplication routine
    virtual ThermoPhase* duplMyselfAsThermoPhase() const;

    //@}
    //! @name  Utilities (VPStandardStateTP)
    //@{
    /**
     * Equation of state type flag. The base class returns
     * zero. Subclasses should define this to return a unique
     * non-zero value. Constants defined for this purpose are
     * listed in mix_defs.h.
     */
    virtual int eosType() const {
        return 0;
    }

    //! This method returns the convention used in specification
    //! of the standard state, of which there are currently two,
    //! temperature based, and variable pressure based.
    /*!
     * Currently, there are two standard state conventions:
     *  - Temperature-based activities,
     *    `cSS_CONVENTION_TEMPERATURE 0` (default)
     *  - Variable Pressure and Temperature-based activities,
     *    `cSS_CONVENTION_VPSS 1`
     */
    virtual int standardStateConvention() const;

    //! Get the array of log concentration-like derivatives of the
    //! log activity coefficients
    /*!
     * This function is a virtual method.  For ideal mixtures
     * (unity activity coefficients), this can return zero.
     * Implementations should take the derivative of the
     * logarithm of the activity coefficient with respect to the
     * logarithm of the concentration-like variable (i.e. moles)
     *  that represents the standard state.
     * This quantity is to be used in conjunction with derivatives of
     * that concentration-like variable when the derivative of the chemical
     * potential is taken.
     *
     *  units = dimensionless
     *
     * @param dlnActCoeffdlnN_diag    Output vector of derivatives of the
     *                         log Activity Coefficients. length = m_kk
     */
    virtual void getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const {
        err("getdlnActCoeffdlnN_diag");
    }

    //@}
    /// @name  Partial Molar Properties of the Solution (VPStandardStateTP)
    //@{

    //! Get the array of non-dimensional species chemical potentials.
    /*!
     * These are partial molar Gibbs free energies,
     * \f$ \mu_k / \hat R T \f$.
     *
     * We close the loop on this function, here, calling
     * getChemPotentials() and then dividing by RT. No need for child
     * classes to handle.
     *
     * @param mu    Output vector of  non-dimensional species chemical potentials
     *              Length: m_kk.
     */
    void getChemPotentials_RT(doublereal* mu) const;

    //@}

    /*!
     * @name  Properties of the Standard State of the Species in the Solution (VPStandardStateTP)
     *
     *  Within VPStandardStateTP, these properties are calculated via a common routine,
     *  _updateStandardStateThermo(), which must be overloaded in inherited
     *  objects. The values are cached within this object, and are not
     *  recalculated unless the temperature or pressure changes.
     */
    //@{

    //!Get the array of chemical potentials at unit activity.
    /*!
     * These are the standard state chemical potentials \f$ \mu^0_k(T,P)
     * \f$. The values are evaluated at the current temperature and pressure.
     *
     * @param mu   Output vector of standard state chemical potentials.
     *             length = m_kk. units are J / kmol.
     */
    virtual void getStandardChemPotentials(doublereal* mu) const;

    /**
     * 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 standard state enthalpies.
     *                length = m_kk. units are unitless.
     */
    virtual void getEnthalpy_RT(doublereal* hrt) const;

    /**
     * Get the array of nondimensional Enthalpy 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
     * at their standard states of solution at the current T and P
     * 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 standard state Gibbs functions for each species
    //! at the current T and P.
    /*!
     *  (Note resolved at this level)
     *
     * @param gpure  Output vector of standard state
     *               Gibbs free energies. length = m_kk.
     *               units are J/kmol.
     */
    void getPureGibbs(doublereal* gpure) const;

    /**
     *  Returns the vector of nondimensional
     *  internal Energies of the standard state at the current temperature
     *  and pressure of the solution for each species.
     * \f[
     *  u^{ss}_k(T,P) = h^{ss}_k(T)  - P * V^{ss}_k
     * \f]
     *
     * @param urt    Output vector of nondimensional standard state
     *               internal energies. length = m_kk.
     */
    virtual void getIntEnergy_RT(doublereal* urt) const;

    /**
     * Get the nondimensional Heat Capacities at constant
     * pressure for the standard state of the species
     * at the current T and P.
     *
     * This is redefined here to call the internal function,  _updateStandardStateThermo(),
     * which calculates all standard state properties at the same time.
     *
     * @param cpr    Output vector containing the
     *               the nondimensional Heat Capacities at constant
     *               pressure for the standard state of the species.
     *               Length: m_kk.
     */
    virtual void getCp_R(doublereal* cpr) const;


    //! Get the molar volumes of each species in their standard
    //! states at the current
    //! <I>T</I> and <I>P</I> of the solution.
    /*!
     * units = m^3 / kmol
     *
     * This is redefined here to call the internal function,  _updateStandardStateThermo(),
     * which calculates all standard state properties at the same time.
     *
     * @param vol Output vector of species volumes. length = m_kk.
     *            units =  m^3 / kmol
     */
    virtual void getStandardVolumes(doublereal* vol) const;
    virtual const vector_fp& getStandardVolumes() const;

