LiquidTransport.h

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/**
 *  @file LiquidTransport.h
 *   Header file defining class LiquidTransport
 */
#ifndef CT_LIQUIDTRAN_H
#define CT_LIQUIDTRAN_H

#include "TransportBase.h"
#include "cantera/numerics/DenseMatrix.h"
#include "LiquidTransportParams.h"

namespace Cantera
{
//! Class LiquidTransport implements models for transport
//! properties for liquid phases.
/*!
 *  Liquid Transport is set up with some flexibility in this class.  Transport
 *  properties like viscosity and thermal conductivity are allowed flexibility
 *  within the constraints of the LiquidTransportProperty and
 *  LiquidTransportInteractions classes. For species diffusion, the
 *  LiquidTransport class focuses on the Stefan-Maxwell equation to determine
 *  the diffusion velocities.  Other options for liquid diffusion include
 *  solvent-dominated diffusion, and a class SolventTransport should be
 *  forthcoming.
 *
 *  The class LiquidTransport has several roles.
 *  -# It brings together the individual species transport
 *     properties, expressed as subclasses of LTPspecies
 *     (Liquid Transport Properties of Species) through
 *     LiquidTransportData, with models for
 *     the composition dependence of liquid transport properties
 *     expressed as subclasses of LiquidTranInteraction
 *     (mixing rules) through LiquidTransportParams.  Calculating
 *     mixture properties generally consists of calling the
 *     getMixTansProp member of LiquidTranInteraction by passing
 *     a vector of LTPSpecies
 *  -# It calculates the bulk velocity \f$ \vec{v} \f$ and
 *     individual species diffusion velocities, \f$ \vec{V_i} \f$
 *     using the Stefan-Maxwell equations.  It is possible to set a
 *     flag to calculate relative to a mass-averaged bulk velocity,
 *     relative to a mole-averaged bulk velocity or relative to a
 *     single species velocity using the <velocityBasis basis="mass">,
 *     <velocityBasis basis="mass">, or <velocityBasis basis="Cl-">
 *     keyword. Mass-averaged velocities are the default for which
 *     the diffusion velocities satisfy
 *     \f[
 *        \sum_{i} Y_i \vec{V_i} = 0
 *     \f]
 *     for mass fraction \f$ Y_i \f$.  For mole-averaged velocities
 *     \f[
 *        \sum_{i} X_i \vec{V_i} = 0
 *     \f]
 *     for mole fraction \f$ X_i \f$. or
 *     \f[
 *        \vec{V_i} = 0
 *     \f]
 *     for reference species \f$ i \f$.
 *  -# It provides access to a number of derived quantities
 *     related to transport properties as described in the
 *     various methods below.
 *
 *  Within LiquidTransport, the state is presumed to be
 *  defined in terms of the  species mole fraction,
 *  temperature and pressure.  Charged species are expected
 *  and quantities like the electric current are computed
 *  based on a combined electrochemical potential.
 *
 *
 *  @ingroup tranprops
 */
class LiquidTransport : public Transport
{
public:
    //! Default constructor.
    /*!
     * This requires call to initLiquid(LiquidTransportParams& tr)
     * after filling LiquidTransportParams to complete instantiation.
     * The filling of LiquidTransportParams is currently carried out
     * in the TransportFactory class, but might be moved at some point.
     *
     * @param thermo  ThermoPhase object holding species information.
     * @param ndim    Number of spatial dimensions.
     */
    LiquidTransport(thermo_t* thermo = 0, int ndim = 1);

    LiquidTransport(const LiquidTransport& right);
    LiquidTransport&  operator=(const  LiquidTransport& right);
    virtual Transport* duplMyselfAsTransport() const;
    virtual ~LiquidTransport();

    //! Initialize the transport object
    /*!
     * Here we change all of the internal dimensions to be sufficient.
     * We get the object ready to do property evaluations.
     * A lot of the input required to do property evaluations is
     * contained in the LiquidTransportParams class that is
     * filled in TransportFactory.
     *
     * @param tr  Transport parameters for all of the species in the phase.
     */
    virtual bool initLiquid(LiquidTransportParams& tr);

    friend class TransportFactory;

    virtual int model() const {
        return cLiquidTransport;
    }

    //! Returns the viscosity of the solution
    /*!
     *  The viscosity calculation is handled by subclasses of
     *  LiquidTranInteraction as specified in the input file.
     *  These in turn employ subclasses of LTPspecies to
     *  determine the individual species viscosities.
     */
    virtual doublereal viscosity();

    //! Returns the pure species viscosities for all species
    /*!
     *  The pure species viscosities are evaluated using the appropriate
     *  subclasses of LTPspecies as specified in the input file.
     *
     * @param visc  array of length "number of species"
     *              to hold returned viscosities.
     */
    virtual void getSpeciesViscosities(doublereal* const visc);

    //! Returns the ionic conductivity of the solution
    /*!
     *  The ionic conductivity calculation is handled by subclasses of
     *  LiquidTranInteraction as specified in the input file.
     *  These in turn employ subclasses of LTPspecies to
     *  determine the individual species ionic conductivities.
     */
    virtual doublereal ionConductivity();

    //! Returns the pure species ionic conductivities for all species
    /*!
     *  The pure species ionic conductivities are evaluated using the
     *  appropriate subclasses of LTPspecies as specified in the
     *  input file.
     *
     * @param ionCond  Array of length "number of species" to hold returned
     *     ionic conductivities.
     */
    virtual void getSpeciesIonConductivity(doublereal* const ionCond);

    //! Returns the pointer to the mobility ratios of the binary
    //! combinations of the transported species for the solution
    //! Has size of the number of binary interactions = nsp*nsp
    /*!
     *  The mobility ratio calculation is handled by subclasses of
     *  LiquidTranInteraction as specified in the input file.
     *  These in turn employ subclasses of LTPspecies to
     *  determine the mobility ratios in the pure species.
     *
     *  @param   mobRat           Vector of mobility ratios
     */
    virtual void mobilityRatio(doublereal* mobRat);

