research/cantera
1
0
Fork 0
Code Issues Pull requests Projects Releases Packages Wiki Activity Actions

Cleaned up Doxygen docs for class VPStandardStateTP and descendants

Browse source
This commit is contained in:
Ray Speth 2013-02-14 01:02:34 +00:00
parent 05abe9d361
commit da33cc66c3
29 changed files with 922 additions and 6367 deletions
Show stats Download patch file Download diff file Expand all files Collapse all files

328
include/cantera/thermo/DebyeHuckel.h
View file

@ -81,7 +81,7 @@ class PDSS_Water;
* The enthalpy function is given by the following relation.
*
* \f[
* \raggedright h^\triangle_k(T,P) = h^{\triangle,ref}_k(T)
* h^\triangle_k(T,P) = h^{\triangle,ref}_k(T)
* + \tilde v \left( P - P_{ref} \right)
* \f]
*
@ -201,7 +201,7 @@ class PDSS_Water;
* \f$ I_s \f$ we need to
* catalog all species in the phase. This is done using the following categories:
*
* - <B>cEST_solvent</B> : Solvent species (neutral)
* - <B>cEST_solvent</B> Solvent species (neutral)
* - <B>cEST_chargedSpecies</B> Charged species (charged)
* - <B>cEST_weakAcidAssociated</B> Species which can break apart into charged species.
* It may or may not be charged. These may or
@ -249,8 +249,7 @@ class PDSS_Water;
*
* DHFORM_DILUTE_LIMIT = 0
*
* This form assumes a dilute limit to DH, and is mainly
* for informational purposes:
* This form assumes a dilute limit to DH, and is mainly for informational purposes:
* \f[
* \ln(\gamma_k^\triangle) = - z_k^2 A_{Debye} \sqrt{I}
* \f]
@ -278,10 +277,9 @@ class PDSS_Water;
* + \log(10) B^{dot}_k I
* \f]
*
* Note, this particular form where \f$ a_k \f$ can differ in
* multielectrolyte
* solutions has problems with respect to a Gibbs-Duhem analysis. However,
* we include it here because there is a lot of data fit to it.
* Note, this particular form where \f$ a_k \f$ can differ in multielectrolyte
* solutions has problems with respect to a Gibbs-Duhem analysis. However,
* we include it here because there is a lot of data fit to it.
*
* The activity for the solvent water,\f$ a_o \f$, is not independent and must be
* determined from the Gibbs-Duhem relation. Here, we use:
@ -305,15 +303,14 @@ class PDSS_Water;
*
* DHFORM_BDOT_AUNIFORM = 2
*
* This form assumes Bethke's format for the Debye-Huckel activity coefficient
* This form assumes Bethke's format for the Debye-Huckel activity coefficient
*
* \f[
* \ln(\gamma_k^\triangle) = -z_k^2 \frac{A_{Debye} \sqrt{I}}{ 1 + B_{Debye} a \sqrt{I}}
* + \log(10) B^{dot}_k I
* \f]
*
* The value of a is determined at the beginning of the
* calculation, and not changed.
* The value of a is determined at the beginning of the calculation, and not changed.
*
* \f[
* \ln(a_o) = \frac{X_o - 1.0}{X_o}
@ -326,19 +323,18 @@ class PDSS_Water;
*
* DHFORM_BETAIJ = 3
*
* This form assumes a linear expansion in a virial coefficient form
* It is used extensively in the book by Newmann, "Electrochemistry Systems",
* and is the beginning of
* more complex treatments for stronger electrolytes, fom Pitzer
* and from Harvey, Moller, and Weire.
* This form assumes a linear expansion in a virial coefficient form.
* It is used extensively in the book by Newmann, "Electrochemistry Systems",
* and is the beginning of more complex treatments for stronger electrolytes,
* fom Pitzer and from Harvey, Moller, and Weire.
*
* \f[
* \ln(\gamma_k^\triangle) = -z_k^2 \frac{A_{Debye} \sqrt{I}}{ 1 + B_{Debye} a \sqrt{I}}
* + 2 \sum_j \beta_{j,k} m_j
* \f]
*
* In the current treatment the binary interaction coefficients, \f$ \beta_{j,k}\f$, are
* independent of temperature and pressure.
* In the current treatment the binary interaction coefficients, \f$ \beta_{j,k}\f$, are
* independent of temperature and pressure.
*
* \f[
* \ln(a_o) = \frac{X_o - 1.0}{X_o}
@ -384,9 +380,9 @@ class PDSS_Water;
*
* DHFORM_PITZER_BETAIJ = 4
*
* This form assumes an activity coefficient formulation consistent
* with a truncated form of Pitzer's formulation. Pitzer's formulation is equivalent
* to the formulations above in the dilute limit, where rigorous theory may be applied.
* This form assumes an activity coefficient formulation consistent
* with a truncated form of Pitzer's formulation. Pitzer's formulation is equivalent
* to the formulations above in the dilute limit, where rigorous theory may be applied.
*
* \f[
* \ln(\gamma_k^\triangle) = -z_k^2 \frac{A_{Debye}}{3} \frac{\sqrt{I}}{ 1 + B_{Debye} a \sqrt{I}}
@ -425,23 +421,19 @@ class PDSS_Water;
* {\left(\frac{N_a e^2}{\epsilon R T }\right)}^{3/2}
* \f]
*
* Units = sqrt(kg/gmol)
* where
* - \f$ N_a \f$ is Avogadro's number
* - \f$ \rho_w \f$ is the density of water
* - \f$ e \f$ is the electronic charge
* - \f$ \epsilon = K \epsilon_o \f$ is the permittivity of water
* - \f$ K \f$ is the dielectric constant of water
* - \f$ \epsilon_o \f$ is the permittivity of free space
* - \f$ \rho_o \f$ is the density of the solvent in its standard state.
*
* where
* - \f$ N_a \f$ is Avogadro's number
* - \f$ \rho_w \f$ is the density of water
* - \f$ e \f$ is the electronic charge
* - \f$ \epsilon = K \epsilon_o \f$ is the permittivity of water
* where \f$ K \f$ is the dielectric constant of water,
* and \f$ \epsilon_o \f$ is the permittivity of free space.
* - \f$ \rho_o \f$ is the density of the solvent in its standard state.
*
* Nominal value at 298 K and 1 atm = 1.172576 (kg/gmol)<SUP>1/2</SUP>
* based on:
* - \f$ \epsilon / \epsilon_0 \f$ = 78.54
* (water at 25C)
* - T = 298.15 K
* - B_Debye = 3.28640E9 (kg/gmol)<SUP>1/2</SUP> m<SUP>-1</SUP>
* Nominal value at 298 K and 1 atm = 1.172576 (kg/gmol)<SUP>1/2</SUP> based on:
* - \f$ \epsilon / \epsilon_0 \f$ = 78.54 (water at 25C)
* - T = 298.15 K
* - B_Debye = 3.28640E9 (kg/gmol)<SUP>1/2</SUP> m<SUP>-1</SUP>
*
* An example of a fixed value implementation is given below.
* @code
@ -607,10 +599,8 @@ class PDSS_Water;
*/
class DebyeHuckel : public MolalityVPSSTP
{
public:
//! Empty Constructor
//! Default Constructor
DebyeHuckel();
//! Copy constructor
@ -622,16 +612,14 @@ public:
//! Full constructor for creating the phase.
/*!
* @param inputFile File name containing the XML description of the phase
* @param id id attribute containing the name of the phase.
* (default is the empty string)
* @param id id attribute containing the name of the phase.
*/
DebyeHuckel(const std::string& inputFile, const std::string& id = "");
//! Full constructor for creating the phase.
/*!
* @param phaseRef XML phase node containing the description of the phase
* @param id id attribute containing the name of the phase.
* (default is the empty string)
* @param id id attribute containing the name of the phase.
*/
DebyeHuckel(XML_Node& phaseRef, const std::string& id = "");
@ -648,11 +636,8 @@ public:
*/
ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
/**
* Equation of state type flag. The base class returns
@ -662,29 +647,18 @@ public:
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties of the Solution --------------
* @{
*/
//! @}
//! @name Molar Thermodynamic Properties of the Solution
//! @{
/// Molar enthalpy. Units: J/kmol.
/**
* Molar enthalpy of the solution. Units: J/kmol.
* (HKM -> Bump up to Parent object)
*/
/// Molar enthalpy of the solution. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/// Molar internal energy. Units: J/kmol.
/**
* Molar internal energy of the solution. Units: J/kmol.
* (HKM -> Bump up to Parent object)
*/
/// Molar internal energy of the solution. Units: J/kmol.
virtual doublereal intEnergy_mole() const;
/// Molar entropy. Units: J/kmol/K.
/**
* Molar entropy of the solution. Units: J/kmol/K.
* For an ideal, constant partial molar volume solution mixture with
* pure species phases which exhibit zero volume expansivity:
* \f[
@ -697,15 +671,10 @@ public:
* property manager. The pure species entropies are independent of
* temperature since the volume expansivities are equal to zero.
* @see SpeciesThermo
*
* (HKM -> Bump up to Parent object)
*/
virtual doublereal entropy_mole() const;
/// Molar Gibbs function. Units: J/kmol.
/*
* (HKM -> Bump up to Parent object)
*/
virtual doublereal gibbs_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
@ -718,7 +687,7 @@ public:
virtual doublereal cv_mole() const;
//@}
/** @name Mechanical Equation of State Properties -------------------------
/** @name Mechanical Equation of State Properties
//@{
*
* In this equation of state implementation, the density is a
@ -787,14 +756,10 @@ public:
* This function will now throw an error condition if the
* input isn't exactly equal to the current density.
*
*
* @todo Now have a compressible ss equation for liquid water.
* Therefore, this phase is compressible. May still
* want to change the independent variable however.
*
* NOTE: This is an overwritten function from the State.h
* class
*
* @param rho Input density (kg/m^3).
*/
void setDensity(const doublereal rho);
@ -807,22 +772,16 @@ public:
* This function will now throw an error condition if the input
* isn't exactly equal to the current molar density.
*
* NOTE: This is a virtual function overwritten from the State.h
* class
*
* @param conc Input molar density (kmol/m^3).
*/
virtual void setMolarDensity(const doublereal conc);
//! Set the temperature (K)
/*!
* Overwritten setTemperature(double) from State.h. This
* function sets the temperature, and makes sure that
* This function sets the temperature, and makes sure that
* the value propagates to underlying objects, such as
* the water standard state model.
*
* @todo Make Phase::setTemperature a virtual function
*
* @param temp Temperature in kelvin
*/
virtual void setTemperature(const doublereal temp);
@ -842,6 +801,9 @@ public:
* \f[
* \kappa_T = -\frac{1}{v}\left(\frac{\partial v}{\partial P}\right)_T
* \f]
*
* It's equal to zero for this model, since the molar volume
* doesn't change with pressure or temperature.
*/
virtual doublereal isothermalCompressibility() const;
@ -852,20 +814,12 @@ public:
* \f[
* \beta = \frac{1}{v}\left(\frac{\partial v}{\partial T}\right)_P
* \f]
*
* It's equal to zero for this model, since the molar volume
* doesn't change with pressure or temperature.
*/
virtual doublereal thermalExpansionCoeff() const;
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/**
* @}
* @name Activities, Standard States, and Activity Concentrations
@ -935,6 +889,10 @@ public:
* Inherited classes are responsible for overriding the default
* values if necessary.
*
* On return uA contains the powers of the units (MKS assumed)
* of the standard concentrations and generalized concentrations
* for the kth species.
*
* @param uA Output vector containing the units
* uA[0] = kmol units - default = 1
* uA[1] = m units - default = -nDim(), the number of spatial
@ -959,7 +917,7 @@ public:
* derived classes may want to override this default
* implementation.
*
* (note solvent is on molar scale).
* (note solvent activity coefficient is on molar scale).
*
* @param ac Output vector of activities. Length: m_kk.
*/
@ -972,6 +930,8 @@ public:
* note solvent is on molar scale. The solvent molar
* based activity coefficient is returned.
*
* Note, most of the work is done in an internal private routine
*
* @param acMolality Vector of Molality-based activity coefficients
* Length: m_kk
*/
@ -979,7 +939,7 @@ public:
getMolalityActivityCoefficients(doublereal* acMolality) const;
//@}
/// @name Partial Molar Properties of the Solution -----------------
/// @name Partial Molar Properties of the Solution
//@{
@ -992,9 +952,6 @@ public:
* \f[
* \mu_k = \mu^{\triangle}_k(T,P) + R T ln(\gamma_k^{\triangle} m_k)
* \f]
* or another way to phrase this is
*
* where
*
* @param mu Output vector of species chemical
* potentials. Length: m_kk. Units: J/kmol
@ -1029,8 +986,9 @@ public:
/**
* Maxwell's equations provide an insight in how to calculate this
* (p.215 Smith and Van Ness)
*
* d(chemPot_i)/dT = -sbar_i
* \f[
* \frac{d\mu_i}{dT} = -\bar{s}_i
* \f]
*
* For this phase, the partial molar entropies are equal to the
* SS species entropies plus the ideal solution contribution.following
@ -1039,7 +997,7 @@ public:
* \bar s_k(T,P) = \hat s^0_k(T) - R log(M0 * molality[k])
* \f]
* \f[
* \bar s_solvent(T,P) = \hat s^0_solvent(T)
* \bar s_{solvent}(T,P) = \hat s^0_{solvent}(T)
* - R ((xmolSolvent - 1.0) / xmolSolvent)
* \f]
*
@ -1066,8 +1024,15 @@ public:
//! Return an array of partial molar volumes for the
//! species in the mixture. Units: m^3/kmol.
/*!
* For this solution, the partial molar volumes are equal to the
* constant species molar volumes.
* For this solution, the partial molar volumes are normally
* equal to theconstant species molar volumes, except
* when the activity coefficients depend on pressure.
*
* The general relation is
*
* vbar_i = d(chemPot_i)/dP at const T, n
* = V0_i + d(Gex)/dP)_T,M
* = V0_i + RT d(lnActCoeffi)dP _T,M
*
* @param vbar Output vector of species partial molar volumes.
* Length = m_kk. units are m^3/kmol.
@ -1076,53 +1041,9 @@ public:
//@}
protected:
//! Updates the standard state thermodynamic functions at the current T and P of the solution.
/*!
* @internal
*
* This function gets called for every call to a public function in this
* class. It checks to see whether the temperature or pressure has changed and
* thus whether the ss thermodynamics functions must be recalculated.
*
* @param pres Pressure at which to evaluate the standard states.
* The default, indicated by a -1.0, is to use the current pressure
*/
//virtual void _updateStandardStateThermo() const;
//@}
/// @name Thermodynamic Values for the Species Reference States ---
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//@}
/**
* @name Chemical Equilibrium
* Chemical equilibrium.
* @{
*/
@ -1143,10 +1064,8 @@ public:
err("setToEquilState");
}
//@}
//! Set the equation of state parameters
/*!
* @internal
@ -1177,21 +1096,14 @@ public:
* model. Note, this method is called before the phase is
* initialized with elements and/or species.
*
* HKM -> Right now, the parameters are set elsewhere (initThermoXML)
* It just didn't seem to fit.
*
* @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);
//---------------------------------------------------------
/// @name Critical state properties.
/// These methods are only implemented by some subclasses.
//@{
//@}
/// @name Saturation properties.
/// These methods are only implemented by subclasses that
/// implement full liquid-vapor equations of state.
@ -1236,12 +1148,10 @@ public:
//@}
/*
* -------------- Utilities -------------------------------
*/
//! Initialize the object's internal lengths after species are set
/**
* @internal Initialize. This method is provided to allow
@ -1292,35 +1202,32 @@ public:
* \f[
* A_{Debye} = \frac{F e B_{Debye}}{8 \pi \epsilon R T} {\left( C_o \tilde{M}_o \right)}^{1/2}
* \f]
* where
*
* where
* \f[
* B_{Debye} = \frac{F} {{(\frac{\epsilon R T}{2})}^{1/2}}
* \f]
* Therefore:
* \f[
* \f[
* A_{Debye} = \frac{1}{8 \pi}
* {\left(\frac{2 N_a \rho_o}{1000}\right)}^{1/2}
* {\left(\frac{N_a e^2}{\epsilon R T }\right)}^{3/2}
* \f]
* \f]
*
* Units = sqrt(kg/gmol)
* where
* - Units = sqrt(kg/gmol)
* - \f$ N_a \f$ is Avogadro's number
* - \f$ \rho_w \f$ is the density of water
* - \f$ e \f$ is the electronic charge
* - \f$ \epsilon = K \epsilon_o \f$ is the permittivity of water
* - \f$ K \f$ is the dielectric constant of water,
* - \f$ \epsilon_o \f$ is the permittivity of free space.
* - \f$ \rho_o \f$ is the density of the solvent in its standard state.
*
* where
* - \f$ N_a \f$ is Avogadro's number
* - \f$ \rho_w \f$ is the density of water
* - \f$ e \f$ is the electronic charge
* - \f$ \epsilon = K \epsilon_o \f$ is the permittivity of water
* where \f$ K \f$ is the dielectric constant of water,
* and \f$ \epsilon_o \f$ is the permittivity of free space.
* = \f$ \rho_o \f$ is the density of the solvent in its standard state.
*
* Nominal value at 298 K and 1 atm = 1.172576 (kg/gmol)<SUP>1/2</SUP>
* based on:
* - \f$ \epsilon / \epsilon_0 \f$ = 78.54
* (water at 25C)
* - T = 298.15 K
* - B_Debye = 3.28640E9 (kg/gmol)<SUP>1/2</SUP> m<SUP>-1</SUP>
* Nominal value at 298 K and 1 atm = 1.172576 (kg/gmol)<SUP>1/2</SUP>
* based on:
* - \f$ \epsilon / \epsilon_0 \f$ = 78.54 (water at 25C)
* - T = 298.15 K
* - B_Debye = 3.28640E9 (kg/gmol)<SUP>1/2</SUP> m<SUP>-1</SUP>
*
* @param temperature Temperature in kelvin. Defaults to -1, in which
* case the temperature of the phase is assumed.
@ -1331,14 +1238,13 @@ public:
virtual double A_Debye_TP(double temperature = -1.0,
double pressure = -1.0) const;
//! Value of the derivative of the Debye Huckel constant with
//! respect to temperature.
/*!
* This is a function of temperature and pressure. See A_Debye_TP() for
* a definition of \f$ A_{Debye} \f$.
*
* Units = sqrt(kg/gmol) K-1
* Units = sqrt(kg/gmol) K-1
*
* @param temperature Temperature in kelvin. Defaults to -1, in which
* case the temperature of the phase is assumed.
@ -1355,7 +1261,7 @@ public:
* This is a function of temperature and pressure. See A_Debye_TP() for
* a definition of \f$ A_{Debye} \f$.
*
* Units = sqrt(kg/gmol) K-2
* Units = sqrt(kg/gmol) K-2
*
* @param temperature Temperature in kelvin. Defaults to -1, in which
* case the temperature of the phase is assumed.
@ -1372,7 +1278,7 @@ public:
* This is a function of temperature and pressure. See A_Debye_TP() for
* a definition of \f$ A_{Debye} \f$.
*
* Units = sqrt(kg/gmol) Pa-1
* Units = sqrt(kg/gmol) Pa-1
*
* @param temperature Temperature in kelvin. Defaults to -1, in which
* case the temperature of the phase is assumed.
@ -1400,8 +1306,6 @@ public:
}
private:
//! Static function that implements the non-polar species
//! salt-out modifications.
/*!
@ -1411,7 +1315,6 @@ private:
*/
double _nonpolarActCoeff(double IionicMolality) const;
//! Formula for the osmotic coefficient that occurs in the GWB.
/*!
* It is originally from Helgeson for a variable
@ -1425,11 +1328,8 @@ private:
* NaCl brine. It's to be used with extreme caution.
*/
double _lnactivityWaterHelgesonFixedForm() const;
//@}
protected:
@ -1497,9 +1397,7 @@ protected:
*/
vector_fp m_Aionic;
/**
* Current value of the ionic strength on the molality scale
*/
//! Current value of the ionic strength on the molality scale
mutable double m_IionicMolality;
/**
@ -1588,18 +1486,16 @@ protected:
//! Array of B_Dot values
/**
* B_Dot -> This expression is an extension of the
* Debye-Huckel expression used in some formulations
* to extend DH to higher molalities.
* B_dot is specific to the major ionic pair.
* This expression is an extension of the Debye-Huckel expression used
* in some formulations to extend DH to higher molalities. B_dot is
* specific to the major ionic pair.
*/
vector_fp m_B_Dot;
/**
* m_npActCoeff -> These are coefficients to describe
* the increase in activity coeff for non-polar molecules
* due to the electrolyte becoming stronger (the so-called
* salt-out effect)
* These are coefficients to describe the increase in activity coeff for
* non-polar molecules due to the electrolyte becoming stronger (the
* so-called salt-out effect)
*/
vector_fp m_npActCoeff;
@ -1616,19 +1512,13 @@ protected:
*/
double m_densWaterSS;
/**
* Pointer to the water property calculator
*/
//! Pointer to the water property calculator
WaterProps* m_waterProps;
/**
* Temporary array used in equilibrium calculations
*/
//! Temporary array used in equilibrium calculations
mutable vector_fp m_pp;
/**
* vector of size m_kk, used as a temporary holding area.
*/
//! vector of size m_kk, used as a temporary holding area.
mutable vector_fp m_tmpV;
/**
@ -1670,6 +1560,8 @@ protected:
mutable vector_fp m_dlnActCoeffMolaldP;
private:
//! Bail out of functions with an error exit if they are not implemented.
doublereal err(const std::string& msg) const;
//! Initialize the internal lengths.
@ -1682,8 +1574,9 @@ private:
private:
//! Calculate the log activity coefficients
/*!
* This function updates the internally stored
* natural logarithm of the molality activity coefficients
* This function updates the internally stored natural logarithm of the
* molality activity coefficients. This is the main routine for
* implementing the activity coefficient formulation.
*/
void s_update_lnMolalityActCoeff() const;
@ -1695,8 +1588,6 @@ private:
*
* We assume that the activity coefficients are current in this routine
*
*
*
* The solvent activity coefficient is on the molality scale. Its derivative is too.
*/
void s_update_dlnMolalityActCoeff_dT() const;
@ -1711,8 +1602,6 @@ private:
*
* solvent activity coefficient is on the molality
* scale. Its derivatives are too.
*
* note: private routine
*/
void s_update_d2lnMolalityActCoeff_dT2() const;
@ -1734,8 +1623,3 @@ private:
}
#endif

138
include/cantera/thermo/GibbsExcessVPSSTP.h
View file

@ -39,14 +39,14 @@ namespace Cantera
* and semi-miscible compounds.
*
* It includes
* . regular solutions
* . Margules expansions
* . NTRL equation
* . Wilson's equation
* . UNIQUAC equation of state.
* - regular solutions
* - Margules expansions
* - NTRL equation
* - Wilson's equation
* - UNIQUAC equation of state.
*
* This class adds additional functions onto the %ThermoPhase interface
* that handles the calculation of the excess Gibbs free energy. The %ThermoPhase
* This class adds additional functions onto the ThermoPhase interface
* that handles the calculation of the excess Gibbs free energy. The ThermoPhase
* class includes a member function, ThermoPhase::activityConvention()
* that indicates which convention the activities are based on. The
* default is to assume activities are based on the molar convention.
@ -55,15 +55,13 @@ namespace Cantera
* All of the Excess Gibbs free energy formulations in this area employ
* symmetrical formulations.
*
*
* Chemical potentials
* Chemical potentials
* of species k, \f$ \mu_o \f$, has the following general format:
*
* \f[
* \mu_k = \mu^o_k(T,P) + R T ln( \gamma_k X_k )
* \f]
*
*
* where \f$ \gamma_k^{\triangle} \f$ is a molar based activity coefficient for species
* \f$k\f$.
*
@ -71,7 +69,6 @@ namespace Cantera
* fraction vector. That's one of its primary usages. In order to keep the mole fraction
* vector constant, all of the setState functions are redesigned at this layer.
*
*
* <H3>
* Activity Concentrations: Relationship of %ThermoPhase to %Kinetics Expressions
* </H3>
@ -96,15 +93,12 @@ namespace Cantera
* All setState functions that set the internal state of the ThermoPhase object are
* overloaded at this level, so that a current mole fraction vector is maintained within
* the object.
*
*
*/
class GibbsExcessVPSSTP : public VPStandardStateTP
{
public:
/// Constructors
//! @name Constructors
//! @{
/*!
* This doesn't do much more than initialize constants with
* default values for water at 25C. Water molecular weight
@ -117,16 +111,12 @@ public:
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
GibbsExcessVPSSTP(const GibbsExcessVPSSTP& b);
/// Assignment operator
/*!
*
* @param b class to be copied.
*/
GibbsExcessVPSSTP& operator=(const GibbsExcessVPSSTP& b);
@ -141,13 +131,7 @@ public:
* a pointer to ThermoPhase to work with.
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @}
//! Equation of state type flag.
/*!
@ -159,23 +143,9 @@ public:
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
/**
* @}
* @name Mechanical Properties
* @{
*/
//! @}
//! @name Mechanical Properties
//! @{
//! Set the internally stored pressure (Pa) at constant
//! temperature and composition
@ -191,7 +161,6 @@ public:
virtual void setPressure(doublereal p);
protected:
/**
* Calculate the density of the mixture using the partial
* molar volumes and mole fractions as input
@ -218,17 +187,6 @@ protected:
void calcDensity();
public:
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/**
* @}
* @name Activities, Standard States, and Activity Concentrations
@ -259,8 +217,6 @@ public:
*/
virtual void getActivityConcentrations(doublereal* c) const;
/**
* The standard concentration \f$ C^0_k \f$ used to normalize
* the generalized concentration. In many cases, this quantity
@ -393,12 +349,10 @@ public:
err("getdlnActCoeffdlnX");
}
//@}
/// @name Partial Molar Properties of the Solution
//@{
/**
* Get the species electrochemical potentials.
* These are partial molar quantities.
@ -425,39 +379,13 @@ public:
virtual void getPartialMolarVolumes(doublereal* vbar) const;
virtual const vector_fp& getPartialMolarVolumes() const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @}
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* These methods set all or part of the thermodynamic state.
* @{
*/
//! Set the temperature (K) and pressure (Pa)
/*!
* Set the temperature and pressure.
@ -467,15 +395,6 @@ public:
*/
virtual void setState_TP(doublereal t, doublereal p);
//@}
/**
* @name Chemical Equilibrium
* Routines that implement the Chemical equilibrium capability
* for a single phase, based on the element-potential method.
* @{
*/
/**
* Set the mass fractions to the specified values, and then
* normalize them so that they sum to 1.0.
@ -500,7 +419,6 @@ public:
*/
virtual void setMassFractions_NoNorm(const doublereal* const y);
/**
* Set the mole fractions to the specified values, and then
* normalize them so that they sum to 1.0.
@ -537,18 +455,8 @@ public:
* of species in the phase.
*/
virtual void setConcentrations(const doublereal* const c);
//@}
/// 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.
/*!
* @internal Initialize. This method is provided to allow
* subclasses to perform any initialization required after all
@ -564,9 +472,7 @@ public:
*/
virtual void initThermo();
private:
//! Initialize lengths of local variables after all species have
//! been identified.
void initLengths();
@ -580,17 +486,14 @@ private:
doublereal err(const std::string& msg) const;
protected:
//! utility routine to check mole fraction sum
/*!
* @param x vector of mole fractions.
* @deprecated
*/
double checkMFSum(const doublereal* const x) const;
protected:
// HKM get rid of _Scaled_ prefix
//! Storage for the current values of the mole fractions of the species
/*!
* This vector is kept up-to-date when the setState functions are called.
@ -634,15 +537,8 @@ protected:
//! Temporary storage space that is fair game
mutable std::vector<doublereal> m_pp;
};
}
#endif