    //! Set the temperature of the phase
    /*!
     *    Currently this passes down to setState_TP(). It does not
     *    make sense to calculate the standard state without first
     *    setting T and P.
     *
     * @param temp  Temperature (kelvin)
     */
    virtual void setTemperature(const doublereal temp);

    //! Set the internally stored pressure (Pa) at constant
    //! temperature and composition
    /*!
     *  Currently this passes down to setState_TP().  It does not
     *    make sense to calculate the standard state without first
     *    setting T and P.
     *
     *  @param p input Pressure (Pa)
     */
    virtual void setPressure(doublereal p);

protected:
    /**
     * Calculate the density of the mixture using the partial
     * molar volumes and mole fractions as input
     *
     * The formula for this is
     *
     * \f[
     * \rho = \frac{\sum_k{X_k W_k}}{\sum_k{X_k V_k}}
     * \f]
     *
     * where \f$X_k\f$ are the mole fractions, \f$W_k\f$ are
     * the molecular weights, and \f$V_k\f$ are the pure species
     * molar volumes.
     *
     * Note, the basis behind this formula is that in an ideal
     * solution the partial molar volumes are equal to the pure
     * species molar volumes. We have additionally specified
     * in this class that the pure species molar volumes are
     * independent of temperature and pressure.
     *
     * NOTE: This is a non-virtual function, which is not a
     *       member of the ThermoPhase base class.
     */
    virtual void calcDensity();

public:
    //! Set the temperature and pressure at the same time
    /*!
     *  Note this function triggers a reevaluation of the standard
     *  state quantities.
     *
     *  @param T  temperature (kelvin)
     *  @param pres pressure (pascal)
     */
    virtual void setState_TP(doublereal T, doublereal pres);

    //! Returns the current pressure of the phase
    /*!
     *  The pressure is an independent variable in this phase. Its current value
     *  is stored in the object VPStandardStateTP.
     *
     * @return return the pressure in pascals.
     */
    doublereal pressure() const {
        return m_Pcurrent;
    }

protected:

    //! Updates the standard state thermodynamic functions at the current T and P of the solution.
    /*!
     * @internal
     *
     * If m_useTmpStandardStateStorage is true,
     * this function must be called for every call to functions in this  class.
     *
     * This function is responsible for updating the following internal members,
     * when  m_useTmpStandardStateStorage is true.
     *
     *  -  m_hss_RT;
     *  -  m_cpss_R;
     *  -  m_gss_RT;
     *  -  m_sss_R;
     *  -  m_Vss
     *
     *  This function doesn't check to see if the temperature or pressure
     *  has changed. It automatically assumes that it has changed.
     *  If m_useTmpStandardStateStorage is not true, this function may be
     *  required to be called by child classes to update internal member data..
     *
     */
    virtual void _updateStandardStateThermo() const;

public:

    //! Updates the standard state thermodynamic functions at the current T and P of the solution.
    /*!
     *
     * If m_useTmpStandardStateStorage is true,
     * this function must be called for every call to functions in this
     * class. It checks to see whether the temperature or pressure has changed and
     * thus the ss thermodynamics functions for all of the species
     * must be recalculated.
     *
     * This function is responsible for updating the following internal members,
     * when  m_useTmpStandardStateStorage is true.
     *
     *  -  m_hss_RT;
     *  -  m_cpss_R;
     *  -  m_gss_RT;
     *  -  m_sss_R;
     *  -  m_Vss
     *
     *  If m_useTmpStandardStateStorage is not true, this function may be
     *  required to be called by child classes to update internal member data.
     *
     */
    virtual void updateStandardStateThermo() const;

    //@}
    /// @name Thermodynamic Values for the Species Reference States (VPStandardStateTP)
    /*!
     *  There are also temporary
     *  variables for holding the species reference-state values of Cp, H, S, and V at the
     *  last temperature and reference pressure called. These functions are not recalculated
     *  if a new call is made using the previous temperature.
     *  All calculations are done within the routine  _updateRefStateThermo().
     */
    //@{

    //!  Returns the vector of nondimensional
    //!  enthalpies of the reference state at the current temperature
    //!  of the solution and the reference pressure for the species.
    /*!
     * @param hrt Output vector contains the nondimensional enthalpies
     *            of the reference state of the species
     *            length = m_kk, units = dimensionless.
     */
    virtual void getEnthalpy_RT_ref(doublereal* hrt) const;

#ifdef H298MODIFY_CAPABILITY
    //!  Modify the value of the 298 K Heat of Formation of the standard state of
    //!  one species in the phase (J kmol-1)
    /*!
     *   The 298K heat of formation is defined as the enthalpy change to create the standard state
     *   of the species from its constituent elements in their standard states at 298 K and 1 bar.
     *
     *   @param  k           Index of the species
     *   @param  Hf298New    Specify the new value of the Heat of Formation at 298K and 1 bar.
     *                       units = J/kmol.
     */
    void modifyOneHf298SS(const size_t& k, const doublereal Hf298New);
#endif