    //! Returns a double pointer to the mobility ratios of the
    //! transported species in each pure species phase.
    /*!
     *  Has size of the number of binary interactions by the number of species
     *  (nsp*nsp X nsp). The pure species mobility ratios are evaluated using
     *  the appropriate subclasses of LTPspecies as specified in the input
     *  file.
     *
     * @param mobRat  array of length "number of species"
     *                to hold returned mobility ratios.
     */
    virtual void getSpeciesMobilityRatio(doublereal** mobRat);

    //! Returns the self diffusion coefficients of the species in the phase.
    //! Has size of nsp(coeffs)
    /*!
     *  The self diffusion coefficient is the diffusion coefficient of a
     *  tracer species at the current temperature and composition of the
     *  species. Therefore, the dilute limit of transport is assumed for the
     *  tracer species. The effective formula may be calculated from the
     *  Stefan-Maxwell formulation by adding another row for the tracer
     *  species, assigning all D's to be equal to the respective species D's,
     *  and then taking the limit as the tracer species mole fraction goes to
     *  zero. The corresponding flux equation for the tracer species k in
     *  units of kmol m-2 s-1 is.
     *
     *  \f[
     *       J_k = - D^{sd}_k \frac{C_k}{R T}  \nabla \mu_k
     *  \f]
     *
     *  The derivative is taken at constant T and P.
     *
     *  The self diffusion calculation is handled by subclasses of
     *  LiquidTranInteraction as specified in the input file.
     *  These in turn employ subclasses of LTPspecies to
     *  determine the individual species self diffusion coeffs.
     *
     *  @param selfDiff Vector of self-diffusion coefficients
     *                  Length = number of species in phase
     *                  units = m**2 s-1
     */
    virtual void selfDiffusion(doublereal* const selfDiff);

    //! Returns the self diffusion coefficients in the pure species phases.
    //! Has size of nsp(coeffs) x nsp(phases)
    /*!
     *  The pure species molar volumes are evaluated using the appropriate
     *  subclasses of LTPspecies as specified in the input file.
     *
     * @param selfDiff  array of length "number of species"
     *              to hold returned self diffusion coeffs.
     */
    virtual void getSpeciesSelfDiffusion(doublereal** selfDiff);

    //! Returns the hydrodynamic radius for all species
    /*!
     *  The species hydrodynamic radii are evaluated using the appropriate
     *  subclasses of LTPspecies as specified in the input file.
     *
     * @param radius  array of length "number of species"
     *                to hold returned radii.
     */
    virtual void getSpeciesHydrodynamicRadius(doublereal* const radius);

    //! Returns the binary diffusion coefficients
    /*!
     *   The binary diffusion coefficients are specified in the input file
     *   through the LiquidTransportInteractions class.  These are the binary
     *   interaction coefficients employed in the Stefan-Maxwell equation.
     *
     *   @param ld  number of species in system
     *   @param d   vector of binary diffusion coefficients
     *          units = m2 s-1. length = ld*ld = (number of species)^2
     */
    virtual void getBinaryDiffCoeffs(const size_t ld, doublereal* const d);

    //! Get the Mixture diffusion coefficients
    /*!
     *  The mixture diffusion coefficients are not well defined
     *  in the context of LiquidTransport because the Stefan Maxwell
     *  equation is solved.  Here the mixture diffusion coefficients
     *  are defined according to Ficks law:
     *  \f[
     *     X_i \vec{V_i} = -D_i \nabla X_i.
     *  \f]
     *  Solving Ficks Law for \f$ D_i \f$ gives a mixture diffusion
     *  coefficient
     *  \f[
     *     D_i = - X_i \vec{V_i} / ( \nabla X_i ).
     *  \f]
     *  If \f$ \nabla X_i = 0 \f$ this is undefined and the
     *  nonsensical value -1 is returned.
     *
     *  Note that this evaluation of \f$ \vec{V_i} \f$  requires
     *  a solve of the Stefan Maxwell equation making this
     *  determination of the mixture averaged diffusion coefficients
     *  a \e slow method for obtaining diffusion coefficients.
     *
     *  Also note that the Stefan Maxwell solve will be based upon
     *  the thermodynamic state (including gradients) most recently
     *  set.  Gradients can be set specifically using set_Grad_V,
     *  set_Grad_X and set_Grad_T or through calls to
     *  getSpeciesFluxes, getSpeciesFluxesES, getSpeciesVdiff,
     *  getSpeciesVdiffES, etc.
     *
     *  @param d vector of mixture diffusion coefficients
     *          units = m2 s-1. length = number of species
     */
    virtual void getMixDiffCoeffs(doublereal* const d);

    //! Return the thermal diffusion coefficients
    /*!
     *  These are all zero for this simple implementation
     *
     *  @param dt thermal diffusion coefficients
     */
    virtual void getThermalDiffCoeffs(doublereal* const dt);

    //! Return the thermal conductivity of the solution
    /*!
     *  The thermal conductivity calculation is handled by subclasses of
     *  LiquidTranInteraction as specified in the input file.
     *  These in turn employ subclasses of LTPspecies to
     *  determine the individual species thermal conductivities.
     */
    virtual doublereal thermalConductivity();

    //! Get the Electrical mobilities (m^2/V/s).
    /*!
     *  The electrical mobilities are not well defined
     *  in the context of LiquidTransport because the Stefan Maxwell
     *  equation is solved.  Here the electrical mobilities
     *  are calculated from the mixture-averaged
     *  diffusion coefficients through a call to getMixDiffCoeffs()
     *  using the Einstein relation
     *
     *     \f[
     *          \mu^e_k = \frac{F D_k}{R T}
     *     \f]
     *
     *  Note that this call to getMixDiffCoeffs() requires
     *  a solve of the Stefan Maxwell equation making this
     *  determination of the mixture averaged diffusion coefficients
     *  a \e slow method for obtaining diffusion coefficients.
     *
     *  Also note that the Stefan Maxwell solve will be based upon the
     *  thermodynamic state (including gradients) most recently set.
     *  Gradients can be set specifically using set_Grad_V, set_Grad_X and
     *  set_Grad_T or through calls to getSpeciesFluxes, getSpeciesFluxesES,
     *  getSpeciesVdiff, getSpeciesVdiffES, etc.
     *
     * @param mobil_e  Returns the electrical mobilities of
     *               the species in array \c mobil_e. The array must be
     *               dimensioned at least as large as the number of species.
     */
    virtual void getMobilities(doublereal* const mobil_e);