632
include/cantera/thermo/HMWSoln.h
View file

File diff suppressed because it is too large Load diff

230
include/cantera/thermo/IdealMolalSoln.h
View file

@ -30,7 +30,6 @@ namespace Cantera
/* @{
*/
/**
* This phase is based upon the mixing-rule assumption that
* all molality-based activity coefficients are equal
@ -65,12 +64,12 @@ namespace Cantera
* depending on the value of the member attribute m_formGC, which
* is supplied in the XML file.
*
* <TABLE>
* <TR><TD> m_formGC </TD><TD> ActivityConc </TD><TD> StandardConc </TD></TR>
* <TR><TD> 0 </TD><TD> \f$ {m_k}/ { m^{\Delta}}\f$ </TD><TD> \f$ 1.0 \f$ </TD></TR>
* <TR><TD> 1 </TD><TD> \f$ m_k / (m^{\Delta} V_k)\f$ </TD><TD> \f$ 1.0 / V_k \f$ </TD></TR>
* <TR><TD> 2 </TD><TD> \f$ m_k / (m^{\Delta} V^0_0)\f$</TD><TD> \f$ 1.0 / V^0_0\f$ </TD></TR>
* </TABLE>
* <TABLE>
* <TR><TD> m_formGC </TD><TD> ActivityConc </TD><TD> StandardConc </TD></TR>
* <TR><TD> 0 </TD><TD> \f$ {m_k}/ { m^{\Delta}}\f$ </TD><TD> \f$ 1.0 \f$ </TD></TR>
* <TR><TD> 1 </TD><TD> \f$ m_k / (m^{\Delta} V_k)\f$ </TD><TD> \f$ 1.0 / V_k \f$ </TD></TR>
* <TR><TD> 2 </TD><TD> \f$ m_k / (m^{\Delta} V^0_0)\f$</TD><TD> \f$ 1.0 / V^0_0\f$ </TD></TR>
* </TABLE>
*
* \f$ V^0_0 \f$ is the solvent standard molar volume. \f$ m^{\Delta} \f$ is a constant equal to a
* molality of \f$ 1.0 \quad\mbox{gm kmol}^{-1} \f$.
@ -80,37 +79,26 @@ namespace Cantera
* The value and form of the activity concentration will affect
* reaction rate constants involving species in this phase.
*
* @verbatim
<thermo model="IdealMolalSoln">
<standardConc model="solvent_volume" />
<solvent> H2O(l) </solvent>
<activityCoefficients model="IdealMolalSoln" >
<idealMolalSolnCutoff model="polyExp">
<gamma_O_limit> 1.0E-5 <gammaOlimit>
<gamma_k_limit> 1.0E-5 <gammaklimit>
<X_o_cutoff> 0.20 </X_o_cutoff>
<C_0_param> 0.05 </C_0_param>
<slope_f_limit> 0.6 </slopefLimit>
<slope_g_limit> 0.0 </slopegLimit>
</idealMolalSolnCutoff>
</activityCoefficients>
</thermo>
@endverbatim
*
* <thermo model="IdealMolalSoln">
* <standardConc model="solvent_volume" />
* <solvent> H2O(l) </solvent>
* <activityCoefficients model="IdealMolalSoln" >
* <idealMolalSolnCutoff model="polyExp">
* <gamma_O_limit> 1.0E-5 </gamma_O_limit>
* <gamma_k_limit> 1.0E-5 <gamma_k_limit>
* <X_o_cutoff> 0.20 </X_o_cutoff>
* <C_0_param> 0.05 </C_0_param>
* <slope_f_limit> 0.6 </slope_f_limit>
* <slope_g_limit> 0.0 </slope_g_limit>
* </idealMolalSolnCutoff>
* </activityCoefficients>
* </thermo>
*/
class IdealMolalSoln : public MolalityVPSSTP
{
public:
/// Constructors
/// Constructor
IdealMolalSoln();
//! Copy Constructor
@ -153,11 +141,8 @@ public:
*/
ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
/**
* Equation of state type flag. The base class returns
@ -169,15 +154,12 @@ public:
return 0;
}
/**
* @}
* @name Molar Thermodynamic Properties of the Solution ---------------
* @{
*/
//! @}
//! @name Molar Thermodynamic Properties of the Solution
//! @{
//! Molar enthalpy of the solution. Units: J/kmol.
/*!
*
* Returns the amount of enthalpy per mole of solution.
* For an ideal molal solution,
* \f[
@ -194,7 +176,6 @@ public:
//! Molar internal energy of the solution: Units: J/kmol.
/*!
*
* Returns the amount of internal energy per mole of solution.
* For an ideal molal solution,
* \f[
@ -223,9 +204,7 @@ public:
//! Molar Gibbs function for the solution: Units J/kmol.
/*!
*
* Returns the gibbs free energy of the solution per mole
* of the solution.
* Returns the gibbs free energy of the solution per mole of the solution.
*
* \f[
* \bar{g}(T, P, X_k) = \sum_k X_k \mu_k(T)
@ -237,7 +216,7 @@ public:
//! Molar heat capacity of the solution at constant pressure. Units: J/kmol/K.
/*!
* \f[
* \f[
* \bar{c}_p(T, P, X_k) = \sum_k X_k \bar{c}_{p,k}(T)
* \f]
*
@ -247,15 +226,12 @@ public:
//! Molar heat capacity of the solution at constant volume. Units: J/kmol/K.
/*!
* Molar heat capacity at constant volume: Units: J/kmol/K.
* NOT IMPLEMENTED.
* Units: J/kmol/K
*/
virtual doublereal cv_mole() const;
//@}
/** @name Mechanical Equation of State Properties -------------------------
//@{
/** @name Mechanical Equation of State Properties
*
* In this equation of state implementation, the density is a
* function only of the mole fractions. Therefore, it can't be
@ -264,8 +240,7 @@ public:
* state by calling setDensity() may cause an exception to be
* thrown.
*/
//@{
/**
* Set the pressure at constant temperature. Units: Pa.
@ -296,9 +271,6 @@ protected:
* 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.
*/
void calcDensity();
@ -316,9 +288,6 @@ public:
*
* This function will now throw an error condition.
*
* NOTE: This is an overwritten function from the State.h
* class
*
* @param rho Input Density
*/
void setDensity(const doublereal rho);
@ -329,9 +298,6 @@ public:
*
* This function will now throw an error condition.
*
* NOTE: This is an overwritten function from the State.h
* class
*
* @param rho Input Density
*/
void setMolarDensity(const doublereal rho);
@ -381,12 +347,9 @@ public:
* @{
*/
//!Set the potential energy of species k to pe.
/*!
* Units: J/kmol.
* This function must be reimplemented in inherited classes
* of ThermoPhase.
*
* @param k Species index
* @param pe Input potential energy.
@ -395,11 +358,9 @@ public:
err("setPotentialEnergy");
}
/*
/**
* Get the potential energy of species k.
* Units: J/kmol.
* This function must be reimplemented in inherited classes
* of ThermoPhase.
*
* @param k Species index
*/
@ -468,13 +429,13 @@ public:
* the program and in the XML input files.
*
* @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
* 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.
@ -510,13 +471,12 @@ public:
getMolalityActivityCoefficients(doublereal* acMolality) const;
//@}
/// @name Partial Molar Properties of the Solution -----------------
/// @name Partial Molar Properties of the Solution
//@{
//!Get the species chemical potentials: Units: J/kmol.
/*!
*
* This function returns a vector of chemical potentials of the
* species in solution.
*
@ -531,7 +491,7 @@ public:
* \f$ w \f$ refers to the solvent species.
* \f$ X_w \f$ is the mole fraction of the solvent.
* \f$ m_k \f$ is the molality of the kth solute.
* \f$ m^\Delta is 1 gmol solute per kg solvent. \f$
* \f$ m^\Delta \f$ is 1 gmol solute per kg solvent.
*
* Units: J/kmol.
*
@ -622,47 +582,9 @@ public:
*/
virtual void getPartialMolarCp(doublereal* cpbar) const;
//@}
/// @name Properties of the Standard State of the Species
// in the Solution --
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States ---
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//@}
/**
* @name Chemical Equilibrium
* Chemical equilibrium.
* @{
*/
//!@}
//! @name Chemical Equilibrium
//! @{
/**
* This method is used by the ChemEquil equilibrium solver.
@ -710,12 +632,15 @@ public:
* any parameters that are specific to that particular phase
* model.
*
* HKM -> Right now, the parameters are set elsewhere (initThermo)
* It just didn't seem to fit.
*
*
* @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);
//---------------------------------------------------------
/// @name Critical state properties.
/// These methods are only implemented by some subclasses.
@ -751,14 +676,6 @@ public:
//@}
/// @name Saturation properties.
/// These methods are only implemented by subclasses that
/// implement full liquid-vapor equations of state.
///
//@}
/*
* -------------- Utilities -------------------------------
*/
@ -793,8 +710,7 @@ public:
//! Report the molar volume of species k
/*!
*
* units - \f$ m^3 kmol^-1 \f$
* units - \f$ m^3 kmol^{-1} \f$
*
* @param k Species index.
*/
@ -802,7 +718,7 @@ public:
/*!
* Fill in a return vector containing the species molar volumes
* units - \f$ m^3 kmol^-1 \f$
* units - \f$ m^3 kmol^{-1} \f$
*
* @param smv Output vector of species molar volumes.
*/
@ -811,7 +727,7 @@ public:
protected:
/**
* Species molar volume \f$ m^3 kmol^-1 \f$
* Species molar volume \f$ m^3 kmol^{-1} \f$
*/
vector_fp m_speciesMolarVolume;
@ -820,12 +736,12 @@ protected:
* depending on the value of the member attribute m_formGC, which
* is supplied in the XML file.
*
* <TABLE>
* <TABLE>
* <TR><TD> m_formGC </TD><TD> ActivityConc </TD><TD> StandardConc </TD></TR>
* <TR><TD> 0 </TD><TD> \f$ {m_k}/ { m^{\Delta}}\f$ </TD><TD> \f$ 1.0 \f$ </TD></TR>
* <TR><TD> 1 </TD><TD> \f$ m_k / (m^{\Delta} V_k)\f$ </TD><TD> \f$ 1.0 / V_k \f$ </TD></TR>
* <TR><TD> 2 </TD><TD> \f$ m_k / (m^{\Delta} V^0_0)\f$</TD><TD> \f$ 1.0 / V^0_0\f$ </TD></TR>
* </TABLE>
* </TABLE>
*/
int m_formGC;
@ -834,7 +750,6 @@ public:
int IMS_typeCutoff_;
private:
/**
* Temporary array used in equilibrium calculations
*/
@ -861,9 +776,6 @@ public:
//! gamma_k minimum for the cutoff process at the zero solvent point
doublereal IMS_gamma_k_min_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_cCut_;
//! Parameter in the polyExp cutoff treatment
/*!
* This is the slope of the f function at the zero solvent point
@ -871,18 +783,6 @@ public:
*/
doublereal IMS_slopefCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_dfCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_efCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_afCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_bfCut_;
//! Parameter in the polyExp cutoff treatment
/*!
* This is the slope of the g function at the zero solvent point
@ -890,17 +790,18 @@ public:
*/
doublereal IMS_slopegCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
//! @name Parameters in the polyExp cutoff treatment having to do with rate of exp decay
//! @{
doublereal IMS_cCut_;
doublereal IMS_dfCut_;
doublereal IMS_efCut_;
doublereal IMS_afCut_;
doublereal IMS_bfCut_;
doublereal IMS_dgCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_egCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_agCut_;
//! Parameter in the polyExp cutoff treatment having to do with rate of exp decay
doublereal IMS_bgCut_;
//! @}
private:
@ -914,7 +815,11 @@ private:
//! natural logarithm of the molality activity coefficients
/*!
* Normally the solutes are all zero. However, sometimes they are not,
* due to stability schemes
* due to stability schemes.
*
* gamma_k_molar = gamma_k_molal / Xmol_solvent
*
* gamma_o_molar = gamma_o_molal
*/
void s_updateIMS_lnMolalityActCoeff() const;
@ -938,8 +843,3 @@ private:
}
#endif

82
include/cantera/thermo/IdealSolnGasVPSS.h
View file

@ -19,12 +19,12 @@
namespace Cantera
{
class XML_Node;
class PDSS;
/*!
* @name CONSTANTS - Models for the Standard State of IdealSolnPhase's
* @name CONSTANTS
* Models for the Standard State of an IdealSolnPhase
*/
//@{
const int cIdealSolnGasPhaseG = 6009;
@ -32,29 +32,26 @@ const int cIdealSolnGasPhase0 = 6010;
const int cIdealSolnGasPhase1 = 6011;
const int cIdealSolnGasPhase2 = 6012;
/**
* @ingroup thermoprops
*
* This class can handle either an ideal solution or an ideal gas approximation
* of a phase.
*
* An ideal solution or an ideal gas approximation of a phase. Uses variable
* pressure standard state methods for calculating thermodynamic properties.
*
* @nosubgrouping
*/
class IdealSolnGasVPSS : public VPStandardStateTP
{
public:
/*!
*
* @name Constructors and Duplicators for %IdealSolnGasVPSS
*
*/
//! @{
/// Constructor.
IdealSolnGasVPSS();
/// Create an object from an XML input file
IdealSolnGasVPSS(const std::string& infile, std::string id="");
/// Copy Constructor.
@ -66,16 +63,11 @@ public:
/// Destructor.
virtual ~IdealSolnGasVPSS();
/*
* Duplication routine
*/
//! Duplication routine
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
//@}
/**
* @name Utilities (IdealSolnGasVPSS)
*/
//! @name Utilities (IdealSolnGasVPSS)
//@{
/**
* Equation of state type flag. The base class returns
@ -85,7 +77,9 @@ public:
*/
virtual int eosType() const;
//@}
//! @}
//! @name Molar Thermodynamic Properties
//! @{
/// Molar enthalpy. Units: J/kmol.
doublereal enthalpy_mole() const;
@ -105,11 +99,9 @@ public:
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal cv_mole() const;
/**
* @}
* @name Mechanical Properties
* @{
*/
//! @}
//! @name Mechanical Properties
//! @{
//! Set the pressure in the fluid
/*!
@ -146,14 +138,11 @@ protected:
* species standard state molar volumes.
* The species molar volumes may be functions
* 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:
//! This method returns an array of generalized concentrations
/*!
* \f$ C^a_k\f$ are defined such that \f$ a_k = C^a_k /
@ -236,7 +225,7 @@ public:
virtual void getActivityCoefficients(doublereal* ac) const;
/// @name Partial Molar Properties of the Solution (IdealSolnGasVPSS)
/// @name Partial Molar Properties of the Solution
//@{
//! Get the array of non-dimensional species chemical potentials
@ -300,34 +289,10 @@ public:
* Length = m_kk. units are m^3/kmol.
*/
virtual void getPartialMolarVolumes(doublereal* vbar) const;
//@}
/*!
* @name Properties of the Standard State of the Species in the Solution
*
* Properties of the standard states are delegated to the VPSSMgr object.
* The values are cached within this object, and are not recalculated unless
* the temperature or pressure changes.
*/
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States (IdealSolnGasVPSS)
/*!
* Properties of the reference states are delegated to the VPSSMgr object.
* The values are cached within this object, and are not recalculated unless
* the temperature or pressure changes.
*/
//@{
//@}
public:
//! @name Initialization Methods - For Internal use (VPStandardState)
//! @name Initialization Methods - For Internal use
/*!
* The following methods are used in the process of constructing
* the phase and setting its parameters from a specification in an
@ -337,9 +302,7 @@ public:
*/
//@{
//! Set equation of state parameter values from XML
//! entries.
//! 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
@ -368,7 +331,6 @@ public:
*/
virtual void initThermo();
//!This method is used by the ChemEquil equilibrium solver.
/*!
* It sets the state such that the chemical potentials satisfy
@ -386,7 +348,6 @@ public:
//! 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
@ -415,15 +376,13 @@ public:
private:
//! @internal Initialize the internal lengths in this object.
/*!
* Note this is not a virtual function and only handles
* this object
* Note this is not a virtual function and only handles this object
*/
void initLengths();
//@}
protected:
//! boolean indicating what ideal solution this is
/*!
* - 1 = ideal gas
@ -441,7 +400,6 @@ protected:
//! Temporary storage - length = m_kk.
vector_fp m_pp;
};
}

210
include/cantera/thermo/IonsFromNeutralVPSSTP.h
View file

@ -5,7 +5,7 @@
* (see \ref thermoprops
* and class \link Cantera::IonsFromNeutralVPSSTP IonsFromNeutralVPSSTP\endlink).
*
* Header file for a derived class of %ThermoPhase that handles
* Header file for a derived class of ThermoPhase that handles
* variable pressure standard state methods for calculating
* thermodynamic properties that are further based upon activities
* based on the molality scale. These include most of the methods for
@ -53,30 +53,29 @@ enum IonSolnType_enumType {
*
* This object actually employs 4 different mole fraction types.
*
* 1) There is a mole fraction associated the the cations and
* 1. There is a mole fraction associated the the cations and
* anions and neutrals from this ThermoPhase object. This
* is the normal mole fraction vector for this object.
* Note, however, it isn't the appropriate mole fraction
* vector to use even for obtaining the correct ideal
* free energies of mixing.
* 2) There is a mole fraction vector associated with the
* 2. There is a mole fraction vector associated with the
* neutral molecule ThermoPhase object.
* 3) There is a mole fraction vector associated with the
* 3. There is a mole fraction vector associated with the
* cation lattice.
* 4) There is a mole fraction vector associated with the
* 4. There is a mole fraction vector associated with the
* anion lattice
*
* This object can translate between any of the four mole
* fraction representations.
*
*
*/
class IonsFromNeutralVPSSTP : public GibbsExcessVPSSTP
{
public:
/// Constructors
//! @name Constructors
//! @{
/*!
* Default constructor
*/
@ -85,12 +84,8 @@ public:
//! Construct and initialize an IonsFromNeutralVPSSTP object
//! directly from an ASCII input file
/*!
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
* This constructor is a shell around the routine initThermo(), with a
* reference to the XML database to get the info for the phase.
*
* @param inputFile Name of the input file containing the phase XML data
* to set up the object
@ -134,16 +129,12 @@ public:
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
IonsFromNeutralVPSSTP(const IonsFromNeutralVPSSTP& b);
/// Assignment operator
/*!
*
* @param b class to be copied.
*/
IonsFromNeutralVPSSTP& operator=(const IonsFromNeutralVPSSTP& b);
@ -159,6 +150,8 @@ public:
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
// @}
/// The following methods are used in the process of constructing
/// the phase and setting its parameters from a specification in an
/// input file.
@ -202,13 +195,8 @@ public:
*/
void constructPhaseXML(XML_Node& phaseNode, std::string id);
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
@ -220,81 +208,36 @@ public:
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
//! @}
//! @name Molar Thermodynamic Properties
//! @{
//! Return the Molar enthalpy. Units: J/kmol.
/*!
* This is calculated from the partial molar enthalpies of the species
* This is calculated from the partial molar enthalpies of the species.
*/
virtual doublereal enthalpy_mole() const;
/**
* Molar internal energy. J/kmol.
* *
*
* This is calculated from the soln enthalpy and then
* subtracting pV.
*/
virtual doublereal intEnergy_mole() const;
/**
* Molar entropy. Units: J/kmol/K.
*
*
*/
//! Molar entropy. Units: J/kmol/K.
virtual doublereal entropy_mole() const;
/**
* Molar Gibbs free Energy for an ideal gas.
* Units = J/kmol.
*/
//! Molar Gibbs free Energy for an ideal gas. Units = J/kmol.
virtual doublereal gibbs_mole() const;
/**
* Molar heat capacity at constant pressure. Units: J/kmol/K.
* For an ideal gas mixture,
*
*/
//! Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/**
* Molar heat capacity at constant volume. Units: J/kmol/K.
*
*/
//! Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
/**
* @}
* @name Utilities
* @{
*/
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/**
* @}
* @name Activities, Standard States, and Activity Concentrations
@ -314,7 +257,6 @@ public:
*/
virtual void getActivityCoefficients(doublereal* ac) const;
//@}
/// @name Partial Molar Properties of the Solution
//@{
@ -330,7 +272,6 @@ public:
*/
virtual void getChemPotentials(doublereal* mu) const;
//! Returns an array of partial molar enthalpies for the species
//! in the mixture.
/*!
@ -387,13 +328,14 @@ public:
//! Get the array of log concentration-like derivatives of the
//! log activity coefficients - diagonal component
/*!
* 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 mole fraction.
* 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 mole
* fraction. 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
* units = dimensionless
*
* @param dlnActCoeffdlnX_diag Output vector of log(mole fraction)
* derivatives of the log Activity Coefficients.
@ -404,11 +346,10 @@ public:
//! Get the array of log concentration-like derivatives of the
//! log activity coefficients - diagonal components
/*!
* 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 species mole numbe. This routine just does the diagonal entries.
* 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 species mole
* numbe. This routine just does the diagonal entries.
*
* units = dimensionless
*
@ -437,7 +378,7 @@ public:
* log Activity Coefficients. length = m_kk * m_kk
*/
virtual void getdlnActCoeffdlnN(const size_t ld, doublereal* const dlnActCoeffdlnN) ;
//! @}
//! Get the Salt Dissociation Coefficients
//! Returns the vector of dissociation coefficients and vector of charges
@ -450,7 +391,6 @@ public:
*/
void getDissociationCoeffs(vector_fp& fm_neutralMolec_ions, vector_fp& charges, std::vector<size_t>& neutMolIndex) const;
//! Return the current value of the neutral mole fraction vector
/*!
* @param neutralMoleculeMoleFractions Vector of neutral molecule mole fractions.
@ -494,36 +434,9 @@ public:
anion=anionList_;
}
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* These methods set all or part of the thermodynamic state.
* @{
*/
@ -540,8 +453,7 @@ public:
virtual void setState_TP(doublereal t, doublereal p);
//! Calculate ion mole fractions from neutral molecule
//! mole fractions.
//! Calculate ion mole fractions from neutral molecule mole fractions.
/*!
* @param mf Dump the mole fractions into this vector.
*/
@ -612,8 +524,7 @@ public:
virtual void setMoleFractions_NoNorm(const doublereal* const x);
/**
* Set the concentrations to the specified values within the
* phase.
* Set the concentrations to the specified values within the phase.
*
* @param c The input vector to this routine is in dimensional
* units. For volumetric phases c[k] is the
@ -641,7 +552,6 @@ public:
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -660,8 +570,6 @@ public:
private:
//! Initialize lengths of local variables after all species have
//! been identified.
void initLengths();
@ -752,16 +660,15 @@ protected:
//! Formula Matrix for composition of neutral molecules
//! in terms of the molecules in this ThermoPhase
/*!
* fm_neutralMolec_ions[ i + jNeut * m_kk ]
* fm_neutralMolec_ions[ i + jNeut * m_kk ]
*
* This is the number of ions of type i in the neutral
* molecule jNeut.
* This is the number of ions of type i in the neutral
* molecule jNeut.
*/
std::vector<double> fm_neutralMolec_ions_;
//! Mapping between ion species and neutral molecule for quick invert.
/*!
*
* fm_invert_ionForNeutral returns vector of int. Each element represents
* an ionic species and stores the value of the corresponding neutral
* molecule
@ -774,11 +681,11 @@ protected:
* We assume that for a selected set of ion species, that that
* ion is only in the neutral molecule, jNeut.
*
* therefore,
* therefore,
*
* NeutralMolecMoleFractions_[jNeut] += moleFractions_[i_ion] / fmij;
*
* where fmij is the number of ions in neutral molecule jNeut.
* where fmij is the number of ions in neutral molecule jNeut.
*
* Thus, we formulate the neutral molecule mole fraction NeutralMolecMoleFractions_[]
* vector from this association. We further assume that there are
@ -791,7 +698,6 @@ protected:
//! Mole fractions using the Neutral Molecule Mole fraction basis
mutable std::vector<doublereal> NeutralMolecMoleFractions_;
//! List of the species in this ThermoPhase which are cation species
std::vector<size_t> cationList_;
@ -845,8 +751,8 @@ private:
* This vector is used as a temporary storage area when calculating the ion chemical
* potentials.
*
* Units = Joules/kmol
* Length = numNeutralMoleculeSpecies_
* - Units = Joules/kmol
* - Length = numNeutralMoleculeSpecies_
*/
mutable std::vector<doublereal> muNeutralMolecule_;
@ -855,18 +761,17 @@ private:
* This vector is used as a temporary storage area when calculating the ion chemical
* potentials and activity coefficients
*
* Units = none
* Length = numNeutralMoleculeSpecies_
* - Units = none
* - Length = numNeutralMoleculeSpecies_
*/
mutable std::vector<doublereal> lnActCoeff_NeutralMolecule_;
//! Storage vector for the neutral molecule d ln activity coefficients dT
/*!
* This vector is used as a temporary storage area when calculating the ion derivatives
*
* Units = 1/Kelvin
* Length = numNeutralMoleculeSpecies_
* - Units = 1/Kelvin
* - Length = numNeutralMoleculeSpecies_
*/
mutable std::vector<doublereal> dlnActCoeffdT_NeutralMolecule_;
@ -874,8 +779,8 @@ private:
/*!
* This vector is used as a temporary storage area when calculating the ion derivatives
*
* Units = none
* Length = numNeutralMoleculeSpecies_
* - Units = none
* - Length = numNeutralMoleculeSpecies_
*/
mutable std::vector<doublereal> dlnActCoeffdlnX_diag_NeutralMolecule_;
@ -883,8 +788,8 @@ private:
/*!
* This vector is used as a temporary storage area when calculating the ion derivatives
*
* Units = none
* Length = numNeutralMoleculeSpecies_
* - Units = none
* - Length = numNeutralMoleculeSpecies_
*/
mutable std::vector<doublereal> dlnActCoeffdlnN_diag_NeutralMolecule_;
@ -892,17 +797,12 @@ private:
/*!
* This vector is used as a temporary storage area when calculating the ion derivatives
*
* Units = none
* Length = numNeutralMoleculeSpecies_
* - Units = none
* - Length = numNeutralMoleculeSpecies_
*/
mutable Array2D dlnActCoeffdlnN_NeutralMolecule_;
};
}
#endif