    //!  Returns the vector of nondimensional
    //!  Gibbs free energies of the reference state at the current temperature
    //!  of the solution and the reference pressure for the species.
    /*!
     * @param grt Output vector contains the nondimensional Gibbs free energies
     *            of the reference state of the species
     *            length = m_kk, units = dimensionless.
     */
    virtual void getGibbs_RT_ref(doublereal* grt) const;

protected:
    const vector_fp& Gibbs_RT_ref() const;
public:
    /*!
     *  Returns the vector of the
     *  gibbs function of the reference state at the current temperature
     *  of the solution and the reference pressure for the species.
     *  units = J/kmol
     *
     * @param g   Output vector contain the Gibbs free energies
     *            of the reference state of the species
     *            length = m_kk, units = J/kmol.
     */
    virtual void getGibbs_ref(doublereal* g) const;

    /*!
     *  Returns the vector of nondimensional
     *  entropies of the reference state at the current temperature
     *  of the solution and the reference pressure for the species.
     *
     * @param er  Output vector contain the nondimensional entropies
     *            of the species in their reference states
     *            length: m_kk, units: dimensionless.
     */
    virtual void getEntropy_R_ref(doublereal* er) const;

    /*!
     *  Returns the vector of nondimensional
     *  constant pressure heat capacities of the reference state
     *  at the current temperature of the solution
     *  and reference pressure for the species.
     *
     * @param cprt Output vector contains the nondimensional heat capacities
     *             of the species in their reference states
     *             length: m_kk, units: dimensionless.
     */
    virtual void getCp_R_ref(doublereal* cprt) const;

    //!  Get the molar volumes of the species reference states at the current
    //!  <I>T</I> and <I>P_ref</I> of the solution.
    /*!
     * units = m^3 / kmol
     *
     * @param vol     Output vector containing the standard state volumes.
     *                Length: m_kk.
     */
    virtual void getStandardVolumes_ref(doublereal* vol) const;
    //@}

public:
    //! @name Initialization Methods - For Internal use (VPStandardState)
    /*!
     * The following methods are used in the process of constructing
     * the phase and setting its parameters from a specification in an
     * input file. They are not normally used in application programs.
     * To see how they are used, see files importCTML.cpp and
     * ThermoFactory.cpp.
     */
    //@{

    /**
     * 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.
     *
     * @param eosdata An XML_Node object corresponding to
     *                the "thermo" entry for this phase in the input file.
     */
    virtual void setParametersFromXML(const XML_Node& eosdata) {}

    virtual void initThermo();

    //!   Initialize a ThermoPhase object, potentially reading activity
    //!   coefficient information from an XML database.
    /*!
     * This routine initializes the lengths in the current object and
     * then calls the parent routine.
     * 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().
     *
     * @param phaseNode This object must be the phase node of a
     *             complete XML tree
     *             description of the phase, including all of the
     *             species data. In other words while "phase" must
     *             point to an XML phase object, it must have
     *             sibling nodes "speciesData" that describe
     *             the species in the phase.
     * @param id   ID of the phase. If nonnull, a check is done
     *             to see if phaseNode is pointing to the phase
     *             with the correct id.
     */
    virtual void initThermoXML(XML_Node& phaseNode, const std::string& id);


    //! set the VPSS Mgr
    /*!
     * @param vp_ptr Pointer to the manager
     */
    void setVPSSMgr(VPSSMgr* vp_ptr);

    //! Return a pointer to the VPSSMgr for this phase
    /*!
     *  @return Returns a pointer to the VPSSMgr for this phase
     */
    VPSSMgr* provideVPSSMgr();

    void createInstallPDSS(size_t k,  const XML_Node& s, const XML_Node* phaseNode_ptr);

    PDSS* providePDSS(size_t k);
    const PDSS* providePDSS(size_t k) const;

private:
    //!  @internal Initialize the internal lengths in this object.
    /*!
     * Note this is not a virtual function.
     */
    void initLengths();

    //@}

protected:

    //! Current value of the pressure - state variable
    /*!
     *  Because we are now using the pressure as a state variable, we need to carry it
     *  along within this object
     *
     *  units = Pascals
     */
    doublereal  m_Pcurrent;

    //! The last temperature at which the standard statethermodynamic properties were calculated at.
    mutable doublereal    m_Tlast_ss;

    //! The last pressure at which the Standard State thermodynamic
    //! properties were calculated at.
    mutable doublereal    m_Plast_ss;

    /*!
     * Reference pressure (Pa) must be the same for all species
     * - defaults to OneAtm
     */
    doublereal m_P0;

    // -> suggest making this private!
protected:

    //! Pointer to the VPSS manager that calculates all of the standard state
    //! info efficiently.
    mutable VPSSMgr* m_VPSS_ptr;

    //! Storage for the PDSS objects for the species
    /*!
     *  Storage is in species index order.
     *  VPStandardStateTp owns each of the objects.
     *  Copy operations are deep.
     */
    std::vector<PDSS*> m_PDSS_storage;

private:
    //! VPStandardStateTP has its own err routine
    /*!
     * @param msg  Error message string
     */
    doublereal err(const std::string& msg) const;

};
}

#endif