    //! Get the fluid mobilities (s kmol/kg).
    /*!
     *  The fluid mobilities are not well defined in the context of
     *  LiquidTransport because the Stefan Maxwell equation is solved.  Here
     *  the fluid mobilities are calculated from the mixture-averaged
     *  diffusion coefficients through a call to getMixDiffCoeffs() using the
     *  Einstein relation
     *
     *     \f[
     *          \mu^f_k = \frac{D_k}{R T}
     *     \f]
     *
     *  Note that this call to getMixDiffCoeffs() requires
     *  a solve of the Stefan Maxwell equation making this
     *  determination of the mixture averaged diffusion coefficients
     *  a \e slow method for obtaining diffusion coefficients.
     *
     *  Also note that the Stefan Maxwell solve will be based upon the
     *  thermodynamic state (including gradients) most recently set.
     *  Gradients can be set specifically using set_Grad_V, set_Grad_X and
     *  set_Grad_T or through calls to getSpeciesFluxes, getSpeciesFluxesES,
     *  getSpeciesVdiff, getSpeciesVdiffES, etc.
     *
     * @param mobil_f  Returns the fluid mobilities of
     *               the species in array \c mobil_f. The array must be
     *               dimensioned at least as large as the number of species.
     */
    virtual void getFluidMobilities(doublereal* const mobil_f);

    //! Specify the value of the gradient of the voltage
    /*!
     * @param grad_V Gradient of the voltage (length num dimensions);
     */
    virtual void set_Grad_V(const doublereal* const grad_V);

    //! Specify the value of the gradient of the temperature
    /*!
     * @param grad_T Gradient of the temperature (length num dimensions);
     */
    virtual void set_Grad_T(const doublereal* const grad_T);

    //! Specify the value of the gradient of the MoleFractions
    /*!
     * @param grad_X Gradient of the mole fractions(length nsp * num dimensions);
     */
    virtual void set_Grad_X(const doublereal* const grad_X);

    //! Compute the mixture electrical conductivity from
    //! the Stefan-Maxwell equation.
    /*!
     *  To compute the mixture electrical conductance, the Stefan
     *  Maxwell equation is solved for zero species gradients and
     *  for unit potential gradient, \f$ \nabla V \f$.
     *  The species fluxes are converted to current by summing over
     *  the charge-weighted fluxes according to
     *  \f[
     *      \vec{i} = \sum_{i} z_i F \rho \vec{V_i} / W_i
     *  \f]
     *  where \f$ z_i \f$ is the charge on species i,
     *  \f$ F \f$ is Faradays constant,  \f$ \rho \f$  is the density,
     *  \f$ W_i \f$ is the molecular mass of species i.
     *  The conductance, \f$ \kappa \f$ is obtained from
     *  \f[
     *      \kappa = \vec{i} / \nabla V.
     *  \f]
     */
    virtual doublereal getElectricConduct();

    //! Compute the electric current density in A/m^2
    /*!
     *  The electric current is computed first by computing the
     *  species diffusive fluxes using  the Stefan Maxwell solution
     *  and then the current, \f$ \vec{i} \f$ by summing over
     *  the charge-weighted fluxes according to
     *  \f[
     *      \vec{i} = \sum_{i} z_i F \rho \vec{V_i} / W_i
     *  \f]
     *  where \f$ z_i \f$ is the charge on species i,
     *  \f$ F \f$ is Faradays constant,  \f$ \rho \f$  is the density,
     *  \f$ W_i \f$ is the molecular mass of species \c i.
     *
     * @param ndim       The number of spatial dimensions (1, 2, or 3).
     * @param grad_T     The temperature gradient (ignored in this model).
     * @param ldx        Leading dimension of the grad_X array.
     * @param grad_X     Gradients of the mole fraction
     *                   Flat vector with the m_nsp in the inner loop.
     *                     length = ldx * ndim
     * @param ldf        Leading dimension of the grad_V and current vectors.
     * @param grad_V     The electrostatic potential gradient.
     * @param current    The electric current in A/m^2.
     */
    virtual void getElectricCurrent(int ndim,
                                    const doublereal* grad_T,
                                    int ldx,
                                    const doublereal* grad_X,
                                    int ldf,
                                    const doublereal* grad_V,
                                    doublereal* current);

    //! Get the species diffusive velocities wrt to the averaged velocity,
    //! given the gradients in mole fraction and temperature
    /*!
     * The average velocity can be computed on a mole-weighted
     * or mass-weighted basis, or the diffusion velocities may
     * be specified as relative to a specific species (i.e. a
     * solvent) all according to the velocityBasis input parameter.
     *
     *  Units for the returned velocities are m s-1.
     *
     *  @param ndim Number of dimensions in the flux expressions
     *  @param grad_T Gradient of the temperature
     *                 (length = ndim)
     * @param ldx  Leading dimension of the grad_X array
     *              (usually equal to m_nsp but not always)
     * @param grad_X Gradients of the mole fraction
     *             Flat vector with the m_nsp in the inner loop.
     *             length = ldx * ndim
     * @param ldf  Leading dimension of the fluxes array
     *              (usually equal to m_nsp but not always)
     * @param Vdiff  Output of the diffusive velocities.
     *             Flat vector with the m_nsp in the inner loop.
     *             length = ldx * ndim
     */
    virtual void getSpeciesVdiff(size_t ndim,
                                 const doublereal* grad_T,
                                 int ldx,
                                 const doublereal* grad_X,
                                 int ldf,
                                 doublereal* Vdiff);