223
include/cantera/thermo/MargulesVPSSTP.h
View file

@ -28,7 +28,6 @@ namespace Cantera
* @ingroup thermoprops
*/
//! MargulesVPSSTP is a derived class of GibbsExcessVPSSTP that employs
//! the Margules approximation for the excess gibbs free energy
/*!
@ -91,7 +90,7 @@ namespace Cantera
* S^E_i = n X_{Ai} X_{Bi} \left( s_{o,i} + s_{1,i} X_{Bi} \right)
* \f]
*
* where n is the total moles in the solution.
* where n is the total moles in the solution.
*
* The activity of a species defined in the phase is given by an excess
* Gibbs free energy formulation.
@ -100,7 +99,7 @@ namespace Cantera
* a_k = \gamma_k X_k
* \f]
*
* where
* where
*
* \f[
* R T \ln( \gamma_k )= \frac{d(n G^E)}{d(n_k)}\Bigg|_{n_i}
@ -188,7 +187,6 @@ namespace Cantera
* C_j^a = C^s a_j \mbox{\quad and \quad} C_k^a = C^s a_k
* \f]
*
*
* \f$ C_j^a \f$ is the activity concentration of species j, and
* \f$ C_k^a \f$ is the activity concentration of species k. \f$ C^s \f$
* is the standard concentration. \f$ a_j \f$ is
@ -224,11 +222,11 @@ namespace Cantera
* \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{RT}
* \f]
*
* %Kinetics managers will calculate the concentration equilibrium constant, \f$ K_c \f$,
* using the second and third part of the above expression as a definition for the concentration
* equilibrium constant.
* %Kinetics managers will calculate the concentration equilibrium constant, \f$ K_c \f$,
* using the second and third part of the above expression as a definition for the concentration
* equilibrium constant.
*
* For completeness, the pressure equilibrium constant may be obtained as well
* For completeness, the pressure equilibrium constant may be obtained as well
*
* \f[
* \frac{P_j P_k}{ P_l P_{ref}} = K_p^1 = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} )
@ -254,65 +252,12 @@ namespace Cantera
*
* \f$k^{-1} \f$ has units of s-1.
*
*
* <HR>
* <H2> Instantiation of the Class </H2>
* <HR>
*
*
* The constructor for this phase is located in the default ThermoFactory
* for %Cantera. A new %IdealGasPhase may be created by the following code
* snippet:
*
* @code
* XML_Node *xc = get_XML_File("silane.xml");
* XML_Node * const xs = xc->findNameID("phase", "silane");
* ThermoPhase *silane_tp = newPhase(*xs);
* IdealGasPhase *silaneGas = dynamic_cast <IdealGasPhase *>(silane_tp);
* @endcode
*
* or by the following constructor:
*
* @code
* XML_Node *xc = get_XML_File("silane.xml");
* XML_Node * const xs = xc->findNameID("phase", "silane");
* IdealGasPhase *silaneGas = new IdealGasPhase(*xs);
* @endcode
*
* <HR>
* <H2> XML Example </H2>
* <HR>
* An example of an XML Element named phase setting up a IdealGasPhase
* object named silane is given below.
*
*
* @verbatim
<!-- phase silane -->
<phase dim="3" id="silane">
<elementArray datasrc="elements.xml"> Si H He </elementArray>
<speciesArray datasrc="#species_data">
H2 H HE SIH4 SI SIH SIH2 SIH3 H3SISIH SI2H6
H2SISIH2 SI3H8 SI2 SI3
</speciesArray>
<reactionArray datasrc="#reaction_data"/>
<thermo model="IdealGas"/>
<kinetics model="GasKinetics"/>
<transport model="None"/>
</phase>
@endverbatim
*
* The model attribute "IdealGas" of the thermo XML element identifies the phase as
* being of the type handled by the IdealGasPhase object.
*
* @ingroup thermoprops
*
*/
* @ingroup thermoprops
*/
class MargulesVPSSTP : public GibbsExcessVPSSTP
{
public:
//! Constructor
/*!
* This doesn't do much more than initialize constants with
@ -350,14 +295,11 @@ public:
*/
MargulesVPSSTP(XML_Node& phaseRef, const std::string& id = "");
//! Special constructor for a hard-coded problem
/*!
*
* @param testProb Hard-coded value. Only the value of 1 is
* used. It's for
* a LiKCl system
* -> test to predict the eutectic and liquidus correctly.
* @param testProb Hard-coded value. Only the value of 1 is used. It's
* for a LiKCl system test to predict the eutectic and
* liquidus correctly.
*/
MargulesVPSSTP(int testProb);
@ -372,7 +314,6 @@ public:
//! Assignment operator
/*!
*
* @param b class to be copied.
*/
MargulesVPSSTP& operator=(const MargulesVPSSTP& b);
@ -388,12 +329,8 @@ public:
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
@ -405,38 +342,21 @@ public:
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
//! @}
//! @name Molar Thermodynamic Properties
//! @{
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/**
* @}
* @name Utilities for Solvent ID and Molality
* @{
*/
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
/**
* @}
@ -450,7 +370,6 @@ public:
* @{
*/
//! Get the array of non-dimensional molar-based ln activity coefficients at
//! the current solution temperature, pressure, and solution concentration.
/*!
@ -458,7 +377,6 @@ public:
*/
virtual void getLnActivityCoefficients(doublereal* lnac) const;
//@}
/// @name Partial Molar Properties of the Solution
//@{
@ -474,18 +392,6 @@ public:
*/
virtual void getChemPotentials(doublereal* mu) const;
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
//! Returns an array of partial molar enthalpies for the species
//! in the mixture.
/*!
@ -598,63 +504,14 @@ public:
*/
virtual void getdlnActCoeffdT(doublereal* dlnActCoeffdT) const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//@}
/**
* @name Chemical Equilibrium
* Routines that implement the Chemical equilibrium capability
* for a single phase, based on the element-potential method.
* @{
*/
//@}
/// @}
/// @name Initialization
/// 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.
/// @{
/*!
* @internal Initialize. This method is provided to allow
@ -671,7 +528,6 @@ public:
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -688,11 +544,9 @@ public:
*/
void initThermoXML(XML_Node& phaseNode, const std::string& id);
/**
* @}
* @name Derivatives of Thermodynamic Variables needed for Applications
* @{
*/
//! @}
//! @name Derivatives of Thermodynamic Variables needed for Applications
//! @{
//! Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
//! a line in parameter space or along a line in physical space
@ -741,7 +595,6 @@ public:
*/
virtual void getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const;
//! Get the array of derivatives of the ln activity coefficients with respect to the ln species mole numbers
/*!
* Implementations should take the derivative of the logarithm of the activity coefficient with respect to a
@ -765,7 +618,6 @@ public:
//@}
private:
//! Process an XML node called "binaryNeutralSpeciesParameters"
/*!
* This node contains all of the parameters necessary to describe
@ -785,7 +637,6 @@ private:
*/
void resizeNumInteractions(const size_t num);
//! Initialize lengths of local variables after all species have
//! been identified.
void initLengths();
@ -831,7 +682,6 @@ private:
*/
void s_update_dlnActCoeff_dlnN() const;
private:
//! Error function
/*!
@ -842,8 +692,6 @@ private:
doublereal err(const std::string& msg) const;
protected:
//! number of binary interaction expressions
size_t numBinaryInteractions_;
@ -895,8 +743,6 @@ protected:
//! excess gibbs free energy expression
mutable vector_fp m_VSE_d_ij;
//! vector of species indices representing species A in the interaction
/*!
* Each Margules excess Gibbs free energy term involves two species, A and B.
@ -922,17 +768,8 @@ protected:
* Currently there is only one form -> constant wrt temperature.
*/
int formTempModel_;
};
}
#endif

224
include/cantera/thermo/MixedSolventElectrolyte.h
View file

@ -24,17 +24,15 @@
namespace Cantera
{
/**
* @ingroup thermoprops
*/
//! MixedSolventElectrolyte is a derived class of GibbsExcessVPSSTP that employs
//! the DH and local Marguless approximations for the excess gibbs free energy
/*!
*
* %MargulesVPSSTP derives from class GibbsExcessVPSSTP which is derived
* MixedSolventElectrolyte derives from class GibbsExcessVPSSTP which is derived
* from VPStandardStateTP,
* and overloads the virtual methods defined there with ones that
* use expressions appropriate for the Margules Excess gibbs free energy
@ -92,7 +90,7 @@ namespace Cantera
* S^E_i = n X_{Ai} X_{Bi} \left( s_{o,i} + s_{1,i} X_{Bi} \right)
* \f]
*
* where n is the total moles in the solution.
* where n is the total moles in the solution.
*
* The activity of a species defined in the phase is given by an excess
* Gibbs free energy formulation.
@ -101,7 +99,7 @@ namespace Cantera
* a_k = \gamma_k X_k
* \f]
*
* where
* where
*
* \f[
* R T \ln( \gamma_k )= \frac{d(n G^E)}{d(n_k)}\Bigg|_{n_i}
@ -255,65 +253,12 @@ namespace Cantera
*
* \f$k^{-1} \f$ has units of s-1.
*
* @ingroup thermoprops
*
* <HR>
* <H2> Instantiation of the Class </H2>
* <HR>
*
*
* The constructor for this phase is located in the default ThermoFactory
* for %Cantera. A new %IdealGasPhase may be created by the following code
* snippet:
*
* @code
* XML_Node *xc = get_XML_File("silane.xml");
* XML_Node * const xs = xc->findNameID("phase", "silane");
* ThermoPhase *silane_tp = newPhase(*xs);
* IdealGasPhase *silaneGas = dynamic_cast <IdealGasPhase *>(silane_tp);
* @endcode
*
* or by the following constructor:
*
* @code
* XML_Node *xc = get_XML_File("silane.xml");
* XML_Node * const xs = xc->findNameID("phase", "silane");
* IdealGasPhase *silaneGas = new IdealGasPhase(*xs);
* @endcode
*
* <HR>
* <H2> XML Example </H2>
* <HR>
* An example of an XML Element named phase setting up a IdealGasPhase
* object named silane is given below.
*
*
* @verbatim
<!-- phase silane -->
<phase dim="3" id="silane">
<elementArray datasrc="elements.xml"> Si H He </elementArray>
<speciesArray datasrc="#species_data">
H2 H HE SIH4 SI SIH SIH2 SIH3 H3SISIH SI2H6
H2SISIH2 SI3H8 SI2 SI3
</speciesArray>
<reactionArray datasrc="#reaction_data"/>
<thermo model="IdealGas"/>
<kinetics model="GasKinetics"/>
<transport model="None"/>
</phase>
@endverbatim
*
* The model attribute "IdealGas" of the thermo XML element identifies the phase as
* being of the type handled by the IdealGasPhase object.
*
* @ingroup thermoprops
*
*/
*/
class MixedSolventElectrolyte : public MolarityIonicVPSSTP
{
public:
//! Constructor
/*!
* This doesn't do much more than initialize constants with
@ -328,13 +273,6 @@ public:
//! Construct and initialize a MixedSolventElectrolyte ThermoPhase object
//! directly from an xml input file
/*!
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*
* @param inputFile Name of the input file containing the phase XML data
* to set up the object
* @param id ID of the phase in the input file. Defaults to the
@ -352,29 +290,22 @@ public:
*/
MixedSolventElectrolyte(XML_Node& phaseRef, const std::string& id = "");
//! Special constructor for a hard-coded problem
/*!
*
* @param testProb Hard-coded value. Only the value of 1 is
* used. It's for
* a LiKCl system
* -> test to predict the eutectic and liquidus correctly.
* @param testProb Hard-coded value. Only the value of 1 is used. It's
* for a LiKCl system -> test to predict the eutectic and
* liquidus correctly.
*/
MixedSolventElectrolyte(int testProb);
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
MixedSolventElectrolyte(const MixedSolventElectrolyte& b);
//! Assignment operator
/*!
*
* @param b class to be copied.
*/
MixedSolventElectrolyte& operator=(const MixedSolventElectrolyte& b);
@ -390,12 +321,8 @@ public:
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
@ -407,38 +334,21 @@ public:
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
//! @}
//! @name Molar Thermodynamic Properties
//! @{
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/**
* @}
* @name Utilities for Solvent ID and Molality
* @{
*/
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
/**
* @}
@ -459,9 +369,6 @@ public:
*/
virtual void getActivityCoefficients(doublereal* ac) const;
//@}
/// @name Partial Molar Properties of the Solution
//@{
@ -477,18 +384,6 @@ public:
*/
virtual void getChemPotentials(doublereal* mu) const;
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
//! Returns an array of partial molar enthalpies for the species
//! in the mixture.
/*!
@ -549,7 +444,6 @@ public:
*/
virtual void getPartialMolarCp(doublereal* cpbar) const;
//! Return an array of partial molar volumes for the
//! species in the mixture. Units: m^3/kmol.
/*!
@ -597,67 +491,17 @@ public:
*
* @param dlnActCoeffdT Output vector of temperature derivatives of the
* log Activity Coefficients. length = m_kk
*
*/
virtual void getdlnActCoeffdT(doublereal* dlnActCoeffdT) const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//@}
/**
* @name Chemical Equilibrium
* Routines that implement the Chemical equilibrium capability
* for a single phase, based on the element-potential method.
* @{
*/
//@}
//! @}
//! @name Initialization
/// 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.
/// @{
/*!
* @internal Initialize. This method is provided to allow
@ -674,7 +518,6 @@ public:
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -744,7 +587,6 @@ public:
*/
virtual void getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const;
//! Get the array of derivatives of the log activity coefficients with respect to the ln species mole numbers
/*!
* Implementations should take the derivative of the logarithm of the activity coefficient with respect to a
@ -764,11 +606,9 @@ public:
* log Activity Coefficients. length = m_kk * m_kk
*/
virtual void getdlnActCoeffdlnN(const size_t ld, doublereal* const dlnActCoeffdlnN) ;
//@}
private:
//! Process an XML node called "binaryNeutralSpeciesParameters"
/*!
* This node contains all of the parameters necessary to describe
@ -788,7 +628,6 @@ private:
*/
void resizeNumInteractions(const size_t num);
//! Initialize lengths of local variables after all species have
//! been identified.
void initLengths();
@ -834,8 +673,6 @@ private:
*/
void s_update_dlnActCoeff_dlnN() const;
private:
//! Error function
/*!
* Print an error string and exit
@ -845,8 +682,6 @@ private:
doublereal err(const std::string& msg) const;
protected:
//! number of binary interaction expressions
size_t numBinaryInteractions_;
@ -898,8 +733,6 @@ protected:
//! excess gibbs free energy expression
mutable vector_fp m_VSE_d_ij;
//! vector of species indices representing species A in the interaction
/*!
* Each Margules excess Gibbs free energy term involves two species, A and B.
@ -925,17 +758,8 @@ protected:
* Currently there is only one form -> constant wrt temperature.
*/
int formTempModel_;
};
}
#endif

174
include/cantera/thermo/MolalityVPSSTP.h
View file

@ -185,14 +185,11 @@ namespace Cantera
* factors. The other one would be for purposes of stoichiometry evaluation. the
* stoichiometry evaluation one would be a 1E-13 limit. Anything less would create
* problems with roundoff error.
*
*/
class MolalityVPSSTP : public VPStandardStateTP
{
public:
/// Constructors
/// Default Constructor
/*!
* This doesn't do much more than initialize constants with
* default values for water at 25C. Water molecular weight
@ -205,18 +202,12 @@ public:
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
MolalityVPSSTP(const MolalityVPSSTP& b);
/// Assignment operator
/*!
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*
* @param b class to be copied.
*/
MolalityVPSSTP& operator=(const MolalityVPSSTP& b);
@ -224,20 +215,16 @@ public:
/// Destructor.
virtual ~MolalityVPSSTP();
//! Duplication routine for objects which inherit from ThermoPhase.
//! Duplication routine for objects which inherit from ThermoPhase.
/*!
* This virtual routine can be used to duplicate thermophase objects
* This virtual routine can be used to duplicate objects
* inherited from ThermoPhase even if the application only has
* a pointer to ThermoPhase to work with.
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
@ -269,48 +256,35 @@ public:
*/
int pHScale() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
//! @}
//! @name Utilities for Solvent ID and Molality
//! @{
/**
* @}
* @name Utilities for Solvent ID and Molality
* @{
*/
/**
* This routine sets the index number of the solvent for
* the phase.
* This routine sets the index number of the solvent for the phase.
*
* Note, having a solvent
* is a precursor to many things having to do with molality.
* Note, having a solvent is a precursor to many things having to do
* with molality.
*
* @param k the solvent index number
*/
void setSolvent(size_t k);
//! Returns the solvent index.
size_t solventIndex() const;
/**
* Sets the minimum mole fraction in the molality formulation.
* Note the molality formulation is singular in the limit that
* the solvent mole fraction goes to zero. Numerically, how
* this limit is treated and resolved is an ongoing issue within
* Cantera.
* Cantera. The minimum mole fraction must be in the range 0 to 0.9.
*
* @param xmolSolventMIN Input double containing the minimum mole fraction
*/
void setMoleFSolventMin(doublereal xmolSolventMIN);
//! Returns the solvent index.
size_t solventIndex() const;
/**
* Returns the minimum mole fraction in the molality
* formulation.
*/
//! Returns the minimum mole fraction in the molality formulation.
doublereal moleFSolventMin() const;
//! Calculates the molality of all species and stores the result internally.
@ -324,7 +298,7 @@ public:
* - \f$ M_o \f$ is the molecular weight of the solvent
* - \f$ X_o \f$ is the mole fraction of the solvent
* - \f$ X_i \f$ is the mole fraction of the solute.
* - \f$ X_{o,p} = max (X_{o}^{min}, X_o) \f$
* - \f$ X_{o,p} = \max (X_{o}^{min}, X_o) \f$
* - \f$ X_{o}^{min} \f$ = minimum mole fraction of solvent allowed
* in the denominator.
*/
@ -402,23 +376,6 @@ public:
*/
void setMolalitiesByName(const std::string& name);
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/**
* @}
* @name Activities, Standard States, and Activity Concentrations
@ -433,19 +390,15 @@ public:
/**
* This method returns the activity convention.
* Currently, there are two activity conventions
* Molar-based activities
* Unit activity of species at either a hypothetical pure
* solution of the species or at a hypothetical
* pure ideal solution at infinite dilution
* cAC_CONVENTION_MOLAR 0
* - default
*
* Molality based activities
* (unit activity of solutes at a hypothetical 1 molal
* solution referenced to infinite dilution at all
* pressures and temperatures).
* cAC_CONVENTION_MOLALITY 1
* Currently, there are two activity conventions:
* - Molar-based activities: %Unit activity of species at either a
* hypothetical pure solution of the species or at a hypothetical
* pure ideal solution at infinite dilution.
* `cAC_CONVENTION_MOLAR 0` (default)
* - Molality based activities: unit activity of solutes at a hypothetical
* 1 molal solution referenced to infinite dilution at all pressures and
* temperatures. The solvent is still on molar basis.
* `cAC_CONVENTION_MOLALITY 1`
*
* We set the convention to molality here.
*/
@ -514,7 +467,6 @@ public:
virtual void getUnitsStandardConc(double* uA, int k = 0,
int sizeUA = 6) const;
//! Get the array of non-dimensional activities (molality
//! based for this class and classes that derive from it) at
//! the current solution temperature, pressure, and solution concentration.
@ -597,8 +549,6 @@ public:
*/
virtual void getMolalityActivityCoefficients(doublereal* acMolality) const;
//! Calculate the osmotic coefficient
/*!
* \f[
@ -619,12 +569,10 @@ public:
/// @name Partial Molar Properties of the Solution
//@{
/**
* Get the species electrochemical potentials.
* These are partial molar quantities.
* This method adds a term \f$ Fz_k \phi_k \f$ to the
* to each chemical potential.
* These are partial molar quantities. This method adds a term
* \f$ Fz_k \phi_k \f$ to each chemical potential.
*
* Units: J/kmol
*
@ -633,41 +581,7 @@ public:
*/
void getElectrochemPotentials(doublereal* mu) const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//@}
/**
* @name Chemical Equilibrium
* Routines that implement the Chemical equilibrium capability
@ -691,10 +605,8 @@ public:
*/
virtual void setToEquilState(const doublereal* lambda_RT);
//@}
//! Set equation of state parameter values from XML entries.
/*!
* This method is called by function importPhase() in
@ -711,7 +623,7 @@ public:
* XML block. The solvent concentration is then set
* to everything else.
*
* The function first calls the overloaded function ,
* The function first calls the overloaded function,
* VPStandardStateTP::setStateFromXML(), to pick up the parent class
* behavior.
*
@ -723,29 +635,17 @@ public:
*/
virtual void setStateFromXML(const XML_Node& state);
//@}
//! @name Initialization
/// 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.
//@{
/*!
* @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.
*
* @see importCTML.cpp
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -762,6 +662,7 @@ public:
*/
void initThermoXML(XML_Node& phaseNode, const std::string& id);
//@}
//! Set the temperature (K), pressure (Pa), and molalities
//!(gmol kg-1) of the solutes
@ -821,7 +722,6 @@ public:
*/
virtual std::string report(bool show_thermo = true) const;
protected:
virtual void getCsvReportData(std::vector<std::string>& names,
@ -953,8 +853,6 @@ private:
* \f]
*
* where j is any one species.
*
*
*/
const int PHSCALE_PITZER = 0;
@ -980,15 +878,9 @@ const int PHSCALE_PITZER = 0;
*
* This is the NBS pH scale, which is used in all conventional pH
* measurements. and is based on the Bates-Guggenheim equations.
*
*/
const int PHSCALE_NBS = 1;
}
#endif