    //! Get the species diffusive velocities wrt to the averaged velocity,
    //! given the gradients in mole fraction, temperature and electrostatic potential.
    /*!
     * The average velocity can be computed on a mole-weighted
     * or mass-weighted basis, or the diffusion velocities may
     * be specified as relative to a specific species (i.e. a
     * solvent) all according to the velocityBasis input parameter.
     *
     *  Units for the returned velocities are m s-1.
     *
     *  @param ndim       Number of dimensions in the flux expressions
     *  @param grad_T     Gradient of the temperature
     *                       (length = ndim)
     * @param ldx         Leading dimension of the grad_X array
     *                       (usually equal to m_nsp but not always)
     * @param grad_X      Gradients of the mole fraction
     *                    Flat vector with the m_nsp in the inner loop.
     *                       length = ldx * ndim
     * @param ldf         Leading dimension of the fluxes array
     *                        (usually equal to m_nsp but not always)
     * @param grad_Phi   Gradients of the electrostatic potential
     *                        (length = ndim)
     * @param Vdiff      Output of the species diffusion velocities
     *                   Flat vector with the m_nsp in the inner loop.
     *                     length = ldx * ndim
     */
    virtual void getSpeciesVdiffES(size_t ndim,  const doublereal* grad_T,
                                   int ldx,  const doublereal* grad_X,
                                   int ldf,  const doublereal* grad_Phi,
                                   doublereal* Vdiff) ;

    //!  Return the species diffusive mass fluxes wrt to
    //!  the averaged velocity in [kmol/m^2/s].
    /*!
     * The diffusive mass flux of species \e k [kmol/m^2/s] is computed
     * using the Stefan-Maxwell equation
     *
     * \f[
     *     X_i \nabla \mu_i  = RT \sum_i \frac{X_i X_j}{D_{ij}}
     *                           ( \vec{V}_j - \vec{V}_i )
     * \f]
     *
     * to determine the diffusion velocity and
     *
     * \f[
     *      \vec{N}_i = C_T X_i \vec{V}_i
     * \f]
     *
     * to determine the diffusion flux.  Here \f$ C_T \f$ is the
     * total concentration of the mixture [kmol/m^3], \f$ D_{ij} \f$
     * are the Stefa-Maxwell interaction parameters in [m^2/s],
     * \f$ \vec{V}_{i} \f$ is the diffusion velocity of species \e i,
     * \f$ \mu_i \f$ is the electrochemical potential of species \e i.
     *
     * Note that for this method, there is no argument for the gradient of the
     * electric potential (voltage).  Electric potential gradients can be set
     * with set_Grad_V() or method getSpeciesFluxesES() can be called.x
     *
     * The diffusion velocity is relative to an average velocity that can be
     * computed on a mole-weighted or mass-weighted basis, or the diffusion
     * velocities may be specified as relative to a specific species (i.e. a
     * solvent) all according to the `velocityBasis` input parameter.
     *
     * @param ndim       The number of spatial dimensions (1, 2, or 3).
     * @param grad_T     The temperature gradient (ignored in this model).
     *                      (length = ndim)
     * @param ldx        Leading dimension of the grad_X array.
     *                       (usually equal to m_nsp but not always)
     * @param grad_X     Gradients of the mole fraction
     *                   Flat vector with the m_nsp in the inner loop.
     *                   length = ldx * ndim
     * @param ldf        Leading dimension of the fluxes array
     *                        (usually equal to m_nsp but not always)
     * @param fluxes     Output of the diffusive mass fluxes
     *                   Flat vector with the m_nsp in the inner loop.
     *                   length = ldx * ndim
     */
    virtual void getSpeciesFluxes(size_t ndim, const doublereal* const grad_T,
                                  size_t ldx, const doublereal* const grad_X,
                                  size_t ldf, doublereal* const fluxes);

    //!  Return the species diffusive mass fluxes wrt to
    //!  the averaged velocity in [kmol/m^2/s].
    /*!
     * The diffusive mass flux of species \e k is computed
     * using the Stefan-Maxwell equation
     * \f[
     *     X_i \nabla \mu_i
     *                     = RT \sum_i \frac{X_i X_j}{D_{ij}}
     *                           ( \vec{V}_j - \vec{V}_i )
     * \f]
     * to determine the diffusion velocity and
     * \f[
     *      \vec{N}_i = C_T X_i \vec{V}_i
     * \f]
     * to determine the diffusion flux.  Here \f$ C_T \f$ is the
     * total concentration of the mixture [kmol/m^3], \f$ D_{ij} \f$
     * are the Stefa-Maxwell interaction parameters in [m^2/s],
     * \f$ \vec{V}_{i} \f$ is the diffusion velocity of species \e i,
     * \f$ \mu_i \f$ is the electrochemical potential of species \e i.
     *
     * The diffusion velocity is relative to an average velocity that can be
     * computed on a mole-weighted or mass-weighted basis, or the diffusion
     * velocities may be specified as relative to a specific species (i.e. a
     * solvent) all according to the `velocityBasis` input parameter.
     *
     * @param ndim      The number of spatial dimensions (1, 2, or 3).
     * @param grad_T    The temperature gradient (ignored in this model).
     *                     (length = ndim)
     * @param ldx       Leading dimension of the grad_X array.
     *                     (usually equal to m_nsp but not always)
     * @param grad_X    Gradients of the mole fraction
     *                  Flat vector with the m_nsp in the inner loop.
     *                     length = ldx * ndim
     * @param ldf       Leading dimension of the fluxes array
     *                     (usually equal to m_nsp but not always)
     * @param grad_Phi  Gradients of the electrostatic potential
     *                     length = ndim
     * @param fluxes    Output of the diffusive mass fluxes
     *                  Flat vector with the m_nsp in the inner loop.
     *                     length = ldx * ndim
     */
    virtual void getSpeciesFluxesES(size_t ndim,
                                    const doublereal* grad_T,
                                    size_t ldx,
                                    const doublereal* grad_X,
                                    size_t ldf,
                                    const doublereal* grad_Phi,
                                    doublereal* fluxes);