144
include/cantera/thermo/MolarityIonicVPSSTP.h
View file

@ -30,16 +30,15 @@ namespace Cantera
*/
/*!
* MolarityIonicVPSSTP is a derived class of ThermoPhase
* GibbsExcessVPSSTP that handles
* MolarityIonicVPSSTP is a derived class of GibbsExcessVPSSTP that handles
* variable pressure standard state methods for calculating
* thermodynamic properties that are further based on
* expressing the Excess Gibbs free energy as a function of
* the mole fractions (or pseudo mole fractions) of the constituents.
* This category is the workhorse for describing ionic systems which are not on the molality scale.
*
* This class adds additional functions onto the %ThermoPhase interface
* that handles the calculation of the excess Gibbs free energy. The %ThermoPhase
* This class adds additional functions onto the ThermoPhase interface
* that handles the calculation of the excess Gibbs free energy. The ThermoPhase
* class includes a member function, ThermoPhase::activityConvention()
* that indicates which convention the activities are based on. The
* default is to assume activities are based on the molar convention.
@ -60,8 +59,7 @@ class MolarityIonicVPSSTP : public GibbsExcessVPSSTP
{
public:
/// Constructors
/// Constructor
/*!
* This doesn't do much more than initialize constants with
* default values for water at 25C. Water molecular weight
@ -73,13 +71,8 @@ public:
MolarityIonicVPSSTP();
//! Construct and initialize a MolarityIonicVPSSTP ThermoPhase object
//! directly from an xml input file
//! directly from an XML input file
/*!
* Working constructors
*
* The two constructors below are the normal way the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the XML database to get the info for the phase.
*
* @param inputFile Name of the input file containing the phase XML data
* to set up the object
* @param id ID of the phase in the input file. Defaults to the
@ -96,19 +89,14 @@ public:
*/
MolarityIonicVPSSTP(XML_Node& phaseRef, const std::string& id = "");
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
MolarityIonicVPSSTP(const MolarityIonicVPSSTP& b);
/// Assignment operator
/*!
*
* @param b class to be copied.
*/
MolarityIonicVPSSTP& operator=(const MolarityIonicVPSSTP& b);
@ -124,12 +112,8 @@ public:
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
@ -141,39 +125,6 @@ public:
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
/**
* @}
* @name Utilities for Solvent ID and Molality
* @{
*/
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/**
* @}
* @name Activities, Standard States, and Activity Concentrations
@ -293,67 +244,18 @@ public:
*/
virtual void getPartialMolarVolumes(doublereal* vbar) const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//! Calculate pseudo binary mole fractions
/*!
*
*/
virtual void calcPseudoBinaryMoleFractions() const;
//@}
/**
* @name Chemical Equilibrium
* Routines that implement the Chemical equilibrium capability
* for a single phase, based on the element-potential method.
* @{
*/
//@}
/// @name Initialization
/// 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.
/// @{
/*!
* @internal Initialize. This method is provided to allow
@ -370,7 +272,6 @@ public:
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -386,7 +287,7 @@ public:
* with the correct id.
*/
void initThermoXML(XML_Node& phaseNode, const std::string& id);
//! @}
//! returns a summary of the state of the phase as a string
/*!
@ -395,10 +296,7 @@ public:
*/
virtual std::string report(bool show_thermo = true) const;
private:
//! Initialize lengths of local variables after all species have been identified.
void initLengths();
@ -414,7 +312,6 @@ private:
*/
void readXMLBinarySpecies(XML_Node& xmlBinarySpecies);
//! Update the activity coefficients
/*!
* This function will be called to update the internally stored
@ -441,7 +338,6 @@ private:
*/
void s_update_dlnActCoeff_dX_() const;
private:
//! Error function
/*!
@ -452,13 +348,12 @@ private:
doublereal err(const std::string& msg) const;
protected:
// Pseudobinary type
/*!
* PBTYPE_PASSTHROUGH All species are passthrough species
* PBTYPE_SINGLEANION there is only one anion in the mixture
* PBTYPE_SINGLECATION there is only one cation in the mixture
* PBTYPE_MULTICATIONANION Complex mixture
* - `PBTYPE_PASSTHROUGH` - All species are passthrough species
* - `PBTYPE_SINGLEANION` - there is only one anion in the mixture
* - `PBTYPE_SINGLECATION` - there is only one cation in the mixture
* - `PBTYPE_MULTICATIONANION` - Complex mixture
*/
int PBType_;
@ -484,10 +379,6 @@ protected:
size_t neutralPBindexStart;
mutable std::vector<doublereal> moleFractionsTmp_;
private:
};
#define PBTYPE_PASSTHROUGH 0
@ -495,13 +386,6 @@ private:
#define PBTYPE_SINGLECATION 2
#define PBTYPE_MULTICATIONANION 3
}
#endif

246
include/cantera/thermo/PhaseCombo_Interaction.h
View file

@ -28,8 +28,7 @@ namespace Cantera
//! the Margules approximation for the excess gibbs free energy while eliminating
//! the entropy of mixing term.
/*!
*
* %PhaseCombo_Interaction derives from class GibbsExcessVPSSTP which is derived from VPStandardStateTP,
* PhaseCombo_Interaction derives from class GibbsExcessVPSSTP which is derived from VPStandardStateTP,
* and overloads the virtual methods defined there with ones that
* use expressions appropriate for the Margules Excess gibbs free energy approximation.
* The reader should refer to the MargulesVPSSTP class for information on that class.
@ -60,7 +59,6 @@ namespace Cantera
* like a series of phases. That's why we named it PhaseCombo.
*
*
*
* <HR>
* <H2> Specification of Species Standard %State Properties </H2>
* <HR>
@ -72,7 +70,6 @@ namespace Cantera
* and pressure of the solution. I don't think it prevents, however,
* some species from being dilute in the solution.
*
*
* <HR>
* <H2> Specification of Solution Thermodynamic Properties </H2>
* <HR>
@ -102,7 +99,7 @@ namespace Cantera
* a_k = \gamma_k X_k
* \f]
*
* where
* where
*
* \f[
* R T \ln( \gamma_k )= \frac{d(n G^E)}{d(n_k)}\Bigg|_{n_i}
@ -227,29 +224,29 @@ namespace Cantera
* \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{RT}
* \f]
*
* %Kinetics managers will calculate the concentration equilibrium constant, \f$ K_c \f$,
* using the second and third part of the above expression as a definition for the concentration
* equilibrium constant.
* %Kinetics managers will calculate the concentration equilibrium constant, \f$ K_c \f$,
* using the second and third part of the above expression as a definition for the concentration
* equilibrium constant.
*
* For completeness, the pressure equilibrium constant may be obtained as well
* For completeness, the pressure equilibrium constant may be obtained as well
*
* \f[
* \f[
* \frac{P_j P_k}{ P_l P_{ref}} = K_p^1 = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} )
* \f]
* \f]
*
* \f$ K_p \f$ is the simplest form of the equilibrium constant for ideal gases. However, it isn't
* necessarily the simplest form of the equilibrium constant for other types of phases; \f$ K_c \f$ is
* used instead because it is completely general.
* \f$ K_p \f$ is the simplest form of the equilibrium constant for ideal gases. However, it isn't
* necessarily the simplest form of the equilibrium constant for other types of phases; \f$ K_c \f$ is
* used instead because it is completely general.
*
* The reverse rate of progress may be written down as
* \f[
* The reverse rate of progress may be written down as
* \f[
* R^{-1} = k^{-1} C_l^a = k^{-1} (C^o a_l)
* \f]
* \f]
*
* where we can use the concept of microscopic reversibility to
* write the reverse rate constant in terms of the
* forward reate constant and the concentration equilibrium
* constant, \f$ K_c \f$.
* constant, \f$ K_c \f$.
*
* \f[
* k^{-1} = k^1 K^1_c
@ -262,7 +259,6 @@ namespace Cantera
* <H2> Instantiation of the Class </H2>
* <HR>
*
*
* The constructor for this phase is located in the default ThermoFactory
* for %Cantera. A new %PhaseCombo_Interaction object may be created by the following code
* snippet:
@ -276,13 +272,12 @@ namespace Cantera
*
* or by the following code
*
* @code
* std::string id = "LiFeS_X";
* @code
* std::string id = "LiFeS_X";
* Cantera::ThermoPhase *LiFeS_X_Phase = Cantera::newPhase("LiFeS_X_combo.xml", id);
* PhaseCombo_Interaction *LiFeS_X_solid = dynamic_cast <PhaseCombo_Interaction *>(l_tp);
* @endcode
*
*
* or by the following constructor:
*
* @code
@ -298,51 +293,46 @@ namespace Cantera
* An example of an XML Element named phase setting up a PhaseCombo_Interaction
* object named LiFeS_X is given below.
*
* @code
* <phase dim="3" id="LiFeS_X">
* <elementArray datasrc="elements.xml">
* Li Fe S
* </elementArray>
* <speciesArray datasrc="#species_LiFeS">
* LiTFe1S2(S) Li2Fe1S2(S)
* </speciesArray>
* <thermo model="PhaseCombo_Interaction">
* <activityCoefficients model="Margules" TempModel="constant">
* <binaryNeutralSpeciesParameters speciesA="LiTFe1S2(S)" speciesB="Li2Fe1S2(S)">
* <excessEnthalpy model="poly_Xb" terms="2" units="kJ/mol">
* 84.67069219, -269.1959421
* </excessEnthalpy>
* <excessEntropy model="poly_Xb" terms="2" units="J/mol/K">
* 100.7511565, -361.4222659
* </excessEntropy>
* <excessVolume_Enthalpy model="poly_Xb" terms="2" units="ml/mol">
* 0, 0
* </excessVolume_Enthalpy>
* <excessVolume_Entropy model="poly_Xb" terms="2" units="ml/mol/K">
* 0, 0
* </excessVolume_Entropy>
* </binaryNeutralSpeciesParameters>
* </activityCoefficients>
* </thermo>
* <transport model="none"/>
* <kinetics model="none"/>
* </phase>
* @endcode
*
* @verbatim
<phase dim="3" id="LiFeS_X">
<elementArray datasrc="elements.xml">
Li Fe S
</elementArray>
<speciesArray datasrc="#species_LiFeS">
LiTFe1S2(S) Li2Fe1S2(S)
</speciesArray>
<thermo model="PhaseCombo_Interaction">
<activityCoefficients model="Margules" TempModel="constant">
<binaryNeutralSpeciesParameters speciesA="LiTFe1S2(S)" speciesB="Li2Fe1S2(S)">
<excessEnthalpy model="poly_Xb" terms="2" units="kJ/mol">
84.67069219, -269.1959421
</excessEnthalpy>
<excessEntropy model="poly_Xb" terms="2" units="J/mol/K">
100.7511565, -361.4222659
</excessEntropy>
<excessVolume_Enthalpy model="poly_Xb" terms="2" units="ml/mol">
0, 0
</excessVolume_Enthalpy>
<excessVolume_Entropy model="poly_Xb" terms="2" units="ml/mol/K">
0, 0
</excessVolume_Entropy>
</binaryNeutralSpeciesParameters>
</activityCoefficients>
</thermo>
<transport model="none"/>
<kinetics model="none"/>
</phase>
@endverbatim
* The model attribute "PhaseCombo_Interaction" of the thermo XML element identifies the phase as
* being of the type handled by the PhaseCombo_Interaction object.
*
* The model attribute "PhaseCombo_Interaction" of the thermo XML element identifies the phase as
* being of the type handled by the PhaseCombo_Interaction object.
* @ingroup thermoprops
*
* @ingroup thermoprops
*
*/
*/
class PhaseCombo_Interaction : public GibbsExcessVPSSTP
{
public:
//! Constructor
/*!
* This doesn't do much more than initialize constants with
@ -357,13 +347,6 @@ public:
//! Construct and initialize a PhaseCombo_Interaction ThermoPhase object
//! directly from an xml input file
/*!
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*
* @param inputFile Name of the input file containing the phase XML data
* to set up the object
* @param id ID of the phase in the input file. Defaults to the
@ -380,29 +363,22 @@ public:
*/
PhaseCombo_Interaction(XML_Node& phaseRef, const std::string& id = "");
//! Special constructor for a hard-coded problem
/*!
*
* @param testProb Hard-coded value. Only the value of 1 is
* used. It's for
* a LiKCl system
* -> test to predict the eutectic and liquidus correctly.
* @param testProb Hard-coded value. Only the value of 1 is used. It's
* for a LiKCl system -> test to predict the eutectic and
* liquidus correctly.
*/
PhaseCombo_Interaction(int testProb);
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
PhaseCombo_Interaction(const PhaseCombo_Interaction& b);
//! Assignment operator
/*!
*
* @param b class to be copied.
*/
PhaseCombo_Interaction& operator=(const PhaseCombo_Interaction& b);
@ -418,55 +394,32 @@ public:
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The MolalityVPSSTP class also returns
* zero, as it is a non-complete class.
* The ThermoPhase base class returns zero. Subclasses should define this
* to return a unique non-zero value. Known constants defined for this
* purpose are listed in mix_defs.h.
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
//! @}
//! @name Molar Thermodynamic Properties
//! @{
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/**
* @}
* @name Utilities for Solvent ID and Molality
* @{
*/
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
/**
* @}
@ -502,18 +455,6 @@ public:
*/
virtual void getChemPotentials(doublereal* mu) const;
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
//! Returns an array of partial molar enthalpies for the species
//! in the mixture.
/*!
@ -574,7 +515,6 @@ public:
*/
virtual void getPartialMolarCp(doublereal* cpbar) const;
//! Return an array of partial molar volumes for the
//! species in the mixture. Units: m^3/kmol.
/*!
@ -626,28 +566,14 @@ public:
*/
virtual void getdlnActCoeffdT(doublereal* dlnActCoeffdT) const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
/// @}
/// @name Initialization
/// 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.
/// @{
/*!
* @internal Initialize. This method is provided to allow
@ -664,7 +590,6 @@ public:
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -681,11 +606,9 @@ public:
*/
void initThermoXML(XML_Node& phaseNode, const std::string& id);
/**
* @}
* @name Derivatives of Thermodynamic Variables needed for Applications
* @{
*/
//! @}
//! @name Derivatives of Thermodynamic Variables needed for Applications
//! @{
//! Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
//! a line in parameter space or along a line in physical space
@ -734,7 +657,6 @@ public:
*/
virtual void getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const;
//! Get the array of derivatives of the log activity coefficients with respect to the ln species mole numbers
/*!
* Implementations should take the derivative of the logarithm of the activity coefficient with respect to a
@ -758,7 +680,6 @@ public:
//@}
private:
//! Process an XML node called "binaryNeutralSpeciesParameters"
/*!
* This node contains all of the parameters necessary to describe
@ -778,7 +699,6 @@ private:
*/
void resizeNumInteractions(const size_t num);
//! Initialize lengths of local variables after all species have
//! been identified.
void initLengths();
@ -824,7 +744,6 @@ private:
*/
void s_update_dlnActCoeff_dlnN() const;
private:
//! Error function
/*!
@ -835,8 +754,6 @@ private:
doublereal err(const std::string& msg) const;
protected:
//! number of binary interaction expressions
size_t numBinaryInteractions_;
@ -888,8 +805,6 @@ protected:
//! excess gibbs free energy expression
mutable vector_fp m_VSE_d_ij;
//! vector of species indices representing species A in the interaction
/*!
* Each Margules excess Gibbs free energy term involves two species, A and B.
@ -915,17 +830,8 @@ protected:
* Currently there is only one form -> constant wrt temperature.
*/
int formTempModel_;
};
}
#endif

151
include/cantera/thermo/PseudoBinaryVPSSTP.h
View file

@ -3,7 +3,7 @@
* Header for intermediate ThermoPhase object for phases which
* employ gibbs excess free energy based formulations
* (see \ref thermoprops
* and class \link Cantera::gibbsExcessVPSSTP gibbsExcessVPSSTP\endlink).
* and class \link Cantera::PseudoBinaryVPSSTP PseudoBinaryVPSSTP\endlink).
*
* Header file for a derived class of ThermoPhase that handles
* variable pressure standard state methods for calculating
@ -23,7 +23,6 @@
namespace Cantera
{
/**
* @ingroup thermoprops
*/
@ -40,14 +39,14 @@ namespace Cantera
* and semi-miscible compounds.
*
* It includes
* . regular solutions
* . Margules expansions
* . NTRL equation
* . Wilson's equation
* . UNIQUAC equation of state.
* - regular solutions
* - Margules expansions
* - NTRL equation
* - Wilson's equation
* - UNIQUAC equation of state.
*
* This class adds additional functions onto the %ThermoPhase interface
* that handles the calculation of the excess Gibbs free energy. The %ThermoPhase
* This class adds additional functions onto the ThermoPhase interface
* that handles the calculation of the excess Gibbs free energy. The ThermoPhase
* class includes a member function, ThermoPhase::activityConvention()
* that indicates which convention the activities are based on. The
* default is to assume activities are based on the molar convention.
@ -62,15 +61,11 @@ namespace Cantera
* The way that it collects the cation and anion based mole numbers
* is via holding two extra ThermoPhase objects. These
* can include standard states for salts.
*
*
*/
class PseudoBinaryVPSSTP : public GibbsExcessVPSSTP
{
public:
/// Constructors
/// Constructor
/*!
* This doesn't do much more than initialize constants with
* default values for water at 25C. Water molecular weight
@ -83,16 +78,12 @@ public:
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
PseudoBinaryVPSSTP(const PseudoBinaryVPSSTP& b);
/// Assignment operator
/*!
*
* @param b class to be copied.
*/
PseudoBinaryVPSSTP& operator=(const PseudoBinaryVPSSTP& b);
@ -108,58 +99,18 @@ public:
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The MolalityVPSSTP class also returns
* zero, as it is a non-complete class.
* listed in mix_defs.h.
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
/**
* @}
* @name Utilities for Solvent ID and Molality
* @{
*/
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/**
* @}
* @name Activities, Standard States, and Activity Concentrations
@ -172,9 +123,6 @@ public:
* @{
*/
/**
* The standard concentration \f$ C^0_k \f$ used to normalize
* the generalized concentration. In many cases, this quantity
@ -197,15 +145,10 @@ public:
* @param k species index
*/
virtual doublereal logStandardConc(size_t k=0) const;
//@}
/// @name Partial Molar Properties of the Solution
//@{
/**
* Get the species electrochemical potentials.
* These are partial molar quantities.
@ -218,69 +161,19 @@ public:
* Length: m_kk.
*/
void getElectrochemPotentials(doublereal* mu) const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//! Calculate pseudo binary mole fractions
/*!
*
*/
virtual void calcPseudoBinaryMoleFractions() const;
//@}
/**
* @name Chemical Equilibrium
* Routines that implement the Chemical equilibrium capability
* for a single phase, based on the element-potential method.
* @{
*/
//@}
/// @name Initialization
/// 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.
/*!
* @internal Initialize. This method is provided to allow
* subclasses to perform any initialization required after all
@ -296,7 +189,6 @@ public:
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -313,7 +205,6 @@ public:
*/
void initThermoXML(XML_Node& phaseNode, const std::string& id);
//! returns a summary of the state of the phase as a string
/*!
* @param show_thermo If true, extra information is printed out
@ -321,17 +212,11 @@ public:
*/
virtual std::string report(bool show_thermo = true) const;
private:
//! Initialize lengths of local variables after all species have
//! been identified.
void initLengths();
private:
//! Error function
/*!
* Print an error string and exit
@ -341,7 +226,6 @@ private:
doublereal err(const std::string& msg) const;
protected:
int PBType_;
//! Number of pseudo binary species
@ -367,10 +251,6 @@ protected:
ThermoPhase* anionPhase_;
mutable std::vector<doublereal> moleFractionsTmp_;
private:
};
#define PBTYPE_PASSTHROUGH 0
@ -383,8 +263,3 @@ private:
}
#endif

264
include/cantera/thermo/RedlichKisterVPSSTP.h
View file

@ -33,7 +33,6 @@ namespace Cantera
//! RedlichKisterVPSSTP is a derived class of GibbsExcessVPSSTP that employs
//! the Redlich-Kister approximation for the excess gibbs free energy
/*!
*
* %RedlichKisterVPSSTP derives from class GibbsExcessVPSSTP which is derived
* from VPStandardStateTP, and overloads the virtual methods defined there with ones that
* use expressions appropriate for the Redlich Kister Excess gibbs free energy approximation.
@ -82,13 +81,13 @@ namespace Cantera
* G^E = \sum_{i} G^E_{i}
* \f]
*
* where
* where
*
* \f[
* G^E_{i} = n X_{Ai} X_{Bi} \sum_m \left( A^{i}_m {\left( X_{Ai} - X_{Bi} \right)}^m \right)
* \f]
*
* and where we can break down the gibbs free energy contributions into enthalpy and entropy contributions
* and where we can break down the gibbs free energy contributions into enthalpy and entropy contributions
*
* \f[
* H^E_i = n X_{Ai} X_{Bi} \sum_m \left( H^{i}_m {\left( X_{Ai} - X_{Bi} \right)}^m \right)
@ -117,8 +116,6 @@ namespace Cantera
* R T \ln( \gamma_k )= \sum_i \delta_{Ai,k} (1 - X_{Ai}) X_{Bi} \sum_m \left( A^{i}_m {\left( X_{Ai} - X_{Bi} \right)}^m \right)
* + \sum_i \delta_{Ai,k} X_{Ai} X_{Bi} \sum_m \left( A^{i}_0 + A^{i}_m {\left( X_{Ai} - X_{Bi} \right)}^{m-1} (1 - X_{Ai} + X_{Bi}) \right)
* \f]
* where
*
*
* This object inherits from the class VPStandardStateTP. Therefore, the specification and
* calculation of all standard state and reference state values are handled at that level. Various functional
@ -215,41 +212,41 @@ namespace Cantera
* We can switch over to expressing the equilibrium constant in terms of the reference
* state chemical potentials
*
* \f[
* K_a^{o,1} = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{P}
* \f]
* \f[
* K_a^{o,1} = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{P}
* \f]
*
* The concentration equilibrium constant, \f$ K_c \f$, may be obtained by changing over
* to activity concentrations. When this is done:
* The concentration equilibrium constant, \f$ K_c \f$, may be obtained by changing over
* to activity concentrations. When this is done:
*
* \f[
* \f[
* \frac{C^a_j C^a_k}{ C^a_l} = C^o K_a^{o,1} = K_c^1 =
* \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{RT}
* \f]
* \f]
*
* %Kinetics managers will calculate the concentration equilibrium constant, \f$ K_c \f$,
* using the second and third part of the above expression as a definition for the concentration
* equilibrium constant.
* %Kinetics managers will calculate the concentration equilibrium constant, \f$ K_c \f$,
* using the second and third part of the above expression as a definition for the concentration
* equilibrium constant.
*
* For completeness, the pressure equilibrium constant may be obtained as well
* For completeness, the pressure equilibrium constant may be obtained as well
*
* \f[
* \f[
* \frac{P_j P_k}{ P_l P_{ref}} = K_p^1 = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} )
* \f]
* \f]
*
* \f$ K_p \f$ is the simplest form of the equilibrium constant for ideal gases. However, it isn't
* necessarily the simplest form of the equilibrium constant for other types of phases; \f$ K_c \f$ is
* used instead because it is completely general.
* \f$ K_p \f$ is the simplest form of the equilibrium constant for ideal gases. However, it isn't
* necessarily the simplest form of the equilibrium constant for other types of phases; \f$ K_c \f$ is
* used instead because it is completely general.
*
* The reverse rate of progress may be written down as
* \f[
* The reverse rate of progress may be written down as
* \f[
* R^{-1} = k^{-1} C_l^a = k^{-1} (C^o a_l)
* \f]
* \f]
*
* where we can use the concept of microscopic reversibility to
* write the reverse rate constant in terms of the
* forward reate constant and the concentration equilibrium
* constant, \f$ K_c \f$.
* constant, \f$ K_c \f$.
*
* \f[
* k^{-1} = k^1 K^1_c
@ -257,65 +254,12 @@ namespace Cantera
*
* \f$k^{-1} \f$ has units of s-1.
*
*
* <HR>
* <H2> Instantiation of the Class </H2>
* <HR>
*
*
* The constructor for this phase is located in the default ThermoFactory
* for %Cantera. A new %IdealGasPhase may be created by the following code
* snippet:
*
* @code
* XML_Node *xc = get_XML_File("silane.xml");
* XML_Node * const xs = xc->findNameID("phase", "silane");
* ThermoPhase *silane_tp = newPhase(*xs);
* IdealGasPhase *silaneGas = dynamic_cast <IdealGasPhase *>(silane_tp);
* @endcode
*
* or by the following constructor:
*
* @code
* XML_Node *xc = get_XML_File("silane.xml");
* XML_Node * const xs = xc->findNameID("phase", "silane");
* IdealGasPhase *silaneGas = new IdealGasPhase(*xs);
* @endcode
*
* <HR>
* <H2> XML Example </H2>
* <HR>
* An example of an XML Element named phase setting up a IdealGasPhase
* object named silane is given below.
*
*
* @verbatim
<!-- phase silane -->
<phase dim="3" id="silane">
<elementArray datasrc="elements.xml"> Si H He </elementArray>
<speciesArray datasrc="#species_data">
H2 H HE SIH4 SI SIH SIH2 SIH3 H3SISIH SI2H6
H2SISIH2 SI3H8 SI2 SI3
</speciesArray>
<reactionArray datasrc="#reaction_data"/>
<thermo model="IdealGas"/>
<kinetics model="GasKinetics"/>
<transport model="None"/>
</phase>
@endverbatim
*
* The model attribute "IdealGas" of the thermo XML element identifies the phase as
* being of the type handled by the IdealGasPhase object.
*
* @ingroup thermoprops
*
*/
*/
class RedlichKisterVPSSTP : public GibbsExcessVPSSTP
{
public:
//! Constructor
/*!
* This doesn't do much more than initialize constants with
@ -326,10 +270,6 @@ public:
//! Construct and initialize a RedlichKisterVPSSTP ThermoPhase object
//! directly from an xml input file
/*!
* Working constructors
*
* The two constructors below are the normal way the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the XML database to get the info for the phase.
*
* @param inputFile Name of the input file containing the phase XML data
* to set up the object
@ -347,29 +287,22 @@ public:
*/
RedlichKisterVPSSTP(XML_Node& phaseRef, const std::string& id = "");
//! Special constructor for a hard-coded problem
/*!
*
* @param testProb Hard-coded value. Only the value of 1 is
* used. It's for
* a LiKCl system
* -> test to predict the eutectic and liquidus correctly.
* @param testProb Hard-coded value. Only the value of 1 is used. It's
* for a LiKCl system -> test to predict the eutectic and
* liquidus correctly.
*/
RedlichKisterVPSSTP(int testProb);
//! Copy constructor
/*!
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* @param b class to be copied
*/
RedlichKisterVPSSTP(const RedlichKisterVPSSTP& b);
//! Assignment operator
/*!
*
* @param b class to be copied.
*/
RedlichKisterVPSSTP& operator=(const RedlichKisterVPSSTP& b);
@ -385,55 +318,33 @@ public:
*/
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
/**
*
* @name Utilities
* @{
*/
//! @name Utilities
//! @{
//! Equation of state type flag.
/*!
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The MolalityVPSSTP class also returns
* zero, as it is a non-complete class.
* listed in mix_defs.h.
*/
virtual int eosType() const;
/**
* @}
* @name Molar Thermodynamic Properties
* @{
*/
//! @}
//! @name Molar Thermodynamic Properties
//! @{
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/**
* @}
* @name Utilities for Solvent ID and Molality
* @{
*/
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/**
* @}
* @name Mechanical Properties
* @{
*/
/**
* @}
* @name Potential Energy
*
* Species may have an additional potential energy due to the
* presence of external gravitation or electric fields. These
* methods allow specifying a potential energy for individual
* species.
* @{
*/
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
/**
* @}
@ -469,18 +380,6 @@ public:
*/
virtual void getChemPotentials(doublereal* mu) const;
/// Molar enthalpy. Units: J/kmol.
virtual doublereal enthalpy_mole() const;
/// Molar entropy. Units: J/kmol.
virtual doublereal entropy_mole() const;
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
virtual doublereal cp_mole() const;
/// Molar heat capacity at constant volume. Units: J/kmol/K.
virtual doublereal cv_mole() const;
//! Returns an array of partial molar enthalpies for the species
//! in the mixture.
/*!
@ -541,7 +440,6 @@ public:
*/
virtual void getPartialMolarCp(doublereal* cpbar) const;
//! Return an array of partial molar volumes for the
//! species in the mixture. Units: m^3/kmol.
/*!
@ -576,7 +474,6 @@ public:
*
* @param d2lnActCoeffdT2 Output vector of temperature 2nd derivatives of the
* log Activity Coefficients. length = m_kk
*
*/
virtual void getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const;
@ -589,68 +486,17 @@ public:
*
* @param dlnActCoeffdT Output vector of temperature derivatives of the
* log Activity Coefficients. length = m_kk
*
*/
virtual void getdlnActCoeffdT(doublereal* dlnActCoeffdT) const;
//@}
/// @name Properties of the Standard State of the Species in the Solution
//@{
//@}
/// @name Thermodynamic Values for the Species Reference States
//@{
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
/**
* @name Specific Properties
* @{
*/
/**
* @name Setting the State
*
* These methods set all or part of the thermodynamic
* state.
* @{
*/
//@}
/**
* @name Chemical Equilibrium
* Routines that implement the Chemical equilibrium capability
* for a single phase, based on the element-potential method.
* @{
*/
//@}
/// @}
/// @name Initialization
/// 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.
/*!
* @internal Initialize. This method is provided to allow
* subclasses to perform any initialization required after all
@ -666,7 +512,6 @@ public:
*/
virtual void initThermo();
/**
* Import and initialize a ThermoPhase object
*
@ -683,11 +528,9 @@ public:
*/
void initThermoXML(XML_Node& phaseNode, const std::string& id);
/**
* @}
* @name Derivatives of Thermodynamic Variables needed for Applications
* @{
*/
//! @}
//! @name Derivatives of Thermodynamic Variables needed for Applications
//! @{
//! Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
//! a line in parameter space or along a line in physical space
@ -736,7 +579,6 @@ public:
*/
virtual void getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const;
//! Get the array of derivatives of the ln activity coefficients with respect to the ln species mole numbers
/*!
* Implementations should take the derivative of the logarithm of the activity coefficient with respect to a
@ -760,7 +602,6 @@ public:
//@}
private:
//! Process an XML node called "binaryNeutralSpeciesParameters"
/*!
* This node contains all of the parameters necessary to describe
@ -780,7 +621,6 @@ private:
*/
void resizeNumInteractions(const size_t num);
//! Initialize lengths of local variables after all species have
//! been identified.
void initLengths();
@ -831,7 +671,6 @@ private:
doublereal err(const std::string& msg) const;
protected:
//! number of binary interaction expressions
size_t numBinaryInteractions_;
@ -849,16 +688,13 @@ protected:
*/
std::vector<size_t> m_pSpecies_B_ij;
//! Vector of the length of the polynomial for the interaction.
std::vector<size_t> m_N_ij;
//! Enthalpy term for the binary mole fraction interaction of the
//! excess gibbs free energy expression
mutable std::vector< vector_fp> m_HE_m_ij;
//! Entropy term for the binary mole fraction interaction of the
//! excess gibbs free energy expression
mutable std::vector< vector_fp> m_SE_m_ij;
@ -875,20 +711,10 @@ protected:
*/
int formTempModel_;
//! Two dimensional array of derivatives of activity coefficients wrt mole fractions
mutable Array2D dlnActCoeff_dX_;
};
}
#endif

74
include/cantera/thermo/VPStandardStateTP.h
View file

@ -60,12 +60,8 @@ class VPStandardStateTP : public ThermoPhase
{
public:
//! @name Constructors and Duplicators for %VPStandardStateTP
/*!
*
* @name Constructors and Duplicators for %VPStandardStateTP
*
*/
/// Constructor.
VPStandardStateTP();
@ -84,16 +80,11 @@ public:
//! Destructor.
virtual ~VPStandardStateTP();
/*
* Duplication routine
*/
//! Duplication routine
virtual ThermoPhase* duplMyselfAsThermoPhase() const;
//@}
/**
* @name Utilities (VPStandardStateTP)
*/
//! @name Utilities (VPStandardStateTP)
//@{
/**
* Equation of state type flag. The base class returns
@ -110,12 +101,10 @@ public:
//! 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
* - Temperature-based activities,
* `cSS_CONVENTION_TEMPERATURE 0` (default)
* - Variable Pressure and Temperature-based activities,
* `cSS_CONVENTION_VPSS 1`
*/
virtual int standardStateConvention() const;
@ -141,17 +130,14 @@ public:
err("getdlnActCoeffdlnN_diag");
}
//@}
/// @name Partial Molar Properties of the Solution (VPStandardStateTP)
/// @name Partial Molar Properties of the Solution (VPStandardStateTP)
//@{
//! Get the array of non-dimensional species chemical potentials
//! These are partial molar Gibbs free energies.
//! Get the array of non-dimensional species chemical potentials.
/*!
* These are partial molar Gibbs free energies,
* \f$ \mu_k / \hat R T \f$.
* Units: unitless
*
* We close the loop on this function, here, calling
* getChemPotentials() and then dividing by RT. No need for child
@ -165,14 +151,12 @@ public:
//@}
/*!
* @name Properties of the Standard State of the Species in the Solution
* (VPStandardStateTP)
* @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.
* _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.
*/
//@{
@ -271,7 +255,6 @@ public:
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
@ -282,7 +265,6 @@ public:
*/
virtual void setTemperature(const doublereal temp);
//! Set the internally stored pressure (Pa) at constant
//! temperature and composition
/*!
@ -405,7 +387,6 @@ public:
*/
//@{
//! Returns the vector of nondimensional
//! enthalpies of the reference state at the current temperature
//! of the solution and the reference pressure for the species.
@ -434,7 +415,6 @@ public:
//! 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.
@ -488,16 +468,9 @@ public:
* Length: m_kk.
*/
virtual void getStandardVolumes_ref(doublereal* vol) const;
protected:
//@}
public:
//! @name Initialization Methods - For Internal use (VPStandardState)
/*!
* The following methods are used in the process of constructing
@ -521,23 +494,6 @@ public:
*/
virtual void setParametersFromXML(const XML_Node& eosdata) {}
//! @internal Initialize the object
/*!
* 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 after calling installSpecies()
* for each species in the phase. It's called before calling
* initThermoXML() for the phase. Therefore, it's the correct
* place for initializing vectors which have lengths equal to the
* number of species.
*
* @see importCTML.cpp
*/
virtual void initThermo();
//! Initialize a ThermoPhase object, potentially reading activity
@ -634,9 +590,7 @@ protected:
*/
std::vector<PDSS*> m_PDSS_storage;
private:
//! VPStandardStateTP has its own err routine
/*!
* @param msg Error message string

522
src/thermo/DebyeHuckel.cpp
View file

@ -30,9 +30,6 @@ using namespace ctml;
namespace Cantera
{
/*
* Default constructor
*/
DebyeHuckel::DebyeHuckel() :
MolalityVPSSTP(),
m_formDH(DHFORM_DILUTE_LIMIT),
@ -55,14 +52,6 @@ DebyeHuckel::DebyeHuckel() :
m_npActCoeff[2] = 1.545E-3;
}
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*/
DebyeHuckel::DebyeHuckel(const std::string& inputFile,
const std::string& id) :
MolalityVPSSTP(),
@ -108,12 +97,6 @@ DebyeHuckel::DebyeHuckel(XML_Node& phaseRoot, const std::string& id) :
importPhase(*findXMLPhase(&phaseRoot, id), this);
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
DebyeHuckel::DebyeHuckel(const DebyeHuckel& b) :
MolalityVPSSTP(),
m_formDH(DHFORM_DILUTE_LIMIT),
@ -136,12 +119,6 @@ DebyeHuckel::DebyeHuckel(const DebyeHuckel& b) :
*this = b;
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
DebyeHuckel& DebyeHuckel::
operator=(const DebyeHuckel& b)
{
@ -187,13 +164,6 @@ operator=(const DebyeHuckel& b)
return *this;
}
/*
* ~DebyeHuckel(): (virtual)
*
* Destructor for DebyeHuckel. Release objects that
* it owns.
*/
DebyeHuckel::~DebyeHuckel()
{
if (m_waterProps) {
@ -202,24 +172,11 @@ DebyeHuckel::~DebyeHuckel()
}
}
/*
* duplMyselfAsThermoPhase():
*
* This routine operates at the ThermoPhase level to
* duplicate the current object. It uses the copy constructor
* defined above.
*/
ThermoPhase* DebyeHuckel::duplMyselfAsThermoPhase() const
{
return new DebyeHuckel(*this);
}
/*
* 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.
*/
int DebyeHuckel::eosType() const
{
int res;
@ -243,23 +200,15 @@ int DebyeHuckel::eosType() const
//
// -------- Molar Thermodynamic Properties of the Solution ---------------
//
/*
* Molar enthalpy of the solution. Units: J/kmol.
*/
doublereal DebyeHuckel::enthalpy_mole() const
{
getPartialMolarEnthalpies(DATA_PTR(m_tmpV));
return mean_X(DATA_PTR(m_tmpV));
}
/*
* Molar internal energy of the solution. Units: J/kmol.
*
* This is calculated from the soln enthalpy and then
* subtracting pV.
*/
doublereal DebyeHuckel::intEnergy_mole() const
{
// This is calculated from the soln enthalpy and then subtracting pV.
double hh = enthalpy_mole();
double pres = pressure();
double molarV = 1.0/molarDensity();
@ -267,30 +216,18 @@ doublereal DebyeHuckel::intEnergy_mole() const
return uu;
}
/*
* Molar soln entropy at constant pressure. Units: J/kmol/K.
*
* This is calculated from the partial molar entropies.
*/
doublereal DebyeHuckel::entropy_mole() const
{
getPartialMolarEntropies(DATA_PTR(m_tmpV));
return mean_X(DATA_PTR(m_tmpV));
}
// Molar Gibbs function. Units: J/kmol.
doublereal DebyeHuckel::gibbs_mole() const
{
getChemPotentials(DATA_PTR(m_tmpV));
return mean_X(DATA_PTR(m_tmpV));
}
/*
* Molar heat capacity at constant pressure. Units: J/kmol/K.
*
* Returns the solution heat capacition at constant pressure.
* This is calculated from the partial molar heat capacities.
*/
doublereal DebyeHuckel::cp_mole() const
{
getPartialMolarCp(DATA_PTR(m_tmpV));
@ -298,7 +235,6 @@ doublereal DebyeHuckel::cp_mole() const
return val;
}
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal DebyeHuckel::cv_mole() const
{
//getPartialMolarCv(m_tmpV.begin());
@ -311,11 +247,6 @@ doublereal DebyeHuckel::cv_mole() const
// ------- Mechanical Equation of State Properties ------------------------
//
/*
* Pressure. Units: Pa.
* For this incompressible system, we return the internally stored
* independent value of the pressure.
*/
doublereal DebyeHuckel::pressure() const
{
return m_Pcurrent;
@ -348,27 +279,6 @@ void DebyeHuckel::setState_TP(doublereal t, doublereal p)
calcDensity();
}
/*
* 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.
*
*/
void DebyeHuckel::calcDensity()
{
if (m_waterSS) {
@ -392,17 +302,6 @@ void DebyeHuckel::calcDensity()
Phase::setDensity(dd);
}
/*
* 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]
*
* It's equal to zero for this model, since the molar volume
* doesn't change with pressure or temperature.
*/
doublereal DebyeHuckel::isothermalCompressibility() const
{
throw CanteraError("DebyeHuckel::isothermalCompressibility",
@ -410,17 +309,6 @@ doublereal DebyeHuckel::isothermalCompressibility() const
return 0.0;
}
/*
* The 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]
*
* It's equal to zero for this model, since the molar volume
* doesn't change with pressure or temperature.
*/
doublereal DebyeHuckel::thermalExpansionCoeff() const
{
throw CanteraError("DebyeHuckel::thermalExpansionCoeff",
@ -428,22 +316,6 @@ doublereal DebyeHuckel::thermalExpansionCoeff() const
return 0.0;
}
/*
* Overwritten setDensity() function is necessary because the
* density is not an independent variable.
*
* This function will now throw an error condition
*
* @internal May have to adjust the strategy here to make
* the eos for these materials slightly compressible, in order
* to create a condition where the density is a function of
* the pressure.
*
* This function will now throw an error condition.
*
* NOTE: This is an overwritten function from the State.h
* class
*/
void DebyeHuckel::setDensity(doublereal rho)
{
double dens = density();
@ -453,15 +325,6 @@ void DebyeHuckel::setDensity(doublereal rho)
}
}
/*
* Overwritten setMolarDensity() function is necessary because the
* density is not an independent variable.
*
* This function will now throw an error condition.
*
* NOTE: This is a virtual function, overwritten function from the State.h
* class
*/
void DebyeHuckel::setMolarDensity(const doublereal conc)
{
double concI = molarDensity();
@ -471,34 +334,15 @@ void DebyeHuckel::setMolarDensity(const doublereal conc)
}
}
/*
* Overwritten setTemperature(double) from State.h. This
* function sets the temperature, and makes sure that
* the value propagates to underlying objects.
*/
void DebyeHuckel::setTemperature(const doublereal temp)
{
setState_TP(temp, m_Pcurrent);
}
//
// ------- Activities and Activity Concentrations
//
/*
* This method returns an array of generalized concentrations
* \f$ C_k\f$ that are defined such that
* \f$ a_k = C_k / C^0_k, \f$ where \f$ C^0_k \f$
* is a standard concentration
* defined below. These generalized concentrations are used
* by kinetics manager classes to compute the forward and
* reverse rates of elementary reactions.
*
* @param c Array of generalized concentrations. The
* units depend upon the implementation of the
* reaction rate expressions within the phase.
*/
void DebyeHuckel::getActivityConcentrations(doublereal* c) const
{
double c_solvent = standardConcentration();
@ -508,61 +352,18 @@ void DebyeHuckel::getActivityConcentrations(doublereal* c) const
}
}
/*
* The standard concentration \f$ C^0_k \f$ used to normalize
* the generalized concentration. In many cases, this quantity
* will be the same for all species in a phase - for example,
* for an ideal gas \f$ C^0_k = P/\hat R T \f$. For this
* reason, this method returns a single value, instead of an
* array. However, for phases in which the standard
* concentration is species-specific (e.g. surface species of
* different sizes), this method may be called with an
* optional parameter indicating the species.
*
* For the time being we will use the concentration of pure
* solvent for the the standard concentration of all species.
* This has the effect of making reaction rates
* based on the molality of species proportional to the
* molality of the species.
*/
doublereal DebyeHuckel::standardConcentration(size_t k) const
{
double mvSolvent = m_speciesSize[m_indexSolvent];
return 1.0 / mvSolvent;
}
/*
* Returns the natural logarithm of the standard
* concentration of the kth species
*/
doublereal DebyeHuckel::logStandardConc(size_t k) const
{
double c_solvent = standardConcentration(k);
return log(c_solvent);
}
/*
* Returns the units of the standard and general concentrations
* Note they have the same units, as their divisor 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.
*
* On return uA contains the powers of the units (MKS assumed)
* of the standard concentrations and generalized concentrations
* for the kth species.
*
* 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
*/
void DebyeHuckel::getUnitsStandardConc(double* uA, int k, int sizeUA) const
{
for (int i = 0; i < sizeUA; i++) {
@ -587,14 +388,6 @@ void DebyeHuckel::getUnitsStandardConc(double* uA, int k, int sizeUA) const
}
}
/*
* Get the array of non-dimensional activities at
* the current solution temperature, pressure, and
* solution concentration.
* (note solvent activity coefficient is on the molar scale).
*
*/
void DebyeHuckel::getActivities(doublereal* ac) const
{
_updateStandardStateThermo();
@ -613,17 +406,6 @@ void DebyeHuckel::getActivities(doublereal* ac) const
exp(m_lnActCoeffMolal[m_indexSolvent]) * xmolSolvent;
}
/*
* getMolalityActivityCoefficients() (virtual, const)
*
* Get the array of non-dimensional Molality based
* activity coefficients at
* the current solution temperature, pressure, and
* solution concentration.
* (note solvent activity coefficient is on the molar scale).
*
* Note, most of the work is done in an internal private routine
*/
void DebyeHuckel::
getMolalityActivityCoefficients(doublereal* acMolality) const
{
@ -639,21 +421,6 @@ getMolalityActivityCoefficients(doublereal* acMolality) const
//
// ------ Partial Molar Properties of the Solution -----------------
//
/*
* Get the species chemical potentials. Units: J/kmol.
*
* This function returns a vector of chemical potentials of the
* species in solution.
*
* \f[
* \mu_k = \mu^{o}_k(T,P) + R T ln(m_k)
* \f]
*
* \f[
* \mu_solvent = \mu^{o}_solvent(T,P) +
* R T ((X_solvent - 1.0) / X_solvent)
* \f]
*/
void DebyeHuckel::getChemPotentials(doublereal* mu) const
{
double xx;
@ -682,19 +449,6 @@ void DebyeHuckel::getChemPotentials(doublereal* mu) const
RT * (log(xx) + m_lnActCoeffMolal[m_indexSolvent]);
}
/*
* Returns an array of partial molar enthalpies for the species
* in the mixture.
* Units (J/kmol)
*
* We calculate this quantity partially from the relation and
* partially by calling the standard state enthalpy function.
*
* hbar_i = - T**2 * d(chemPot_i/T)/dT
*
* We calculate
*/
void DebyeHuckel::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
@ -729,35 +483,6 @@ void DebyeHuckel::getPartialMolarEnthalpies(doublereal* hbar) const
}
}
/*
*
* getPartialMolarEntropies() (virtual, const)
*
* Returns an array of partial molar entropies of the species in the
* solution. Units: J/kmol.
*
* Maxwell's equations provide an insight in how to calculate this
* (p.215 Smith and Van Ness)
*
* d(chemPot_i)/dT = -sbar_i
*
* For this phase, the partial molar entropies are equal to the
* SS species entropies plus the ideal solution contribution.following
* contribution:
* \f[
* \bar s_k(T,P) = \hat s^0_k(T) - R log(M0 * molality[k])
* \f]
* \f[
* \bar s_solvent(T,P) = \hat s^0_solvent(T)
* - R ((xmolSolvent - 1.0) / xmolSolvent)
* \f]
*
* The reference-state pure-species entropies,\f$ \hat s^0_k(T) \f$,
* at the reference pressure, \f$ P_{ref} \f$, are computed by the
* species thermodynamic
* property manager. They are polynomial functions of temperature.
* @see SpeciesThermo
*/
void DebyeHuckel::
getPartialMolarEntropies(doublereal* sbar) const
{
@ -807,25 +532,6 @@ getPartialMolarEntropies(doublereal* sbar) const
}
}
/*
* getPartialMolarVolumes() (virtual, const)
*
* returns an array of partial molar volumes of the species
* in the solution. Units: m^3 kmol-1.
*
* For this solution, the partial molar volumes are normally
* equal to theconstant species molar volumes, except
* when the activity coefficients depend on pressure.
*
* The general relation is
*
* vbar_i = d(chemPot_i)/dP at const T, n
*
* = V0_i + d(Gex)/dP)_T,M
*
* = V0_i + RT d(lnActCoeffi)dP _T,M
*
*/
void DebyeHuckel::getPartialMolarVolumes(doublereal* vbar) const
{
getStandardVolumes(vbar);
@ -841,15 +547,6 @@ void DebyeHuckel::getPartialMolarVolumes(doublereal* vbar) const
}
}
/*
* Partial molar heat capacity of the solution:
* The kth partial molar heat capacity is equal to
* the temperature derivative of the partial molar
* enthalpy of the kth species in the solution at constant
* P and composition (p. 220 Smith and Van Ness).
*
* Cp = -T d2(chemPot_i)/dT2
*/
void DebyeHuckel::getPartialMolarCp(doublereal* cpbar) const
{
/*
@ -886,19 +583,10 @@ void DebyeHuckel::getPartialMolarCp(doublereal* cpbar) const
}
}
/*
* -------------- Utilities -------------------------------
*/
/*
* Initialization routine for a DebyeHuckel phase.
*
* This is a virtual routine. This routine will call initThermo()
* for the parent class as well.
*/
void DebyeHuckel::initThermo()
{
MolalityVPSSTP::initThermo();
@ -934,24 +622,6 @@ static int interp_est(const std::string& estString)
return rval;
}
/*
* Process the XML file after species are set up.
*
* This gets called from importPhase(). It processes the XML file
* after the species are set up. This is the main routine for
* reading in activity coefficient parameters.
*
* @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.
*/
void DebyeHuckel::
initThermoXML(XML_Node& phaseNode, const std::string& id)
{
@ -1461,14 +1131,6 @@ initThermoXML(XML_Node& phaseNode, const std::string& id)
}
/*
* @internal
* Set equation of state parameters. The number and meaning of
* these depends on the subclass.
* @param n number of parameters
* @param c array of \i n coefficients
*
*/
void DebyeHuckel::setParameters(int n, doublereal* const c)
{
}
@ -1477,44 +1139,10 @@ void DebyeHuckel::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.
*
* @param eosdata An XML_Node object corresponding to
* the "thermo" entry for this phase in the input file.
*
* HKM -> Right now, the parameters are set elsewhere (initThermoXML)
* It just didn't seem to fit.
*/
void DebyeHuckel::setParametersFromXML(const XML_Node& eosdata)
{
}
/*
* Report the molar volume of species k
*
* units - \f$ m^3 kmol^-1 \f$
*/
// double DebyeHuckel::speciesMolarVolume(int k) const {
// return m_speciesSize[k];
//}
/*
* A_Debye_TP() (virtual)
*
* Returns the A_Debye parameter as a function of temperature
* and pressure.
*
* The default is to assume that it is constant, given
* in the initialization process and stored in the
* member double, m_A_Debye
*/
double DebyeHuckel::A_Debye_TP(double tempArg, double presArg) const
{
double T = temperature();
@ -1542,16 +1170,6 @@ double DebyeHuckel::A_Debye_TP(double tempArg, double presArg) const
return A;
}
/*
* dA_DebyedT_TP() (virtual)
*
* Returns the derivative of the A_Debye parameter with
* respect to temperature as a function of temperature
* and pressure.
*
* units = A_Debye has units of sqrt(gmol kg-1).
* Temp has units of Kelvin.
*/
double DebyeHuckel::dA_DebyedT_TP(double tempArg, double presArg) const
{
double T = temperature();
@ -1577,16 +1195,6 @@ double DebyeHuckel::dA_DebyedT_TP(double tempArg, double presArg) const
return dAdT;
}
/*
* d2A_DebyedT2_TP() (virtual)
*
* Returns the 2nd derivative of the A_Debye parameter with
* respect to temperature as a function of temperature
* and pressure.
*
* units = A_Debye has units of sqrt(gmol kg-1).
* Temp has units of Kelvin.
*/
double DebyeHuckel::d2A_DebyedT2_TP(double tempArg, double presArg) const
{
double T = temperature();
@ -1612,16 +1220,6 @@ double DebyeHuckel::d2A_DebyedT2_TP(double tempArg, double presArg) const
return d2AdT2;
}
/*
* dA_DebyedP_TP() (virtual)
*
* Returns the derivative of the A_Debye parameter with
* respect to pressure, as a function of temperature
* and pressure.
*
* units = A_Debye has units of sqrt(gmol kg-1).
* Pressure has units of pascals.
*/
double DebyeHuckel::dA_DebyedP_TP(double tempArg, double presArg) const
{
double T = temperature();
@ -1647,13 +1245,10 @@ double DebyeHuckel::dA_DebyedP_TP(double tempArg, double presArg) const
return dAdP;
}
/*
* ----------- Critical State Properties --------------------------
*/
/*
* ---------- Other Property Functions
*/
double DebyeHuckel::AionicRadius(int k) const
{
return m_Aionic[k];
@ -1663,10 +1258,6 @@ double DebyeHuckel::AionicRadius(int k) const
* ------------ Private and Restricted Functions ------------------
*/
/*
* Bail out of functions with an error exit if they are not
* implemented.
*/
doublereal DebyeHuckel::err(const std::string& msg) const
{
throw CanteraError("DebyeHuckel",
@ -1674,13 +1265,6 @@ doublereal DebyeHuckel::err(const std::string& msg) const
return 0.0;
}
/*
* initLengths():
*
* This internal function adjusts the lengths of arrays based on
* the number of species
*/
void DebyeHuckel::initLengths()
{
m_kk = nSpecies();
@ -1705,13 +1289,6 @@ void DebyeHuckel::initLengths()
}
}
/*
* nonpolarActCoeff() (private)
*
* Static function that implements the non-polar species
* salt-out modifications.
* Returns the calculated activity coefficients.
*/
double DebyeHuckel::_nonpolarActCoeff(double IionicMolality) const
{
double I2 = IionicMolality * IionicMolality;
@ -1722,16 +1299,7 @@ double DebyeHuckel::_nonpolarActCoeff(double IionicMolality) const
return pow(10.0 , l10actCoeff);
}
/**
* _osmoticCoeffHelgesonFixedForm()
*
* Formula for the osmotic coefficient that occurs in
* the GWB. It is originally from Helgeson for a variable
* NaCl brine. It's to be used with extreme caution.
*/
double DebyeHuckel::
_osmoticCoeffHelgesonFixedForm() const
double DebyeHuckel::_osmoticCoeffHelgesonFixedForm() const
{
const double a0 = 1.454;
const double b0 = 0.02236;
@ -1750,17 +1318,7 @@ _osmoticCoeffHelgesonFixedForm() const
return oc;
}
/*
* _activityWaterHelgesonFixedForm()
*
* Formula for the log of the activity of the water
* solvent that occurs in
* the GWB. It is originally from Helgeson for a variable
* NaCl brine. It's to be used with extreme caution.
*/
double DebyeHuckel::
_lnactivityWaterHelgesonFixedForm() const
double DebyeHuckel::_lnactivityWaterHelgesonFixedForm() const
{
/*
* Update the internally stored vector of molalities
@ -1780,19 +1338,6 @@ _lnactivityWaterHelgesonFixedForm() const
return lac;
}
/*
* s_update_lnMolalityActCoeff():
*
* Using internally stored values, this function calculates
* the activity coefficients for all species.
*
* The ln(activity_solvent) is first calculated for the
* solvent. Then the molar based activity coefficient
* is calculated and returned.
*
* ( Note this is the main routine for implementing the
* activity coefficient formulation.)
*/
void DebyeHuckel::s_update_lnMolalityActCoeff() const
{
double z_k, zs_k1, zs_k2;
@ -2051,18 +1596,6 @@ void DebyeHuckel::s_update_lnMolalityActCoeff() const
lnActivitySolvent - log(xmolSolvent);
}
/*
* s_update_dMolalityActCoeff_dT() (private, const )
*
* Using internally stored values, this function calculates
* the temperature derivative of the logarithm of the
* activity coefficient for all species in the mechanism.
*
* We assume that the activity coefficients are current.
*
* solvent activity coefficient is on the molality
* scale. Its derivative is too.
*/
void DebyeHuckel::s_update_dlnMolalityActCoeff_dT() const
{
double z_k, coeff, tmp, y, yp1, sigma, tmpLn;
@ -2190,19 +1723,6 @@ void DebyeHuckel::s_update_dlnMolalityActCoeff_dT() const
}
/*
* s_update_d2lnMolalityActCoeff_dT2() (private, const )
*
* Using internally stored values, this function calculates
* the temperature 2nd derivative of the logarithm of the
* activity coefficient
* for all species in the mechanism.
*
* We assume that the activity coefficients are current.
*
* solvent activity coefficient is on the molality
* scale. Its derivatives are too.
*/
void DebyeHuckel::s_update_d2lnMolalityActCoeff_dT2() const
{
double z_k, coeff, tmp, y, yp1, sigma, tmpLn;
@ -2325,19 +1845,6 @@ void DebyeHuckel::s_update_d2lnMolalityActCoeff_dT2() const
}
}
/*
* s_update_dlnMolalityActCoeff_dP() (private, const )
*
* Using internally stored values, this function calculates
* the pressure derivative of the logarithm of the
* activity coefficient for all species in the mechanism.
*
* We assume that the activity coefficients, molalities,
* and A_Debye are current.
*
* solvent activity coefficient is on the molality
* scale. Its derivatives are too.
*/
void DebyeHuckel::s_update_dlnMolalityActCoeff_dP() const
{
double z_k, coeff, tmp, y, yp1, sigma, tmpLn;
@ -2464,25 +1971,4 @@ void DebyeHuckel::s_update_dlnMolalityActCoeff_dP() const
}
}
/*
* Updates the standard state thermodynamic functions at the current T and P of the solution.
*
* @internal
*
* This function gets 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.
*/
// void DebyeHuckel::_updateStandardStateThermo() const {
// doublereal tnow = temperature();
// doublereal pnow = m_Pcurrent;
// if (m_waterSS) {
// m_waterSS->setTempPressure(tnow, pnow);
// }
// m_VPSS_ptr->setState_TP(tnow, pnow);
// VPStandardStateTP::updateStandardStateThermo();
//}
}