    //!  Return the species diffusive velocities relative to
    //!  the averaged velocity.
    /*!
     * This method acts similarly to getSpeciesVdiffES() but requires all
     * gradients to be preset using methods set_Grad_X(), set_Grad_V(),
     * set_Grad_T(). See the documentation of getSpeciesVdiffES() for details.
     *
     *  @param ldf  Leading dimension of the Vdiff array.
     *  @param Vdiff  Output of the diffusive velocities.
     *             Flat vector with the m_nsp in the inner loop.
     *             length = ldx * ndim
     */
    virtual void getSpeciesVdiffExt(size_t ldf, doublereal* Vdiff);

    //!  Return the species diffusive fluxes relative to
    //!  the averaged velocity.
    /*!
     * This method acts similarly to getSpeciesFluxesES() but
     * requires all gradients to be preset using methods
     * set_Grad_X(), set_Grad_V(), set_Grad_T().
     * See the documentation of getSpeciesFluxesES() for details.
     *
     *  units = kg/m2/s
     *
     *  @param ldf  Leading dimension of the Vdiff array.
     *  @param fluxes  Output of the diffusive fluxes.
     *             Flat vector with the m_nsp in the inner loop.
     *             length = ldx * ndim
     */
    virtual void getSpeciesFluxesExt(size_t ldf, doublereal* fluxes);

protected:
    //! Returns true if temperature has changed,
    //! in which case flags are set to recompute transport properties.
    /*!
     *  This is called whenever a transport property is requested.
     *  The first task is to check whether the temperature has changed
     *  since the last call to update_T().
     *  If it hasn't then an immediate return is carried out.
     *
     *   Note this should be a lightweight function since it's
     *   part of all of the interfaces.
     *
     * @return  Returns true if the temperature has changed, and false otherwise
     */
    virtual bool update_T();

    //! Returns true if mixture composition has changed,
    //! in which case flags are set to recompute transport properties.
    /*!
     *   This is called for every interface call to check whether
     *   the concentrations have changed. Concentrations change
     *   whenever the pressure or the mole fraction has changed.
     *   If it has changed, the recalculations should be done.
     *
     *   Note this should be a lightweight function since it's
     *   part of all of the interfaces.
     *
     * @return  Returns true if the mixture composition has changed, and false otherwise.
     */
    virtual bool update_C();

    //!  Updates the internal value of the gradient of the
    //!  logarithm of the activity, which is
    //!  used in the gradient of the chemical potential.
    /*!
     * Evaluate the gradients of the activity
     * as they alter the diffusion coefficient.
     *
     *  The gradient of the chemical potential can be written in terms of
     *  gradient of the logarithm of the mole fraction times a correction
     *  associated with the gradient of the activity coefficient relative to
     *  that of the mole fraction.  Specifically, the gradients of the
     *  logarithms of each are involved according to the formula
     *
     *  \f[
     *      \nabla \mu_k = RT \left[ \nabla ( \ln X_k ) +
     *      \nabla ( \ln \gamma_k ) \right] = RT \left[
     *      \nabla ( \ln a_k ) \right]
     *  \f]
     *
     *  The gradient in the activity coefficient requires the use of ThermoPhase
     *  getdlnActCoeff that calculates its change based on a change in the state
     *  (i.e. temperature and composition of each species) which was first
     *  implemented in MargulesVPSSTP.cpp (LiquidTransport.h doxygen)
     */
    virtual void update_Grad_lnAC();

    //! Solve the Stefan-Maxwell equations for the diffusive fluxes.
    /*!
     * The diffusive mass flux of species \e k is computed
     * using the Stefan-Maxwell equation
     * \f[
     *     X_i \nabla \mu_i
     *                     = RT \sum_i \frac{X_i X_j}{D_{ij}}
     *                           ( \vec{V}_j - \vec{V}_i )
     * \f]
     * to determine the diffusion velocity and
     * \f[
     *      \vec{N}_i = C_T X_i \vec{V}_i
     * \f]
     * to determine the diffusion flux.  Here \f$ C_T \f$ is the
     * total concentration of the mixture [kmol/m^3], \f$ D_{ij} \f$
     * are the Stefa-Maxwell interaction parameters in [m^2/s],
     * \f$ \vec{V}_{i} \f$ is the diffusion velocity of species \e i,
     * \f$ \mu_i \f$ is the electrochemical potential of species \e i.
     *
     * The diffusion velocity is relative to an average velocity that can be
     * computed on a mole-weighted or mass-weighted basis, or the diffusion
     * velocities may be specified as relative to a specific species (i.e. a
     * solvent) all according to the `velocityBasis` input parameter.
     *
     *  The gradient in the activity coefficient requires the use of ThermoPhase
     *  getdlnActCoeff that calculates its change based on a change in the state
     *  i.e. temperature and composition of each species.
     *  First implemented in MargulesVPSSTP.cpp.
     *
     * One of the Stefan Maxwell equations is replaced by the appropriate
     * definition of the mass-averaged velocity, the mole-averaged velocity
     * or the specification that velocities are relative to that
     * of one species.
     */
    void stefan_maxwell_solve();

    //!  Updates the array of pure species viscosities internally.
    /*!
     * The flag m_visc_ok is set to true.
     *
     * Note that for viscosity, a positive activation energy
     * corresponds to the typical case of a positive argument
     * to the exponential so that the Arrhenius expression is
     *
     * \f[
     *      \mu = A T^n \exp( + E / R T )
     * \f]
     */
    void updateViscosity_T();

    //!  Update the temperature-dependent ionic conductivity terms
    //!  for each species internally
    /*!
     * The flag m_ionCond_temp_ok is set to true.
     */
    void updateIonConductivity_T();

    //!  Updates the array of pure species mobility ratios internally.
    /*!
     * The flag m_mobRat_ok is set to true.
     */
    void updateMobilityRatio_T();

    //!  Updates the array of pure species self diffusion coeffs internally.
    /*!
     * The flag m_selfDiff_ok is set to true.
     */
    void updateSelfDiffusion_T();