113
src/thermo/GibbsExcessVPSSTP.cpp
View file

@ -26,10 +26,6 @@ using namespace std;
namespace Cantera
{
/*
* Default constructor.
*
*/
GibbsExcessVPSSTP::GibbsExcessVPSSTP() :
VPStandardStateTP(),
moleFractions_(0),
@ -43,12 +39,6 @@ GibbsExcessVPSSTP::GibbsExcessVPSSTP() :
{
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
GibbsExcessVPSSTP::GibbsExcessVPSSTP(const GibbsExcessVPSSTP& b) :
VPStandardStateTP(),
moleFractions_(0),
@ -63,12 +53,6 @@ GibbsExcessVPSSTP::GibbsExcessVPSSTP(const GibbsExcessVPSSTP& b) :
GibbsExcessVPSSTP::operator=(b);
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
GibbsExcessVPSSTP& GibbsExcessVPSSTP::
operator=(const GibbsExcessVPSSTP& b)
{
@ -90,31 +74,16 @@ operator=(const GibbsExcessVPSSTP& b)
return *this;
}
/*
*
* ~GibbsExcessVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
GibbsExcessVPSSTP::~GibbsExcessVPSSTP()
{
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
GibbsExcessVPSSTP::duplMyselfAsThermoPhase() const
{
return new GibbsExcessVPSSTP(*this);
}
/*
* -------------- Utilities -------------------------------
*/
void GibbsExcessVPSSTP::setMassFractions(const doublereal* const y)
{
Phase::setMassFractions(y);
@ -139,44 +108,21 @@ void GibbsExcessVPSSTP::setMoleFractions_NoNorm(const doublereal* const x)
getMoleFractions(DATA_PTR(moleFractions_));
}
void GibbsExcessVPSSTP::setConcentrations(const doublereal* const c)
{
Phase::setConcentrations(c);
getMoleFractions(DATA_PTR(moleFractions_));
}
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The GibbsExcessVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int GibbsExcessVPSSTP::eosType() const
{
return 0;
}
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
/*
*
* ------------ Mechanical Properties ------------------------------
*
*/
/*
* Set the pressure at constant temperature. Units: Pa.
* This method sets a constant within the object.
* The mass density is not a function of pressure.
*/
void GibbsExcessVPSSTP::setPressure(doublereal p)
{
setState_TP(temperature(), p);
@ -215,17 +161,15 @@ void GibbsExcessVPSSTP::setState_TP(doublereal t, doublereal p)
calcDensity();
}
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
void GibbsExcessVPSSTP::getActivityConcentrations(doublereal* c) const
{
getActivities(c);
}
doublereal GibbsExcessVPSSTP::standardConcentration(size_t k) const
{
return 1.0;
@ -261,7 +205,6 @@ void GibbsExcessVPSSTP::getActivityCoefficients(doublereal* const ac) const
}
}
}
//====================================================================================================================
void GibbsExcessVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
@ -276,16 +219,6 @@ void GibbsExcessVPSSTP::getElectrochemPotentials(doublereal* mu) const
* ------------ Partial Molar Properties of the Solution ------------
*/
// Return an array of partial molar volumes for the
// species in the mixture. Units: m^3/kmol.
/*
* Frequently, for this class of thermodynamics representations,
* the excess Volume due to mixing is zero. Here, we set it as
* a default. It may be overridden in derived classes.
*
* @param vbar Output vector of species partial molar volumes.
* Length = m_kk. units are m^3/kmol.
*/
void GibbsExcessVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
{
/*
@ -299,7 +232,6 @@ const vector_fp& GibbsExcessVPSSTP::getPartialMolarVolumes() const
return getStandardVolumes();
}
doublereal GibbsExcessVPSSTP::err(const std::string& msg) const
{
throw CanteraError("GibbsExcessVPSSTP","Base class method "
@ -307,8 +239,6 @@ doublereal GibbsExcessVPSSTP::err(const std::string& msg) const
return 0;
}
double GibbsExcessVPSSTP::checkMFSum(const doublereal* const x) const
{
doublereal norm = accumulate(x, x + m_kk, 0.0);
@ -319,28 +249,6 @@ double GibbsExcessVPSSTP::checkMFSum(const doublereal* const x) const
return norm;
}
/*
* Returns the units of the standard and general concentrations
* Note they have the same units, as their divisor 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.
*
* On return uA contains the powers of the units (MKS assumed)
* of the standard concentrations and generalized concentrations
* for the kth species.
*
* 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
*/
void GibbsExcessVPSSTP::getUnitsStandardConc(double* uA, int k, int sizeUA) const
{
for (int i = 0; i < sizeUA; i++) {
@ -365,20 +273,6 @@ void GibbsExcessVPSSTP::getUnitsStandardConc(double* uA, int k, int sizeUA) cons
}
}
/*
* @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.
*
* @see importCTML.cpp
*/
void GibbsExcessVPSSTP::initThermo()
{
initLengths();
@ -386,9 +280,6 @@ void GibbsExcessVPSSTP::initThermo()
getMoleFractions(DATA_PTR(moleFractions_));
}
// Initialize lengths of local variables after all species have
// been identified.
void GibbsExcessVPSSTP::initLengths()
{
m_kk = nSpecies();
@ -402,6 +293,4 @@ void GibbsExcessVPSSTP::initLengths()
m_pp.resize(m_kk);
}
}

742
src/thermo/HMWSoln.cpp
View file

File diff suppressed because it is too large Load diff

128
src/thermo/HMWSoln_input.cpp
View file

@ -28,13 +28,6 @@ using namespace ctml;
namespace Cantera
{
//! utility function to assign an integer value from a string
//! for the ElectrolyteSpeciesType field.
/*!
* @param estString string name of the electrolyte species type
*/
int HMWSoln::interp_est(const std::string& estString)
{
const char* cc = estString.c_str();
@ -60,13 +53,6 @@ int HMWSoln::interp_est(const std::string& estString)
return rval;
}
/*
* Process an XML node called "SimpleSaltParameters.
* This node contains all of the parameters necessary to describe
* the Pitzer model for that particular binary salt.
* This function reads the XML file and writes the coefficients
* it finds to an internal data structures.
*/
void HMWSoln::readXMLBinarySalt(XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -268,11 +254,6 @@ void HMWSoln::readXMLBinarySalt(XML_Node& BinSalt)
}
}
/**
* Process an XML node called "thetaAnion".
* This node contains all of the parameters necessary to describe
* the binary interactions between two anions.
*/
void HMWSoln::readXMLThetaAnion(XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -355,11 +336,6 @@ void HMWSoln::readXMLThetaAnion(XML_Node& BinSalt)
}
}
/**
* Process an XML node called "thetaCation".
* This node contains all of the parameters necessary to describe
* the binary interactions between two cation.
*/
void HMWSoln::readXMLThetaCation(XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -442,11 +418,6 @@ void HMWSoln::readXMLThetaCation(XML_Node& BinSalt)
}
}
/*
* Process an XML node called "readXMLPsiCommonCation".
* This node contains all of the parameters necessary to describe
* the binary interactions between two anions and one common cation.
*/
void HMWSoln::readXMLPsiCommonCation(XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -588,11 +559,6 @@ void HMWSoln::readXMLPsiCommonCation(XML_Node& BinSalt)
}
}
/**
* Process an XML node called "PsiCommonAnion".
* This node contains all of the parameters necessary to describe
* the binary interactions between two cations and one common anion.
*/
void HMWSoln::readXMLPsiCommonAnion(XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -735,14 +701,6 @@ void HMWSoln::readXMLPsiCommonAnion(XML_Node& BinSalt)
}
}
/**
* Process an XML node called "LambdaNeutral".
* This node contains all of the parameters necessary to describe
* the binary interactions between one neutral species and
* any other species (neutral or otherwise) in the mechanism.
*/
void HMWSoln::readXMLLambdaNeutral(XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -824,11 +782,6 @@ void HMWSoln::readXMLLambdaNeutral(XML_Node& BinSalt)
}
}
/**
* Process an XML node called "MunnnNeutral".
* This node contains all of the parameters necessary to describe
* the self-ternary interactions for one neutral species.
*/
void HMWSoln::readXMLMunnnNeutral(XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -899,11 +852,6 @@ void HMWSoln::readXMLMunnnNeutral(XML_Node& BinSalt)
}
}
/*
* Process an XML node called "readXMLZetaCation".
* This node contains all of the parameters necessary to describe
* the ternary interactions between a neutral, a cation and an anion
*/
void HMWSoln::readXMLZetaCation(const XML_Node& BinSalt)
{
string xname = BinSalt.name();
@ -1004,11 +952,6 @@ void HMWSoln::readXMLZetaCation(const XML_Node& BinSalt)
}
}
// Process an XML node called "croppingCoefficients"
// for the cropping coefficients values
/*
* @param acNode Activity Coefficient XML Node
*/
void HMWSoln::readXMLCroppingCoefficients(const XML_Node& acNode)
{
@ -1035,32 +978,12 @@ void HMWSoln::readXMLCroppingCoefficients(const XML_Node& acNode)
}
}
/*
* Initialization routine for a HMWSoln phase.
*
* This is a virtual routine. This routine will call initThermo()
* for the parent class as well.
*/
void HMWSoln::initThermo()
{
MolalityVPSSTP::initThermo();
initLengths();
}
/*
* Import, construct, and initialize a HMWSoln phase
* specification from an XML tree into the current object.
*
* This routine is a precursor to constructPhaseXML(XML_Node*)
* routine, which does most of the work.
*
* @param infile XML file containing the description of the
* phase
*
* @param id Optional parameter identifying the name of the
* phase. If none is given, the first XML
* phase element will be used.
*/
void HMWSoln::constructPhaseFile(std::string inputFile, std::string id)
{
@ -1092,33 +1015,6 @@ void HMWSoln::constructPhaseFile(std::string inputFile, std::string id)
delete fxml;
}
/*
* Import, construct, and initialize a HMWSoln phase
* specification from an XML tree into the current object.
*
* Most of the work is carried out by the cantera base
* routine, importPhase(). That routine imports all of the
* species and element data, including the standard states
* of the species.
*
* Then, In this routine, we read the information
* particular to the specification of the activity
* coefficient model for the Pitzer parameterization.
*
* We also read information about the molar volumes of the
* standard states if present in the XML file.
*
* @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.
*/
void HMWSoln::constructPhaseXML(XML_Node& phaseNode, std::string id)
{
string stemp;
@ -1247,26 +1143,6 @@ void HMWSoln::constructPhaseXML(XML_Node& phaseNode, std::string id)
}
/**
* Process the XML file after species are set up.
*
* This gets called from importPhase(). It processes the XML file
* after the species are set up. This is the main routine for
* reading in activity coefficient parameters.
*
* @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.
*/
void HMWSoln::
initThermoXML(XML_Node& phaseNode, const std::string& id)
{
@ -1825,8 +1701,7 @@ initThermoXML(XML_Node& phaseNode, const std::string& id)
//}
}
//====================================================================================================================
// Precalculate the IMS Cutoff parameters for typeCutoff = 2
void HMWSoln::calcIMSCutoffParams_()
{
IMS_afCut_ = 1.0 / (std::exp(1.0) * IMS_gamma_k_min_);
@ -1877,7 +1752,6 @@ void HMWSoln::calcIMSCutoffParams_()
}
}
// Precalculate the MC Cutoff parameters
void HMWSoln::calcMCCutoffParams_()
{
MC_X_o_min_ = 0.35;