    //!  Update the temperature-dependent hydrodynamic radius terms
    //!  for each species internally
    /*!
     * The flag m_radi_temp_ok is set to true.
     */
    void updateHydrodynamicRadius_T();

    //! Update the temperature-dependent parts of the mixture-averaged
    //! thermal conductivity internally
    void updateCond_T();

    //! Update the concentration parts of the viscosities
    /*!
     *  Internal routine is run whenever the update_boolean
     *  m_visc_conc_ok is false. Currently there is no concentration
     *  dependence for the pure species viscosities.
     */
    void updateViscosities_C();

    //! Update the concentration parts of the ionic conductivity
    /*!
     *  Internal routine is run whenever the update_boolean
     *  m_ionCond_conc_ok is false. Currently there is no concentration
     *  dependence for the pure species ionic conductivity.
     */
    void updateIonConductivity_C();

    //! Update the concentration parts of the mobility ratio
    /*!
     *  Internal routine is run whenever the update_boolean
     *  m_mobRat_conc_ok is false. Currently there is no concentration
     *  dependence for the pure species mobility ratio.
     */
    void updateMobilityRatio_C();

    //! Update the concentration parts of the self diffusion
    /*!
     *  Internal routine is run whenever the update_boolean
     *  m_selfDiff_conc_ok is false. Currently there is no concentration
     *  dependence for the pure species self diffusion.
     */
    void updateSelfDiffusion_C();

    //! Update the concentration dependence of the hydrodynamic radius
    /*!
     *  Internal routine is run whenever the update_boolean
     *  m_radi_conc_ok is false. Currently there is no concentration
     *  dependence for the hydrodynamic radius.
     */
    void updateHydrodynamicRadius_C();

    //! Update the binary Stefan-Maxwell diffusion coefficients
    //! wrt T using calls to the appropriate LTPspecies subclass
    void updateDiff_T();

private:
    //! Number of species squared
    size_t m_nsp2;

    //! Local copy of the molecular weights of the species
    /*!
     *  Length is equal to the number of species in the phase
     */
    vector_fp m_mw;

    //! Viscosity for each species expressed as an appropriate subclass
    //! of LTPspecies
    /*!
     *  These subclasses of LTPspecies evaluate the species-specific
     *  transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidSpeciesTransportData().
     */
    std::vector<LTPspecies*> m_viscTempDep_Ns;

    //! Viscosity of the mixture expressed as a subclass of
    //! LiquidTranInteraction
    /*!
     *  These subclasses of LiquidTranInteraction evaluate the
     *  mixture transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidInteractionsTransportData().
     */
    LiquidTranInteraction* m_viscMixModel;

    //! Ionic conductivity for each species expressed as an appropriate subclass
    //! of LTPspecies
    /*!
     *  These subclasses of LTPspecies evaluate the species-specific
     *  transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidSpeciesTransportData().
     */
    std::vector<LTPspecies*> m_ionCondTempDep_Ns;

    //! Ionic Conductivity of the mixture expressed as a subclass of
    //! LiquidTranInteraction
    /*!
     *  These subclasses of LiquidTranInteraction evaluate the
     *  mixture transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidInteractionsTransportData().
     */
    LiquidTranInteraction* m_ionCondMixModel;

    //! Type def for LTPvector equating it with a vector of pointers to LTPspecies
    typedef std::vector<LTPspecies*> LTPvector;

    //! Mobility ratio for the binary combinations of each species in each
    //! pure phase expressed as an appropriate subclass of LTPspecies
    /*!
     *  These subclasses of LTPspecies evaluate the species-specific
     *  transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidSpeciesTransportData().
     */
    std::vector<LTPvector> m_mobRatTempDep_Ns;

    //! Mobility ratio for each binary combination of mobile species in the mixture
    //! expressed as a subclass of LiquidTranInteraction
    /*!
     *  These subclasses of LiquidTranInteraction evaluate the
     *  mixture transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidInteractionsTransportData().
     */
    std::vector<LiquidTranInteraction*> m_mobRatMixModel;

    //! Self Diffusion for each species in each pure species phase
    //! expressed as an appropriate subclass of LTPspecies
    /*!
     *  These subclasses of LTPspecies evaluate the species-specific
     *  transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidSpeciesTransportData().
     */
    std::vector<LTPvector> m_selfDiffTempDep_Ns;

    //! Self Diffusion for each species in the mixture expressed as a subclass of
    //! LiquidTranInteraction
    /*!
     *  These subclasses of LiquidTranInteraction evaluate the
     *  mixture transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidInteractionsTransportData().
     */
    std::vector<LiquidTranInteraction*> m_selfDiffMixModel;

    //! Thermal conductivity for each species expressed as an
    //! appropriate subclass of LTPspecies
    /*!
     *  These subclasses of LTPspecies evaluate the species-specific
     *  transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidSpeciesTransportData().
     */
    std::vector<LTPspecies*> m_lambdaTempDep_Ns;

    //! Thermal conductivity of the mixture expressed as a subclass of
    //! LiquidTranInteraction
    /*!
     *  These subclasses of LiquidTranInteraction evaluate the
     *  mixture transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidInteractionsTransportData().
     */
    LiquidTranInteraction* m_lambdaMixModel;

    //! (NOT USED IN LiquidTransport.)
    //! Diffusion coefficient model for each species expressed as an
    //! appropriate subclass of LTPspecies
    /*!
     *  These subclasses of LTPspecies evaluate the species-specific
     *  transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidSpeciesTransportData().
     *
     *  Since the LiquidTransport class uses the Stefan-Maxwell equation
     * to describe species diffusivity, the species-specific
     * diffusivity is irrelevant.
     */
    std::vector<LTPspecies*> m_diffTempDep_Ns;

    //! Species diffusivity of the mixture expressed as a subclass of
    //! LiquidTranInteraction.  This will return an array of Stefan-Maxwell
    //! interaction parameters for use in the Stefan-Maxwell solution.
    /*!
     *  These subclasses of LiquidTranInteraction evaluate the
     *  mixture transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidInteractionsTransportData().
     */
    LiquidTranInteraction* m_diffMixModel;