394
src/thermo/IdealMolalSoln.cpp
View file

@ -28,9 +28,6 @@ using namespace ctml;
namespace Cantera
{
/*
* Default constructor
*/
IdealMolalSoln::IdealMolalSoln() :
MolalityVPSSTP(),
m_formGC(2),
@ -38,13 +35,13 @@ IdealMolalSoln::IdealMolalSoln() :
IMS_X_o_cutoff_(0.20),
IMS_gamma_o_min_(0.00001),
IMS_gamma_k_min_(10.0),
IMS_cCut_(.05),
IMS_slopefCut_(0.6),
IMS_slopegCut_(0.0),
IMS_cCut_(.05),
IMS_dfCut_(0.0),
IMS_efCut_(0.0),
IMS_afCut_(0.0),
IMS_bfCut_(0.0),
IMS_slopegCut_(0.0),
IMS_dgCut_(0.0),
IMS_egCut_(0.0),
IMS_agCut_(0.0),
@ -52,12 +49,6 @@ IdealMolalSoln::IdealMolalSoln() :
{
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
IdealMolalSoln::IdealMolalSoln(const IdealMolalSoln& b) :
MolalityVPSSTP(b)
{
@ -68,12 +59,6 @@ IdealMolalSoln::IdealMolalSoln(const IdealMolalSoln& b) :
*this = b;
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
IdealMolalSoln& IdealMolalSoln::
operator=(const IdealMolalSoln& b)
{
@ -111,13 +96,13 @@ IdealMolalSoln::IdealMolalSoln(const std::string& inputFile,
IMS_X_o_cutoff_(0.2),
IMS_gamma_o_min_(0.00001),
IMS_gamma_k_min_(10.0),
IMS_cCut_(.05),
IMS_slopefCut_(0.6),
IMS_slopegCut_(0.0),
IMS_cCut_(.05),
IMS_dfCut_(0.0),
IMS_efCut_(0.0),
IMS_afCut_(0.0),
IMS_bfCut_(0.0),
IMS_slopegCut_(0.0),
IMS_dgCut_(0.0),
IMS_egCut_(0.0),
IMS_agCut_(0.0),
@ -133,13 +118,13 @@ IdealMolalSoln::IdealMolalSoln(XML_Node& root, const std::string& id) :
IMS_X_o_cutoff_(0.2),
IMS_gamma_o_min_(0.00001),
IMS_gamma_k_min_(10.0),
IMS_cCut_(.05),
IMS_slopefCut_(0.6),
IMS_slopegCut_(0.0),
IMS_cCut_(.05),
IMS_dfCut_(0.0),
IMS_efCut_(0.0),
IMS_afCut_(0.0),
IMS_bfCut_(0.0),
IMS_slopegCut_(0.0),
IMS_dgCut_(0.0),
IMS_egCut_(0.0),
IMS_agCut_(0.0),
@ -148,43 +133,15 @@ IdealMolalSoln::IdealMolalSoln(XML_Node& root, const std::string& id) :
importPhase(*findXMLPhase(&root, id), this);
}
/*
*
* ~IdealMolalSoln(): (virtual)
*
* Destructor: does nothing:
*
*/
IdealMolalSoln::~IdealMolalSoln()
{
}
/**
*
*/
ThermoPhase* IdealMolalSoln::duplMyselfAsThermoPhase() const
{
return new IdealMolalSoln(*this);
}
//
// -------- Molar Thermodynamic Properties of the Solution ---------------
//
/*
* Molar enthalpy of the solution: Units: J/kmol.
*
* Returns the amount of enthalpy per mole of solution.
* For an ideal molal solution,
* \f[
* \bar{h}(T, P, X_k) = \sum_k X_k \bar{h}_k(T)
* \f]
* The formula is written in terms of the partial molar enthalpies.
* \f$ \bar{h}_k(T, p, m_k) \f$.
* See the partial molar enthalpy function, getPartialMolarEnthalpies(),
* for details.
*
* Units: J/kmol
*/
doublereal IdealMolalSoln::enthalpy_mole() const
{
getPartialMolarEnthalpies(DATA_PTR(m_tmpV));
@ -193,70 +150,24 @@ doublereal IdealMolalSoln::enthalpy_mole() const
return val;
}
/*
* Molar internal energy of the solution: Units: J/kmol.
*
* Returns the amount of internal energy per mole of solution.
* For an ideal molal solution,
* \f[
* \bar{u}(T, P, X_k) = \sum_k X_k \bar{u}_k(T)
* \f]
* The formula is written in terms of the partial molar internal energy.
* \f$ \bar{u}_k(T, p, m_k) \f$.
*/
doublereal IdealMolalSoln::intEnergy_mole() const
{
getPartialMolarEnthalpies(DATA_PTR(m_tmpV));
return mean_X(DATA_PTR(m_tmpV));
}
/*
* Molar entropy of the solution: Units J/kmol/K.
*
* Returns the amount of entropy per mole of solution.
* For an ideal molal solution,
* \f[
* \bar{s}(T, P, X_k) = \sum_k X_k \bar{s}_k(T)
* \f]
* The formula is written in terms of the partial molar entropies.
* \f$ \bar{s}_k(T, p, m_k) \f$.
* See the partial molar entropies function, getPartialMolarEntropies(),
* for details.
*
* Units: J/kmol/K.
*/
doublereal IdealMolalSoln::entropy_mole() const
{
getPartialMolarEntropies(DATA_PTR(m_tmpV));
return mean_X(DATA_PTR(m_tmpV));
}
/*
* Molar Gibbs function for the solution: Units J/kmol.
*
* Returns the gibbs free energy of the solution per mole
* of the solution.
*
* \f[
* \bar{g}(T, P, X_k) = \sum_k X_k \mu_k(T)
* \f]
*
* Units: J/kmol
*/
doublereal IdealMolalSoln::gibbs_mole() const
{
getChemPotentials(DATA_PTR(m_tmpV));
return mean_X(DATA_PTR(m_tmpV));
}
/*
* Molar heat capacity at constant pressure: Units: J/kmol/K.
* * \f[
* \bar{c}_p(T, P, X_k) = \sum_k X_k \bar{c}_{p,k}(T)
* \f]
*
* Units: J/kmol/K
*/
doublereal IdealMolalSoln::cp_mole() const
{
getPartialMolarCp(DATA_PTR(m_tmpV));
@ -264,11 +175,6 @@ doublereal IdealMolalSoln::cp_mole() const
return val;
}
/*
* Molar heat capacity at constant volume: Units: J/kmol/K.
* NOT IMPLEMENTED.
* Units: J/kmol/K
*/
doublereal IdealMolalSoln::cv_mole() const
{
return err("not implemented");
@ -278,13 +184,6 @@ doublereal IdealMolalSoln::cv_mole() const
// ------- Mechanical Equation of State Properties ------------------------
//
/*
* Set the pressure at constant temperature. Units: Pa.
* This method sets a constant within the object.
* The mass density is not a function of pressure.
*/
void IdealMolalSoln::setPressure(doublereal p)
{
setState_TP(temperature(), p);
@ -304,53 +203,16 @@ void IdealMolalSoln::calcDensity()
Phase::setDensity(dd);
}
/*
* 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]
*
* It's equal to zero for this model, since the molar volume
* doesn't change with pressure or temperature.
*/
doublereal IdealMolalSoln::isothermalCompressibility() const
{
return 0.0;
}
/*
* The 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]
*
* It's equal to zero for this model, since the molar volume
* doesn't change with pressure or temperature.
*/
doublereal IdealMolalSoln::thermalExpansionCoeff() const
{
return 0.0;
}
/*
* Overwritten setDensity() function is necessary because the
* density is not an independent variable.
*
* This function will now throw an error condition
*
* @internal May have to adjust the strategy here to make
* the eos for these materials slightly compressible, in order
* to create a condition where the density is a function of
* the pressure.
*
* This function will now throw an error condition.
*
* NOTE: This is an overwritten function from the State.h
* class
*/
void IdealMolalSoln::setDensity(const doublereal rho)
{
double dens = density();
@ -360,15 +222,6 @@ void IdealMolalSoln::setDensity(const doublereal rho)
}
}
/*
* Overwritten setMolarDensity() function is necessary because the
* density is not an independent variable.
*
* This function will now throw an error condition.
*
* NOTE: This is a virtual function, overwritten function from the State.h
* class
*/
void IdealMolalSoln::setMolarDensity(const doublereal conc)
{
double concI = Phase::molarDensity();
@ -391,19 +244,6 @@ void IdealMolalSoln::setState_TP(doublereal temp, doublereal pres)
// ------- Activities and Activity Concentrations
//
/*
* This method returns an array of activity concentrations \f$ C^a_k\f$.
* \f$ C^a_k\f$ are defined such that
* \f$ a_k = C^a_k / C^s_k, \f$ where \f$ C^s_k \f$
* is a standard concentration
* defined below. These activity concentrations are used
* by kinetics manager classes to compute the forward and
* reverse rates of elementary reactions.
*
* @param c Array of activity concentrations. The
* units depend upon the implementation of the
* reaction rate expressions within the phase.
*/
void IdealMolalSoln::getActivityConcentrations(doublereal* c) const
{
if (m_formGC != 1) {
@ -421,18 +261,6 @@ void IdealMolalSoln::getActivityConcentrations(doublereal* c) const
}
}
/*
* The standard concentration \f$ C^s_k \f$ used to normalize
* the activity concentration. In many cases, this quantity
* will be the same for all species in a phase - for example,
* for an ideal gas \f$ C^s_k = P/\hat R T \f$. For this
* reason, this method returns a single value, instead of an
* array. However, for phases in which the standard
* concentration is species-specific (e.g. surface species of
* different sizes), this method may be called with an
* optional parameter indicating the species.
*
*/
doublereal IdealMolalSoln::standardConcentration(size_t k) const
{
double c0 = 1.0, mvSolvent;
@ -450,38 +278,12 @@ doublereal IdealMolalSoln::standardConcentration(size_t k) const
return c0;
}
/*
* Returns the natural logarithm of the standard
* concentration of the kth species
*/
doublereal IdealMolalSoln::logStandardConc(size_t k) const
{
double c0 = standardConcentration(k);
return log(c0);
}
/*
* Returns the units of the standard and general concentrations
* Note they have the same units, as their divisor 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.
*
* On return uA contains the powers of the units (MKS assumed)
* of the standard concentrations and generalized concentrations
* for the kth species.
*
* 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
*/
void IdealMolalSoln::getUnitsStandardConc(double* uA, int k, int sizeUA) const
{
int eos = eosType();
@ -513,14 +315,6 @@ void IdealMolalSoln::getUnitsStandardConc(double* uA, int k, int sizeUA) const
}
}
/*
* Get the array of non-dimensional molality-based
* activities at the current solution temperature,
* pressure, and solution concentration.
*
* The max against xmolSolventMIN is to limit the activity
* coefficient to be finite as the solvent mf goes to zero.
*/
void IdealMolalSoln::getActivities(doublereal* ac) const
{
_updateStandardStateThermo();
@ -534,6 +328,8 @@ void IdealMolalSoln::getActivities(doublereal* ac) const
ac[k] = m_molalities[k];
}
double xmolSolvent = moleFraction(m_indexSolvent);
// Limit the activity coefficient to be finite as the solvent mole
// fraction goes to zero.
xmolSolvent = std::max(m_xmolSolventMIN, xmolSolvent);
ac[m_indexSolvent] =
exp((xmolSolvent - 1.0)/xmolSolvent);
@ -553,17 +349,6 @@ void IdealMolalSoln::getActivities(doublereal* ac) const
}
}
/*
* Get the array of non-dimensional Molality based
* activity coefficients at
* the current solution temperature, pressure, and
* solution concentration.
* See Denbigh
* (note solvent activity coefficient is on the molar scale).
*
* The max against xmolSolventMIN is to limit the activity
* coefficient to be finite as the solvent mf goes to zero.
*/
void IdealMolalSoln::
getMolalityActivityCoefficients(doublereal* acMolality) const
{
@ -572,6 +357,8 @@ getMolalityActivityCoefficients(doublereal* acMolality) const
acMolality[k] = 1.0;
}
double xmolSolvent = moleFraction(m_indexSolvent);
// Limit the activity coefficient to be finite as the solvent mole
// fraction goes to zero.
xmolSolvent = std::max(m_xmolSolventMIN, xmolSolvent);
acMolality[m_indexSolvent] =
exp((xmolSolvent - 1.0)/xmolSolvent) / xmolSolvent;
@ -588,27 +375,6 @@ getMolalityActivityCoefficients(doublereal* acMolality) const
// ------ Partial Molar Properties of the Solution -----------------
//
/*
* Get the species chemical potentials: Units: J/kmol.
*
* This function returns a vector of chemical potentials of the
* species in solution.
*
* \f[
* \mu_k = \mu^{o}_k(T,P) + R T \ln(\frac{m_k}{m^\Delta})
* \f]
* \f[
* \mu_w = \mu^{o}_w(T,P) +
* R T ((X_w - 1.0) / X_w)
* \f]
*
* \f$ w \f$ refers to the solvent species.
* \f$ X_w \f$ is the mole fraction of the solvent.
* \f$ m_k \f$ is the molality of the kth solute.
* \f$ m^\Delta is 1 gmol solute per kg solvent. \f$
*
* Units: J/kmol.
*/
void IdealMolalSoln::getChemPotentials(doublereal* mu) const
{
double xx;
@ -667,11 +433,6 @@ void IdealMolalSoln::getChemPotentials(doublereal* mu) const
}
/*
* Returns an array of partial molar enthalpies for the species
* in the mixture: Units (J/kmol).
*
*/
void IdealMolalSoln::getPartialMolarEnthalpies(doublereal* hbar) const
{
getEnthalpy_RT(hbar);
@ -681,33 +442,6 @@ void IdealMolalSoln::getPartialMolarEnthalpies(doublereal* hbar) const
}
}
/*
* Returns an array of partial molar entropies of the species in the
* solution: Units: J/kmol.
*
* Maxwell's equations provide an insight in how to calculate this
* (p.215 Smith and Van Ness)
* \f[
* \frac{d(\mu_k)}{dT} = -\bar{s}_i
* \f]
* For this phase, the partial molar entropies are equal to the
* standard state species entropies plus the ideal molal solution contribution.
*
* \f[
* \bar{s}_k(T,P) = s^0_k(T) - R log( m_k )
* \f]
* \f[
* \bar{s}_w(T,P) = s^0_w(T) - R ((X_w - 1.0) / X_w)
* \f]
*
* The subscript, w, refers to the solvent species. \f$ X_w \f$ is
* the mole fraction of solvent.
* The reference-state pure-species entropies,\f$ s^0_k(T) \f$,
* at the reference pressure, \f$ P_{ref} \f$, are computed by the
* species thermodynamic
* property manager. They are polynomial functions of temperature.
* @see SpeciesThermo
*/
void IdealMolalSoln::getPartialMolarEntropies(doublereal* sbar) const
{
getEntropy_R(sbar);
@ -747,36 +481,11 @@ void IdealMolalSoln::getPartialMolarEntropies(doublereal* sbar) const
}
}
/*
* Returns an array of partial molar volumes of the species
* in the solution: Units: m^3 kmol-1.
*
* For this solution, the partial molar volumes are equal to the
* constant species molar volumes.
*
* Units: m^3 kmol-1.
*/
void IdealMolalSoln::getPartialMolarVolumes(doublereal* vbar) const
{
getStandardVolumes(vbar);
}
/*
* Partial molar heat capacity of the solution: Units: J/kmol/K.
*
* The kth partial molar heat capacity is equal to
* the temperature derivative of the partial molar
* enthalpy of the kth species in the solution at constant
* P and composition (p. 220 Smith and Van Ness).
* \f[
* \bar{Cp}_k(T,P) = {Cp}^0_k(T)
* \f]
*
* For this solution, this is equal to the reference state
* heat capacities.
*
* Units: J/kmol/K
*/
void IdealMolalSoln::getPartialMolarCp(doublereal* cpbar) const
{
/*
@ -790,54 +499,16 @@ void IdealMolalSoln::getPartialMolarCp(doublereal* cpbar) const
}
}
/*
* -------- Properties of the Standard State of the Species
* in the Solution ------------------
*/
/*
* ------ Thermodynamic Values for the Species Reference States ---
*/
// -> This is handled by VPStandardStatesTP
/*
* -------------- Utilities -------------------------------
*/
/*
* Initialization routine for an IdealMolalSoln phase.
*
* This is a virtual routine. This routine will call initThermo()
* for the parent class as well.
*/
void IdealMolalSoln::initThermo()
{
initLengths();
MolalityVPSSTP::initThermo();
}
/*
* Import and initialize an IdealMolalSoln phase
* specification in an XML tree into the current object.
*
* This routine is called from importPhase() to finish
* up the initialization of the thermo object. It reads in the
* species molar volumes.
*
* @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.
*/
void IdealMolalSoln::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
/*
@ -1010,14 +681,6 @@ void IdealMolalSoln::initThermoXML(XML_Node& phaseNode, const std::string& id)
}
/*
* @internal
* Set equation of state parameters. The number and meaning of
* these depends on the subclass.
* @param n number of parameters
* @param c array of \i n coefficients
*
*/
void IdealMolalSoln::setParameters(int n, doublereal* const c)
{
}
@ -1026,28 +689,10 @@ void IdealMolalSoln::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.
*
* @param eosdata An XML_Node object corresponding to
* the "thermo" entry for this phase in the input file.
*
* HKM -> Right now, the parameters are set elsewhere (initThermo)
* It just didn't seem to fit.
*/
void IdealMolalSoln::setParametersFromXML(const XML_Node& eosdata)
{
}
/*
* ----------- Critical State Properties --------------------------
*/
/*
* ------------ Private and Restricted Functions ------------------
*/
@ -1063,18 +708,6 @@ doublereal IdealMolalSoln::err(const std::string& msg) const
return 0.0;
}
// This function will be called to update the internally stored
// natural logarithm of the molality activity coefficients
/*
* Normally they are all one. However, sometimes they are not,
* due to stability schemes
*
* gamma_k_molar = gamma_k_molal / Xmol_solvent
*
* gamma_o_molar = gamma_o_molal
*/
void IdealMolalSoln::s_updateIMS_lnMolalityActCoeff() const
{
double tmp;
@ -1187,11 +820,6 @@ void IdealMolalSoln::s_updateIMS_lnMolalityActCoeff() const
return;
}
/*
* This internal function adjusts the lengths of arrays.
*
* This function is not virtual nor is it inherited
*/
void IdealMolalSoln::initLengths()
{
m_kk = nSpecies();
@ -1205,7 +833,6 @@ void IdealMolalSoln::initLengths()
IMS_lnActCoeffMolal_.resize(m_kk);
}
void IdealMolalSoln::calcIMSCutoffParams_()
{
IMS_afCut_ = 1.0 / (std::exp(1.0) * IMS_gamma_k_min_);
@ -1257,4 +884,3 @@ void IdealMolalSoln::calcIMSCutoffParams_()
}
}

118
src/thermo/IdealSolnGasVPSS.cpp
View file

@ -24,9 +24,6 @@ using namespace std;
namespace Cantera
{
/*
* Default constructor
*/
IdealSolnGasVPSS::IdealSolnGasVPSS() :
VPStandardStateTP(),
m_idealGas(0),
@ -34,7 +31,6 @@ IdealSolnGasVPSS::IdealSolnGasVPSS() :
{
}
IdealSolnGasVPSS::IdealSolnGasVPSS(const std::string& infile, std::string id) :
VPStandardStateTP(),
m_idealGas(0),
@ -52,15 +48,6 @@ IdealSolnGasVPSS::IdealSolnGasVPSS(const std::string& infile, std::string id) :
importPhase(*xphase, this);
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor.
*
* The copy constructor just calls the assignment operator
* to do the heavy lifting.
*/
IdealSolnGasVPSS::IdealSolnGasVPSS(const IdealSolnGasVPSS& b) :
VPStandardStateTP(),
m_idealGas(0),
@ -69,12 +56,6 @@ IdealSolnGasVPSS::IdealSolnGasVPSS(const IdealSolnGasVPSS& b) :
*this = b;
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
IdealSolnGasVPSS& IdealSolnGasVPSS::
operator=(const IdealSolnGasVPSS& b)
{
@ -93,18 +74,10 @@ operator=(const IdealSolnGasVPSS& b)
return *this;
}
/*
* ~IdealSolnGasVPSS(): (virtual)
*
*/
IdealSolnGasVPSS::~IdealSolnGasVPSS()
{
}
/*
* Duplication function.
* This calls the copy constructor for this object.
*/
ThermoPhase* IdealSolnGasVPSS::duplMyselfAsThermoPhase() const
{
return new IdealSolnGasVPSS(*this);
@ -118,12 +91,10 @@ int IdealSolnGasVPSS::eosType() const
return cIdealSolnGasVPSS_iscv;
}
/*
* ------------Molar Thermodynamic Properties -------------------------
*/
/// Molar enthalpy. Units: J/kmol.
doublereal IdealSolnGasVPSS::enthalpy_mole() const
{
updateStandardStateThermo();
@ -132,7 +103,6 @@ doublereal IdealSolnGasVPSS::enthalpy_mole() const
mean_X(DATA_PTR(enth_RT)));
}
/// Molar internal energy. Units: J/kmol.
doublereal IdealSolnGasVPSS::intEnergy_mole() const
{
doublereal p0 = pressure();
@ -140,7 +110,6 @@ doublereal IdealSolnGasVPSS::intEnergy_mole() const
return (enthalpy_mole() - p0 / md);
}
/// Molar entropy. Units: J/kmol/K.
doublereal IdealSolnGasVPSS::entropy_mole() const
{
updateStandardStateThermo();
@ -149,13 +118,11 @@ doublereal IdealSolnGasVPSS::entropy_mole() const
}
/// Molar Gibbs function. Units: J/kmol.
doublereal IdealSolnGasVPSS::gibbs_mole() const
{
return enthalpy_mole() - temperature() * entropy_mole();
}
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
doublereal IdealSolnGasVPSS::cp_mole() const
{
updateStandardStateThermo();
@ -163,11 +130,9 @@ doublereal IdealSolnGasVPSS::cp_mole() const
return GasConstant * (mean_X(DATA_PTR(cp_R)));
}
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal IdealSolnGasVPSS::cv_mole() const
{
return cp_mole() - GasConstant;
}
void IdealSolnGasVPSS::setPressure(doublereal p)
@ -236,10 +201,6 @@ void IdealSolnGasVPSS::getActivityConcentrations(doublereal* c) const
}
}
/*
* Returns the standard concentration \f$ C^0_k \f$, which is used to normalize
* the generalized concentration.
*/
doublereal IdealSolnGasVPSS::standardConcentration(size_t k) const
{
if (m_idealGas) {
@ -260,10 +221,6 @@ doublereal IdealSolnGasVPSS::standardConcentration(size_t k) const
}
}
/*
* Returns the natural logarithm of the standard
* concentration of the kth species
*/
doublereal IdealSolnGasVPSS::logStandardConc(size_t k) const
{
double c = standardConcentration(k);
@ -271,32 +228,6 @@ doublereal IdealSolnGasVPSS::logStandardConc(size_t k) const
return lc;
}
/*
*
* getUnitsStandardConcentration()
*
* Returns the units of the standard and general concentrations
* Note they have the same units, as their divisor 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.
*
* 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
*
* For EOS types other than cIdealSolidSolnPhase1, the default
* kmol/m3 holds for standard concentration units. For
* cIdealSolidSolnPhase0 type, the standard concentration is
* unitless.
*/
void IdealSolnGasVPSS::getUnitsStandardConc(double* uA, int, int sizeUA) const
{
int eos = eosType();
@ -328,10 +259,6 @@ void IdealSolnGasVPSS::getUnitsStandardConc(double* uA, int, int sizeUA) const
}
}
/*
* Get the array of non-dimensional activity coefficients
*/
void IdealSolnGasVPSS::getActivityCoefficients(doublereal* ac) const
{
for (size_t k = 0; k < m_kk; k++) {
@ -343,15 +270,6 @@ void IdealSolnGasVPSS::getActivityCoefficients(doublereal* ac) const
* ---- Partial Molar Properties of the Solution -----------------
*/
/*
* Get the array of non-dimensional species chemical potentials
* These are partial molar Gibbs free energies.
* \f$ \mu_k / \hat R T \f$.
* Units: unitless
*
* We close the loop on this function, here, calling
* getChemPotentials() and then dividing by RT.
*/
void IdealSolnGasVPSS::getChemPotentials_RT(doublereal* muRT) const
{
getChemPotentials(muRT);
@ -372,7 +290,6 @@ void IdealSolnGasVPSS::getChemPotentials(doublereal* mu) const
}
}
void IdealSolnGasVPSS::getPartialMolarEnthalpies(doublereal* hbar) const
{
getEnthalpy_RT(hbar);
@ -410,24 +327,12 @@ void IdealSolnGasVPSS::getPartialMolarVolumes(doublereal* vbar) const
getStandardVolumes(vbar);
}
/*
* ----- Thermodynamic Values for the Species Reference States ----
*/
/*
* Perform initializations after all species have been
* added.
*/
void IdealSolnGasVPSS::initThermo()
{
initLengths();
VPStandardStateTP::initThermo();
}
void IdealSolnGasVPSS::setToEquilState(const doublereal* mu_RT)
{
double tmp, tmp2;
@ -461,33 +366,12 @@ void IdealSolnGasVPSS::setToEquilState(const doublereal* mu_RT)
setState_PX(pres, &m_pp[0]);
}
/*
* Initialize the internal lengths.
* (this is not a virtual function)
*/
void IdealSolnGasVPSS::initLengths()
{
m_kk = nSpecies();
m_pp.resize(m_kk, 0.0);
}
/*
* Import and initialize a ThermoPhase object
*
* 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.
*
* This routine initializes the lengths in the current object and
* then calls the parent routine.
*/
void IdealSolnGasVPSS::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
IdealSolnGasVPSS::initLengths();
@ -555,5 +439,3 @@ void IdealSolnGasVPSS::setParametersFromXML(const XML_Node& thermoNode)
}
}