    //! Stefan-Maxwell diffusion coefficients
    DenseMatrix m_diff_Dij;

    //!   Hydrodynamic radius for each species expressed as an  appropriate subclass of LTPspecies
    /*!
     *  These subclasses of LTPspecies evaluate the species-specific
     *  transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidSpeciesTransportData().
     *         length = nsp
     */
    std::vector<LTPspecies*> m_radiusTempDep_Ns;

    //! (Not used in LiquidTransport)
    //! Hydrodynamic radius of the mixture expressed as a subclass of
    //! LiquidTranInteraction
    /*!
     *  These subclasses of LiquidTranInteraction evaluate the
     *  mixture transport properties according to the parameters parsed in
     *  TransportFactory::getLiquidInteractionsTransportData().
     */
    LiquidTranInteraction* m_radiusMixModel;

    //! Species hydrodynamic radius
    vector_fp  m_hydrodynamic_radius;

    //! Internal value of the gradient of the mole fraction vector
    /*!
     *  Note, this is the only gradient value that can and perhaps
     *  should reflect the true state of the mole fractions in the
     *  application solution vector. In other words no cropping or
     *  massaging of the values to make sure they are above zero
     *  should occur. - developing ....
     *
     *  m_nsp is the number of species in the fluid
     *  k is the species index
     *  n is the dimensional index (x, y, or z). It has a length
     *    equal to m_nDim
     *
     *    m_Grad_X[n*m_nsp + k]
     */
    vector_fp m_Grad_X;

    //! Gradient of the logarithm of the activity
    /*!
     *  This quantity appears in the gradient of the chemical potential.
     *  It replaces the gradient of the mole fraction, and in this way
     * serves to "modify" the diffusion coefficient.
     *
     *  \f[
     *      m\_Grad\_lnAC[k] = \nabla ( \ln X_k ) +
     *      \nabla ( \ln \gamma_k )
     *  \f]
     *
     *  k is the species index
     *  n is the dimensional index (x, y, or z). It has a length
     *    equal to m_nDim
     *
     *    m_Grad_X[n*m_nsp + k]
     */
    vector_fp m_Grad_lnAC;

    //! Internal value of the gradient of the Temperature vector
    /*!
     *  Generally, if a transport property needs this in its evaluation it
     *  will look to this place to get it.
     *
     *  No internal property is precalculated based on gradients. Gradients
     *  are assumed to be freshly updated before every property call.
     */
    vector_fp m_Grad_T;

    //! Internal value of the gradient of the Pressure vector
    /*!
     *  Generally, if a transport property needs this in its evaluation it
     *  will look to this place to get it.
     *
     *  No internal property is precalculated based on gradients. Gradients
     *  are assumed to be freshly updated before every property call.
     */
    vector_fp m_Grad_P;

    //! Internal value of the gradient of the Electric Voltage
    /*!
     *  Generally, if a transport property needs this in its evaluation it
     *  will look to this place to get it.
     *
     *  No internal property is precalculated based on gradients. Gradients
     *  are assumed to be freshly updated before every property call.
     */
    vector_fp m_Grad_V;

    //! Gradient of the electrochemical potential
    /*!
     *  m_nsp is the number of species in the fluid. k is the species index. n
     *  is the dimensional index (x, y, or z)
     *
     *  \f[
     *     m\_Grad\_mu[n*m_nsp + k]
     *  \f]
     */
    vector_fp m_Grad_mu;

    // property values

    //! Array of Binary Diffusivities
    /*!
     *   These are evaluated according to the subclass of
     *  LiquidTranInteraction stored in m_diffMixModel.
     *
     *  This has a size equal to nsp x nsp. It is a symmetric matrix. D_ii is
     *  the self diffusion coefficient. D_ii is not needed except for when
     *  there is one species in the mixture.
     *
     * units m2/sec
     */
    DenseMatrix  m_bdiff;

    //! Internal value of the species viscosities
    /*!
     *  Viscosity of the species evaluated using subclass of LTPspecies
     *  held in m_viscTempDep_Ns.
     *
     *   Length = number of species
     *
     * controlling update boolean -> m_visc_temp_ok
     */
    vector_fp m_viscSpecies;

    //! Internal value of the species ionic conductivities
    /*!
     *  Ionic conductivity of the species evaluated using subclass of LTPspecies
     *  held in m_ionCondTempDep_Ns.
     *
     *   Length = number of species
     *
     * controlling update boolean -> m_ionCond_temp_ok
     */
    vector_fp m_ionCondSpecies;

    //! Internal value of the species mobility ratios
    /*!
     *  Mobility ratio of the species evaluated using subclass of LTPspecies
     *  held in m_mobRatTempDep_Ns.
     *
     *   Length = number of species
     *
     * controlling update boolean -> m_mobRat_temp_ok
     */
    DenseMatrix m_mobRatSpecies;

    //! Internal value of the species self diffusion coefficients
    /*!
     *  Self diffusion of the species evaluated using subclass of LTPspecies
     *  held in m_selfDiffTempDep_Ns.
     *
     *   Length = number of species
     *
     * controlling update boolean -> m_selfDiff_temp_ok
     */
    DenseMatrix m_selfDiffSpecies;

    //! Internal value of the species individual thermal conductivities
    /*!
     *  Thermal conductivities of the species evaluated using subclass
     *  of LTPspecies held in m_lambdaTempDep_Ns.
     *
     *   Length = number of species
     *
     */
    vector_fp  m_lambdaSpecies;

    //! State of the mole fraction vector.
    int m_iStateMF;

    //! Local copy of the mass fractions of the species in the phase
    /*!
     *  The mass fraction vector comes from the ThermoPhase object.
     *
     * length = m_nsp
     */
    vector_fp m_massfracs;

    //! Local copy of the mass fractions of the species in the phase
    /**
     * This version of the mass fraction vector is adjusted to a
     * minimum lower bound of *Tiny* for use in transport calculations.
     */
    vector_fp m_massfracs_tran;

    //! Local copy of the mole fractions of the species in the phase
    /*!
     *  The mole fractions here are assumed to be bounded by 0.0 and 1.0
     *  and they are assumed to add up to one exactly. This mole
     *  fraction vector comes from the ThermoPhase object. Derivative
     *  quantities from this are referred to as bounded.
     *
     * Update info?
     * length = m_nsp
     */
    vector_fp m_molefracs;

    //! Non-zero mole fraction vector used in transport property calculations
    /*!
     *  The mole fractions here are assumed to be bounded by *Tiny* and 1.0
     *  and they may not be assumed to add up to one. This
     *  mole fraction vector is created from the ThermoPhase object.
     *  Derivative quantities of this use the _tran suffix.
     *
     * Update info?
     * length = m_nsp
     */
    vector_fp m_molefracs_tran;

    //! Local copy of the concentrations of the species in the phase
    /*!
     *  The concentrations are consistent with the m_molefracs
     *  vector which is bounded and sums to one.
     *
     * Update info?
     * length = m_nsp
     */
    vector_fp m_concentrations;

    //! Local copy of the total concentration.
    /*!
     * This is consistent with the m_concentrations[] and
     *  m_molefracs[] vector.
     */
    doublereal concTot_;

    //! Local copy of the total concentration.
    /*!
     *  This is consistent with the x_molefracs_tran vector and
     *  with the concTot_ number;
     */
    doublereal concTot_tran_;

    //! Mean molecular mass
    doublereal meanMolecularWeight_;

    //! Density
    doublereal dens_;

    //! Local copy of the charge of each species
    /*!
     *  Contains the charge of each species (length m_nsp)
     */
    vector_fp m_chargeSpecies;

    //! Specific volume for each species.  Local copy from thermo object.
    vector_fp m_volume_spec;

    //! Vector of activity coefficients
    vector_fp m_actCoeff;

    //! RHS to the Stefan-Maxwell equation
    DenseMatrix   m_B;

    //! Matrix for the Stefan-Maxwell equation.
    DenseMatrix m_A;

    //! Current Temperature -> locally stored
    /*!
     * This is used to test whether new temperature computations
     * should be performed.
     */
    doublereal m_temp;

    //! Current value of the pressure
    doublereal m_press;

    //! Solution of the Stefan Maxwell equation in terms of flux
    /*!
     *  This is the mass flux of species k in units of kg m-3 s-1.
     */
    Array2D m_flux;

    //! Solution of the Stefan Maxwell equation
    /*!
     *  This is the diffusion velocity of species k
     *  in units of m/s and relative to the mole-averaged velocity.
     */
    Array2D m_Vdiff;

    //! Saved value of the mixture thermal conductivity
    doublereal m_lambda;

    //! Saved value of the mixture viscosity
    doublereal m_viscmix;

    //! Saved value of the mixture ionic conductivity
    doublereal m_ionCondmix;

    //! Saved values of the mixture mobility ratios
    vector_fp m_mobRatMix;

    //! Saved values of the mixture self diffusion coefficients
    vector_fp m_selfDiffMix;

    //! work space
    /*!
     *   Length is equal to m_nsp
     */
    vector_fp  m_spwork;

private:
    //! Boolean indicating that the top-level mixture viscosity is current
    /*!
     *  This is turned false for every change in T, P, or C.
     */
    bool m_visc_mix_ok;

    //! Boolean indicating that weight factors wrt viscosity is current
    bool m_visc_temp_ok;

    //! Flag to indicate that the pure species viscosities
    //! are current wrt the concentration
    bool m_visc_conc_ok;

    //! Boolean indicating that the top-level mixture ionic conductivity is current
    /*!
     *  This is turned false for every change in T, P, or C.
     */
    bool m_ionCond_mix_ok;

    //! Boolean indicating that weight factors wrt ionic conductivity is current
    bool m_ionCond_temp_ok;

    //! Flag to indicate that the pure species ionic conductivities
    //! are current wrt the concentration
    bool m_ionCond_conc_ok;

    //! Flag to indicate that the mixture conductivity is current
    bool m_cond_mix_ok;

    //! Boolean indicating that the top-level mixture mobility ratio is current
    /*!
     *  This is turned false for every change in T, P, or C.
     */
    bool m_mobRat_mix_ok;

    //! Boolean indicating that weight factors wrt mobility ratio is current
    bool m_mobRat_temp_ok;

    //! Flag to indicate that the pure species mobility ratios
    //! are current wrt the concentration
    bool m_mobRat_conc_ok;

    //! Boolean indicating that the top-level mixture self diffusion is current
    /*!
     *  This is turned false for every change in T, P, or C.
     */
    bool m_selfDiff_mix_ok;

    //! Boolean indicating that weight factors wrt self diffusion is current
    bool m_selfDiff_temp_ok;

    //! Flag to indicate that the pure species self diffusion
    //! are current wrt the concentration
    bool m_selfDiff_conc_ok;

    //! Boolean indicating that mixture diffusion coeffs are current
    bool m_radi_mix_ok;

    //! Boolean indicating that temperature dependence of
    //! hydrodynamic radius is current
    bool m_radi_temp_ok;

    //! Flag to indicate that the hydrodynamic radius is current
    //! is current wrt the concentration
    bool m_radi_conc_ok;

    //! Boolean indicating that mixture diffusion coeffs are current
    bool m_diff_mix_ok;

    //! Boolean indicating that binary diffusion coeffs are current
    bool m_diff_temp_ok;

    //! Flag to indicate that the pure species conductivities
    //! are current wrt the temperature
    bool m_lambda_temp_ok;

    //! Boolean indicating that mixture conductivity is current
    bool m_lambda_mix_ok;

    //! Mode indicator for transport models -- currently unused.
    int m_mode;

    //! Debugging flags
    /*!
     *  Turn on to get debugging information
     */
    bool m_debug;
};
}
#endif