375
src/thermo/IonsFromNeutralVPSSTP.cpp
View file

@ -31,11 +31,6 @@ using namespace std;
namespace Cantera
{
//====================================================================================================================
/*
* Default constructor.
*
*/
IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP() :
GibbsExcessVPSSTP(),
ionSolnType_(cIonSolnType_SINGLEANION),
@ -54,32 +49,6 @@ IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP() :
{
}
//====================================================================================================================
// Construct and initialize an IonsFromNeutralVPSSTP object
// directly from an ASCII input file
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*
* @param inputFile Name of the input file containing the phase XML data
* to set up the object
* @param id ID of the phase in the input file. Defaults to the
* empty string.
* @param neutralPhase The object takes a neutralPhase ThermoPhase
* object as input. It can either take a pointer
* to an existing object in the parameter list,
* in which case it does not own the object, or
* it can construct a neutral Phase as a slave
* object, in which case, it does own the slave
* object, for purposes of who gets to destroy
* the object.
* If this parameter is zero, then a slave
* neutral phase object is created and used.
*/
IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP(const std::string& inputFile,
const std::string& id,
ThermoPhase* neutralPhase) :
@ -107,7 +76,7 @@ IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP(const std::string& inputFile,
//dlnActCoeff_NeutralMolecule.resize(numNeutMolSpec);
//dX_NeutralMolecule.resize(numNeutMolSpec);
}
//====================================================================================================================
IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP(XML_Node& phaseRoot,
const std::string& id, ThermoPhase* neutralPhase) :
GibbsExcessVPSSTP(),
@ -136,14 +105,6 @@ IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP(XML_Node& phaseRoot,
dX_NeutralMolecule.resize(numNeutMolSpec);
}
//====================================================================================================================
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP(const IonsFromNeutralVPSSTP& b) :
GibbsExcessVPSSTP(),
ionSolnType_(cIonSolnType_SINGLEANION),
@ -163,13 +124,7 @@ IonsFromNeutralVPSSTP::IonsFromNeutralVPSSTP(const IonsFromNeutralVPSSTP& b) :
{
IonsFromNeutralVPSSTP::operator=(b);
}
//====================================================================================================================
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
IonsFromNeutralVPSSTP& IonsFromNeutralVPSSTP::
operator=(const IonsFromNeutralVPSSTP& b)
{
@ -232,13 +187,6 @@ operator=(const IonsFromNeutralVPSSTP& b)
return *this;
}
/*
*
* ~IonsFromNeutralVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
IonsFromNeutralVPSSTP::~IonsFromNeutralVPSSTP()
{
if (IOwnNThermoPhase_) {
@ -247,30 +195,12 @@ IonsFromNeutralVPSSTP::~IonsFromNeutralVPSSTP()
}
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
IonsFromNeutralVPSSTP::duplMyselfAsThermoPhase() const
{
return new IonsFromNeutralVPSSTP(*this);
}
/*
* Import, construct, and initialize a phase
* specification from an XML tree into the current object.
*
* This routine is a precursor to constructPhaseXML(XML_Node*)
* routine, which does most of the work.
*
* @param infile XML file containing the description of the
* phase
*
* @param id Optional parameter identifying the name of the
* phase. If none is given, the first XML
* phase element will be used.
*/
void IonsFromNeutralVPSSTP::constructPhaseFile(std::string inputFile, std::string id)
{
@ -302,34 +232,6 @@ void IonsFromNeutralVPSSTP::constructPhaseFile(std::string inputFile, std::strin
delete fxml;
}
/*
* Import, construct, and initialize a HMWSoln phase
* specification from an XML tree into the current object.
*
* Most of the work is carried out by the cantera base
* routine, importPhase(). That routine imports all of the
* species and element data, including the standard states
* of the species.
*
* Then, In this routine, we read the information
* particular to the specification of the activity
* coefficient model for the Pitzer parameterization.
*
* We also read information about the molar volumes of the
* standard states if present in the XML file.
*
* @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.
*/
void IonsFromNeutralVPSSTP::constructPhaseXML(XML_Node& phaseNode, std::string id)
{
string stemp;
@ -398,45 +300,25 @@ void IonsFromNeutralVPSSTP::constructPhaseXML(XML_Node& phaseNode, std::string i
}
/*
* -------------- Utilities -------------------------------
*/
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The IonsFromNeutralVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int IonsFromNeutralVPSSTP::eosType() const
{
return cIonsFromNeutral;
}
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
/*
* Molar enthalpy of the solution. Units: J/kmol.
*/
doublereal IonsFromNeutralVPSSTP::enthalpy_mole() const
{
getPartialMolarEnthalpies(DATA_PTR(m_pp));
return mean_X(DATA_PTR(m_pp));
}
/**
* Molar internal energy of the solution. Units: J/kmol.
*
* This is calculated from the soln enthalpy and then
* subtracting pV.
*/
doublereal IonsFromNeutralVPSSTP::intEnergy_mole() const
{
double hh = enthalpy_mole();
@ -446,28 +328,18 @@ doublereal IonsFromNeutralVPSSTP::intEnergy_mole() const
return uu;
}
/**
* Molar soln entropy at constant pressure. Units: J/kmol/K.
*
* This is calculated from the partial molar entropies.
*/
doublereal IonsFromNeutralVPSSTP::entropy_mole() const
{
getPartialMolarEntropies(DATA_PTR(m_pp));
return mean_X(DATA_PTR(m_pp));
}
/// Molar Gibbs function. Units: J/kmol.
doublereal IonsFromNeutralVPSSTP::gibbs_mole() const
{
getChemPotentials(DATA_PTR(m_pp));
return mean_X(DATA_PTR(m_pp));
}
/** Molar heat capacity at constant pressure. Units: J/kmol/K.
*
* Returns the solution heat capacition at constant pressure.
* This is calculated from the partial molar heat capacities.
*/
doublereal IonsFromNeutralVPSSTP::cp_mole() const
{
getPartialMolarCp(DATA_PTR(m_pp));
@ -475,7 +347,6 @@ doublereal IonsFromNeutralVPSSTP::cp_mole() const
return val;
}
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal IonsFromNeutralVPSSTP::cv_mole() const
{
// Need to revisit this, as it is wrong
@ -484,11 +355,11 @@ doublereal IonsFromNeutralVPSSTP::cv_mole() const
//err("not implemented");
//return 0.0;
}
//===========================================================================================================
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
//===========================================================================================================
void IonsFromNeutralVPSSTP::getDissociationCoeffs(vector_fp& coeffs,
vector_fp& charges, std::vector<size_t>& neutMolIndex) const
{
@ -496,12 +367,7 @@ void IonsFromNeutralVPSSTP::getDissociationCoeffs(vector_fp& coeffs,
charges = m_speciesCharge;
neutMolIndex = fm_invert_ionForNeutral;
}
//===========================================================================================================
// Get the array of non-dimensional molar-based activity coefficients at
// the current solution temperature, pressure, and solution concentration.
/*
* @param ac Output vector of activity coefficients. Length: m_kk.
*/
void IonsFromNeutralVPSSTP::getActivityCoefficients(doublereal* ac) const
{
@ -524,20 +390,10 @@ void IonsFromNeutralVPSSTP::getActivityCoefficients(doublereal* ac) const
}
/*
* --------- Partial Molar Properties of the Solution -------------------------------
* --------- Partial Molar Properties of the Solution -------------
*/
// Get the species chemical potentials. Units: J/kmol.
/*
* This function returns a vector of chemical potentials of the
* species in solution at the current temperature, pressure
* and mole fraction of the solution.
*
* @param mu Output vector of species chemical
* potentials. Length: m_kk. Units: J/kmol
*/
void
IonsFromNeutralVPSSTP::getChemPotentials(doublereal* mu) const
void IonsFromNeutralVPSSTP::getChemPotentials(doublereal* mu) const
{
size_t icat, jNeut;
doublereal xx, fact2;
@ -602,21 +458,6 @@ IonsFromNeutralVPSSTP::getChemPotentials(doublereal* mu) const
}
}
// Returns an array of partial molar enthalpies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* molality-based activity coefficient wrt temperature
*
* \f[
* \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void IonsFromNeutralVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
@ -643,20 +484,6 @@ void IonsFromNeutralVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
}
}
// Returns an array of partial molar entropies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void IonsFromNeutralVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
{
double xx;
@ -684,26 +511,6 @@ void IonsFromNeutralVPSSTP::getPartialMolarEntropies(doublereal* sbar) 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. mole fraction,
* molality, etc.) 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 dlnActCoeffdlnX Output vector of log(mole fraction)
* derivatives of the log Activity Coefficients.
* length = m_kk
*/
void IonsFromNeutralVPSSTP::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_diag) const
{
s_update_lnActCoeff();
@ -713,26 +520,7 @@ void IonsFromNeutralVPSSTP::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_
dlnActCoeffdlnX_diag[k] = dlnActCoeffdlnX_diag_[k];
}
}
//====================================================================================================================
// 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 log(mole fraction)
* derivatives of the log Activity Coefficients.
* length = m_kk
*/
void IonsFromNeutralVPSSTP::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const
{
s_update_lnActCoeff();
@ -742,7 +530,7 @@ void IonsFromNeutralVPSSTP::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_
dlnActCoeffdlnN_diag[k] = dlnActCoeffdlnN_diag_[k];
}
}
//====================================================================================================================
void IonsFromNeutralVPSSTP::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnActCoeffdlnN)
{
s_update_lnActCoeff();
@ -754,26 +542,19 @@ void IonsFromNeutralVPSSTP::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnA
}
}
}
//====================================================================================================================
void IonsFromNeutralVPSSTP::setTemperature(const doublereal temp)
{
double p = pressure();
IonsFromNeutralVPSSTP::setState_TP(temp, p);
}
//====================================================================================================================
void IonsFromNeutralVPSSTP::setPressure(doublereal p)
{
double t = temperature();
IonsFromNeutralVPSSTP::setState_TP(t, p);
}
//====================================================================================================================
// Set the temperature (K) and pressure (Pa)
/*
* Setting the pressure may involve the solution of a nonlinear equation.
*
* @param t Temperature (K)
* @param p Pressure (Pa)
*/
void IonsFromNeutralVPSSTP::setState_TP(doublereal t, doublereal p)
{
/*
@ -792,11 +573,6 @@ void IonsFromNeutralVPSSTP::setState_TP(doublereal t, doublereal p)
Phase::setDensity(dd);
}
// Calculate ion mole fractions from neutral molecule
// mole fractions.
/*
* @param mf Dump the mole fractions into this vector.
*/
void IonsFromNeutralVPSSTP::calcIonMoleFractions(doublereal* const mf) const
{
doublereal fmij;
@ -833,21 +609,7 @@ void IonsFromNeutralVPSSTP::calcIonMoleFractions(doublereal* const mf) const
}
}
//====================================================================================================================
// Calculate neutral molecule mole fractions
/*
* This routine calculates the neutral molecule mole
* fraction given the vector of ion mole fractions,
* i.e., the mole fractions from this ThermoPhase.
* Note, this routine basically assumes that there
* is charge neutrality. If there isn't, then it wouldn't
* make much sense.
*
* for the case of cIonSolnType_SINGLEANION, some slough
* in the charge neutrality is allowed. The cation number
* is followed, while the difference in charge neutrality
* is dumped into the anion mole number to fix the imbalance.
*/
void IonsFromNeutralVPSSTP::calcNeutralMoleculeMoleFractions() const
{
size_t icat, jNeut;
@ -956,21 +718,7 @@ void IonsFromNeutralVPSSTP::calcNeutralMoleculeMoleFractions() const
}
}
//====================================================================================================================
// Calculate neutral molecule mole fractions
/*
* This routine calculates the neutral molecule mole
* fraction given the vector of ion mole fractions,
* i.e., the mole fractions from this ThermoPhase.
* Note, this routine basically assumes that there
* is charge neutrality. If there isn't, then it wouldn't
* make much sense.
*
* for the case of cIonSolnType_SINGLEANION, some slough
* in the charge neutrality is allowed. The cation number
* is followed, while the difference in charge neutrality
* is dumped into the anion mole number to fix the imbalance.
*/
void IonsFromNeutralVPSSTP::getNeutralMoleculeMoleGrads(const doublereal* const dx, doublereal* const dy) const
{
doublereal fmij;
@ -1075,7 +823,6 @@ void IonsFromNeutralVPSSTP::getNeutralMoleculeMoleGrads(const doublereal* const
}
}
void IonsFromNeutralVPSSTP::setMassFractions(const doublereal* const y)
{
GibbsExcessVPSSTP::setMassFractions(y);
@ -1104,7 +851,6 @@ void IonsFromNeutralVPSSTP::setMoleFractions_NoNorm(const doublereal* const x)
neutralMoleculePhase_->setMoleFractions_NoNorm(DATA_PTR(NeutralMolecMoleFractions_));
}
void IonsFromNeutralVPSSTP::setConcentrations(const doublereal* const c)
{
GibbsExcessVPSSTP::setConcentrations(c);
@ -1116,7 +862,6 @@ void IonsFromNeutralVPSSTP::setConcentrations(const doublereal* const c)
* ------------ Partial Molar Properties of the Solution ------------
*/
doublereal IonsFromNeutralVPSSTP::err(const std::string& msg) const
{
throw CanteraError("IonsFromNeutralVPSSTP","Base class method "
@ -1124,29 +869,12 @@ doublereal IonsFromNeutralVPSSTP::err(const std::string& msg) const
return 0;
}
//====================================================================================================================
/*
* @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.
*
* @see importCTML.cpp
*/
void IonsFromNeutralVPSSTP::initThermo()
{
initLengths();
GibbsExcessVPSSTP::initThermo();
}
//====================================================================================================================
// Initialize lengths of local variables after all species have
// been identified.
void IonsFromNeutralVPSSTP::initLengths()
{
m_kk = nSpecies();
@ -1171,7 +899,7 @@ void IonsFromNeutralVPSSTP::initLengths()
dX_NeutralMolecule.resize(numNeutralMoleculeSpecies_, 0.0);
}
//====================================================================================================================
//! Return the factor overlap
/*!
* @param elnamesVN
@ -1180,7 +908,6 @@ void IonsFromNeutralVPSSTP::initLengths()
* @param elnamesVI
* @param elemVectorI
* @param nElementsI
*
*/
static double factorOverlap(const std::vector<std::string>& elnamesVN ,
const std::vector<double>& elemVectorN,
@ -1207,22 +934,7 @@ static double factorOverlap(const std::vector<std::string>& elnamesVN ,
}
return fMax;
}
//====================================================================================================================
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void IonsFromNeutralVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
string stemp;
@ -1426,13 +1138,7 @@ void IonsFromNeutralVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string
* have charge conservation.
*/
}
//====================================================================================================================
// Update the activity coefficients
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
*/
void IonsFromNeutralVPSSTP::s_update_lnActCoeff() const
{
size_t icat, jNeut;
@ -1481,17 +1187,7 @@ void IonsFromNeutralVPSSTP::s_update_lnActCoeff() const
}
}
//====================================================================================================================
// Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
// a line in parameter space or along a line in physical space
/*
*
* @param dTds Input of temperature change along the path
* @param dXds Input vector of changes in mole fraction along the path. length = m_kk
* Along the path length it must be the case that the mole fractions sum to one.
* @param dlnActCoeffds Output vector of the directional derivatives of the
* log Activity Coefficients along the path. length = m_kk
*/
void IonsFromNeutralVPSSTP::getdlnActCoeffds(const doublereal dTds, const doublereal* const dXds,
doublereal* dlnActCoeffds) const
{
@ -1556,12 +1252,7 @@ void IonsFromNeutralVPSSTP::getdlnActCoeffds(const doublereal dTds, const double
}
}
//====================================================================================================================
// Update the temperature derivative of the ln activity coefficients
/*
* This function will be called to update the internally stored
* temperature derivative of the natural logarithm of the activity coefficients
*/
void IonsFromNeutralVPSSTP::s_update_dlnActCoeffdT() const
{
size_t icat, jNeut;
@ -1615,11 +1306,7 @@ void IonsFromNeutralVPSSTP::s_update_dlnActCoeffdT() const
}
}
//====================================================================================================================
/*
* This function will be called to update the internally stored
* temperature derivative of the natural logarithm of the activity coefficients
*/
void IonsFromNeutralVPSSTP::s_update_dlnActCoeff_dlnX_diag() const
{
size_t icat, jNeut;
@ -1673,11 +1360,7 @@ void IonsFromNeutralVPSSTP::s_update_dlnActCoeff_dlnX_diag() const
}
}
//====================================================================================================================
/*
* This function will be called to update the internally stored
* temperature derivative of the natural logarithm of the activity coefficients
*/
void IonsFromNeutralVPSSTP::s_update_dlnActCoeff_dlnN_diag() const
{
size_t icat, jNeut;
@ -1731,14 +1414,7 @@ void IonsFromNeutralVPSSTP::s_update_dlnActCoeff_dlnN_diag() const
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients
// wrt log(number of moles) - diagonal components
/*
* This function will be called to update the internally stored
* derivative of the natural logarithm of the activity coefficients
* wrt logarithm of the number of moles of given species.
*/
void IonsFromNeutralVPSSTP::s_update_dlnActCoeff_dlnN() const
{
size_t kcat = 0, kNeut = 0, mcat = 0, mNeut = 0;
@ -1823,6 +1499,5 @@ void IonsFromNeutralVPSSTP::s_update_dlnActCoeff_dlnN() const
break;
}
}
//====================================================================================================================
}
//======================================================================================================================

240
src/thermo/MargulesVPSSTP.cpp
View file

@ -4,7 +4,6 @@
* employ excess gibbs free energy formulations related to Margules
* expansions (see \ref thermoprops
* and class \link Cantera::MargulesVPSSTP MargulesVPSSTP\endlink).
*
*/
/*
* Copyright (2009) Sandia Corporation. Under the terms of
@ -22,11 +21,6 @@ using namespace std;
namespace Cantera
{
/*
* Default constructor.
*
*/
MargulesVPSSTP::MargulesVPSSTP() :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -35,15 +29,6 @@ MargulesVPSSTP::MargulesVPSSTP() :
{
}
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*/
MargulesVPSSTP::MargulesVPSSTP(const std::string& inputFile, const std::string& id) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -62,25 +47,12 @@ MargulesVPSSTP::MargulesVPSSTP(XML_Node& phaseRoot, const std::string& id) :
importPhase(*findXMLPhase(&phaseRoot, id), this);
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
MargulesVPSSTP::MargulesVPSSTP(const MargulesVPSSTP& b) :
GibbsExcessVPSSTP()
{
MargulesVPSSTP::operator=(b);
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
MargulesVPSSTP& MargulesVPSSTP::
operator=(const MargulesVPSSTP& b)
{
@ -111,34 +83,16 @@ operator=(const MargulesVPSSTP& b)
return *this;
}
/**
*
* ~MargulesVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
MargulesVPSSTP::~MargulesVPSSTP()
{
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
MargulesVPSSTP::duplMyselfAsThermoPhase() const
{
return new MargulesVPSSTP(*this);
}
// Special constructor for a hard-coded problem
/*
*
* LiKCl treating the PseudoBinary layer as passthrough.
* -> test to predict the eutectic and liquidus correctly.
*
*/
MargulesVPSSTP::MargulesVPSSTP(int testProb) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -197,41 +151,19 @@ MargulesVPSSTP::MargulesVPSSTP(int testProb) :
m_pSpecies_A_ij[0] = iKCl;
}
/*
* -------------- Utilities -------------------------------
*/
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The MargulesVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int MargulesVPSSTP::eosType() const
{
return 0;
}
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
//====================================================================================================================
// Get the array of non-dimensional molar-based ln activity coefficients at
// the current solution temperature, pressure, and solution concentration.
/*
* @param lnac Output vector of ln activity coefficients. Length: m_kk.
*/
void MargulesVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
{
/*
@ -246,13 +178,11 @@ void MargulesVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
lnac[k] = lnActCoeff_Scaled_[k];
}
}
//====================================================================================================================
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
void MargulesVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
getChemPotentials(mu);
@ -262,7 +192,6 @@ void MargulesVPSSTP::getElectrochemPotentials(doublereal* mu) const
}
}
void MargulesVPSSTP::getChemPotentials(doublereal* mu) const
{
doublereal xx;
@ -284,7 +213,6 @@ void MargulesVPSSTP::getChemPotentials(doublereal* mu) const
}
}
/// Molar enthalpy. Units: J/kmol.
doublereal MargulesVPSSTP::enthalpy_mole() const
{
size_t kk = nSpecies();
@ -297,7 +225,6 @@ doublereal MargulesVPSSTP::enthalpy_mole() const
return h;
}
/// Molar entropy. Units: J/kmol.
doublereal MargulesVPSSTP::entropy_mole() const
{
size_t kk = nSpecies();
@ -310,7 +237,6 @@ doublereal MargulesVPSSTP::entropy_mole() const
return s;
}
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
doublereal MargulesVPSSTP::cp_mole() const
{
size_t kk = nSpecies();
@ -323,26 +249,11 @@ doublereal MargulesVPSSTP::cp_mole() const
return cp;
}
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal MargulesVPSSTP::cv_mole() const
{
return cp_mole() - GasConstant;
}
// Returns an array of partial molar enthalpies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* molality-based activity coefficient wrt temperature
*
* \f[
* \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MargulesVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
@ -369,20 +280,6 @@ void MargulesVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
}
}
// Returns an array of partial molar heat capacities for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* ??????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MargulesVPSSTP::getPartialMolarCp(doublereal* cpbar) const
{
/*
@ -408,20 +305,6 @@ void MargulesVPSSTP::getPartialMolarCp(doublereal* cpbar) const
}
}
// Returns an array of partial molar entropies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MargulesVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
{
double xx;
@ -449,20 +332,6 @@ void MargulesVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
}
}
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
// Return an array of partial molar volumes for the
// species in the mixture. Units: m^3/kmol.
/*
* Frequently, for this class of thermodynamics representations,
* the excess Volume due to mixing is zero. Here, we set it as
* a default. It may be overridden in derived classes.
*
* @param vbar Output vector of species partial molar volumes.
* Length = m_kk. units are m^3/kmol.
*/
void MargulesVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
{
@ -505,50 +374,18 @@ doublereal MargulesVPSSTP::err(const std::string& msg) const
return 0;
}
/*
* @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.
*
* @see importCTML.cpp
*/
void MargulesVPSSTP::initThermo()
{
initLengths();
GibbsExcessVPSSTP::initThermo();
}
// Initialize lengths of local variables after all species have
// been identified.
void MargulesVPSSTP::initLengths()
{
m_kk = nSpecies();
dlnActCoeffdlnN_.resize(m_kk, m_kk);
}
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void MargulesVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
string stemp;
@ -617,15 +454,7 @@ void MargulesVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
}
//===================================================================================================================
// Update the activity coefficients
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*/
void MargulesVPSSTP::s_update_lnActCoeff() const
{
size_t iA, iB, iK;
@ -653,14 +482,7 @@ void MargulesVPSSTP::s_update_lnActCoeff() const
lnActCoeff_Scaled_[iB] += XA * g0g1XB + XAXB * g1;
}
}
//===================================================================================================================
// Update the derivative of the log of the activity coefficients wrt T
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*/
void MargulesVPSSTP::s_update_dlnActCoeff_dT() const
{
size_t iA, iB, iK;
@ -696,7 +518,7 @@ void MargulesVPSSTP::s_update_dlnActCoeff_dT() const
d2lnActCoeffdT2_Scaled_[iB] -= mult * XA * g0g1XB + XAXB * g1;
}
}
//====================================================================================================================
void MargulesVPSSTP::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
{
s_update_dlnActCoeff_dT();
@ -704,7 +526,7 @@ void MargulesVPSSTP::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
dlnActCoeffdT[k] = dlnActCoeffdT_Scaled_[k];
}
}
//====================================================================================================================
void MargulesVPSSTP::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const
{
s_update_dlnActCoeff_dT();
@ -712,24 +534,10 @@ void MargulesVPSSTP::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const
d2lnActCoeffdT2[k] = d2lnActCoeffdT2_Scaled_[k];
}
}
//====================================================================================================================
// Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
// a line in parameter space or along a line in physical space
/*
*
* @param dTds Input of temperature change along the path
* @param dXds Input vector of changes in mole fraction along the path. length = m_kk
* Along the path length it must be the case that the mole fractions sum to one.
* @param dlnActCoeffds Output vector of the directional derivatives of the
* log Activity Coefficients along the path. length = m_kk
* units are 1/units(s). if s is a physical coordinate then the units are 1/m.
*/
void MargulesVPSSTP::getdlnActCoeffds(const doublereal dTds, const doublereal* const dXds,
doublereal* dlnActCoeffds) const
{
size_t iA, iB, iK;
double XA, XB, g0 , g1, dXA, dXB;
double T = temperature();
@ -763,15 +571,7 @@ void MargulesVPSSTP::getdlnActCoeffds(const doublereal dTds, const doublereal*
dlnActCoeffds[iB] += dXA * g02g1XB + g2XAdXB;
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt dlnN
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
* he = X_A X_B(B + C X_B)
*/
void MargulesVPSSTP::s_update_dlnActCoeff_dlnN_diag() const
{
size_t iA, iB, iK, delAK, delBK;
@ -827,14 +627,6 @@ void MargulesVPSSTP::s_update_dlnActCoeff_dlnN_diag() const
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt dlnN
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
*/
void MargulesVPSSTP::s_update_dlnActCoeff_dlnN() const
{
size_t iA, iB;
@ -902,7 +694,7 @@ void MargulesVPSSTP::s_update_dlnActCoeff_dlnN() const
}
}
}
//====================================================================================================================
void MargulesVPSSTP::s_update_dlnActCoeff_dlnX_diag() const
{
doublereal T = temperature();
@ -924,7 +716,6 @@ void MargulesVPSSTP::s_update_dlnActCoeff_dlnX_diag() const
}
}
//====================================================================================================================
void MargulesVPSSTP::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const
{
s_update_dlnActCoeff_dlnN_diag();
@ -932,7 +723,7 @@ void MargulesVPSSTP::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) c
dlnActCoeffdlnN_diag[k] = dlnActCoeffdlnN_diag_[k];
}
}
//====================================================================================================================
void MargulesVPSSTP::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_diag) const
{
s_update_dlnActCoeff_dlnX_diag();
@ -940,7 +731,7 @@ void MargulesVPSSTP::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_diag) c
dlnActCoeffdlnX_diag[k] = dlnActCoeffdlnX_diag_[k];
}
}
//====================================================================================================================
void MargulesVPSSTP::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnActCoeffdlnN)
{
s_update_dlnActCoeff_dlnN();
@ -951,7 +742,7 @@ void MargulesVPSSTP::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnActCoeff
}
}
}
//====================================================================================================================
void MargulesVPSSTP::resizeNumInteractions(const size_t num)
{
numBinaryInteractions_ = num;
@ -970,17 +761,8 @@ void MargulesVPSSTP::resizeNumInteractions(const size_t num)
m_pSpecies_A_ij.resize(num, npos);
m_pSpecies_B_ij.resize(num, npos);
}
//====================================================================================================================
/*
* Process an XML node called "binaryNeutralSpeciesParameters"
* This node contains all of the parameters necessary to describe
* the Margules Interaction for a single binary interaction
* This function reads the XML file and writes the coefficients
* it finds to an internal data structures.
*/
void MargulesVPSSTP::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
{
string xname = xmLBinarySpecies.name();
@ -1096,11 +878,7 @@ void MargulesVPSSTP::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
m_VSE_b_ij[iSpot] = vParams[0];
m_VSE_c_ij[iSpot] = vParams[1];
}
}
}
}

239
src/thermo/MixedSolventElectrolyte.cpp
View file

@ -23,11 +23,6 @@ using namespace std;
namespace Cantera
{
/*
* Default constructor.
*
*/
MixedSolventElectrolyte::MixedSolventElectrolyte() :
MolarityIonicVPSSTP(),
numBinaryInteractions_(0),
@ -36,15 +31,6 @@ MixedSolventElectrolyte::MixedSolventElectrolyte() :
{
}
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*/
MixedSolventElectrolyte::MixedSolventElectrolyte(const std::string& inputFile,
const std::string& id) :
MolarityIonicVPSSTP(),
@ -65,25 +51,12 @@ MixedSolventElectrolyte::MixedSolventElectrolyte(XML_Node& phaseRoot,
importPhase(*findXMLPhase(&phaseRoot, id), this);
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
MixedSolventElectrolyte::MixedSolventElectrolyte(const MixedSolventElectrolyte& b) :
MolarityIonicVPSSTP()
{
MixedSolventElectrolyte::operator=(b);
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
MixedSolventElectrolyte& MixedSolventElectrolyte::
operator=(const MixedSolventElectrolyte& b)
{
@ -114,42 +87,22 @@ operator=(const MixedSolventElectrolyte& b)
return *this;
}
/**
*
* ~MixedSolventElectrolyte(): (virtual)
*
* Destructor: does nothing:
*
*/
MixedSolventElectrolyte::~MixedSolventElectrolyte()
{
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
MixedSolventElectrolyte::duplMyselfAsThermoPhase() const
{
return new MixedSolventElectrolyte(*this);
}
// Special constructor for a hard-coded problem
/*
*
* LiKCl treating the PseudoBinary layer as passthrough.
* -> test to predict the eutectic and liquidus correctly.
*
*/
MixedSolventElectrolyte::MixedSolventElectrolyte(int testProb) :
MolarityIonicVPSSTP(),
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
initThermoFile("LiKCl_liquid.xml", "");
@ -201,39 +154,19 @@ MixedSolventElectrolyte::MixedSolventElectrolyte(int testProb) :
m_pSpecies_A_ij[0] = iKCl;
}
/*
* -------------- Utilities -------------------------------
*/
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The MixedSolventElectrolyte class also returns
* zero, as it is a non-complete class.
*/
int MixedSolventElectrolyte::eosType() const
{
return 0;
}
//====================================================================================================================
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
//====================================================================================================================
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
//====================================================================================================================
// Get the array of non-dimensional molar-based activity coefficients at
// the current solution temperature, pressure, and solution concentration.
/*
* @param ac Output vector of activity coefficients. Length: m_kk.
*/
void MixedSolventElectrolyte::getActivityCoefficients(doublereal* ac) const
{
/*
@ -248,13 +181,11 @@ void MixedSolventElectrolyte::getActivityCoefficients(doublereal* ac) const
ac[k] = exp(lnActCoeff_Scaled_[k]);
}
}
//====================================================================================================================
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
void MixedSolventElectrolyte::getElectrochemPotentials(doublereal* mu) const
{
getChemPotentials(mu);
@ -264,7 +195,6 @@ void MixedSolventElectrolyte::getElectrochemPotentials(doublereal* mu) const
}
}
void MixedSolventElectrolyte::getChemPotentials(doublereal* mu) const
{
doublereal xx;
@ -289,7 +219,6 @@ void MixedSolventElectrolyte::getChemPotentials(doublereal* mu) const
}
}
/// Molar enthalpy. Units: J/kmol.
doublereal MixedSolventElectrolyte::enthalpy_mole() const
{
size_t kk = nSpecies();
@ -302,7 +231,6 @@ doublereal MixedSolventElectrolyte::enthalpy_mole() const
return h;
}
/// Molar entropy. Units: J/kmol.
doublereal MixedSolventElectrolyte::entropy_mole() const
{
size_t kk = nSpecies();
@ -315,7 +243,6 @@ doublereal MixedSolventElectrolyte::entropy_mole() const
return s;
}
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
doublereal MixedSolventElectrolyte::cp_mole() const
{
size_t kk = nSpecies();
@ -328,26 +255,11 @@ doublereal MixedSolventElectrolyte::cp_mole() const
return cp;
}
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal MixedSolventElectrolyte::cv_mole() const
{
return cp_mole() - GasConstant;
}
// Returns an array of partial molar enthalpies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* molality-based activity coefficient wrt temperature
*
* \f[
* \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MixedSolventElectrolyte::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
@ -374,20 +286,6 @@ void MixedSolventElectrolyte::getPartialMolarEnthalpies(doublereal* hbar) const
}
}
// Returns an array of partial molar heat capacities for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* ??????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MixedSolventElectrolyte::getPartialMolarCp(doublereal* cpbar) const
{
/*
@ -413,20 +311,6 @@ void MixedSolventElectrolyte::getPartialMolarCp(doublereal* cpbar) const
}
}
// Returns an array of partial molar entropies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MixedSolventElectrolyte::getPartialMolarEntropies(doublereal* sbar) const
{
double xx;
@ -454,20 +338,6 @@ void MixedSolventElectrolyte::getPartialMolarEntropies(doublereal* sbar) const
}
}
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
// Return an array of partial molar volumes for the
// species in the mixture. Units: m^3/kmol.
/*
* Frequently, for this class of thermodynamics representations,
* the excess Volume due to mixing is zero. Here, we set it as
* a default. It may be overridden in derived classes.
*
* @param vbar Output vector of species partial molar volumes.
* Length = m_kk. units are m^3/kmol.
*/
void MixedSolventElectrolyte::getPartialMolarVolumes(doublereal* vbar) const
{
int delAK, delBK;
@ -510,50 +380,18 @@ doublereal MixedSolventElectrolyte::err(const std::string& msg) const
return 0;
}
/*
* @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.
*
* @see importCTML.cpp
*/
void MixedSolventElectrolyte::initThermo()
{
initLengths();
MolarityIonicVPSSTP::initThermo();
}
// Initialize lengths of local variables after all species have
// been identified.
void MixedSolventElectrolyte::initLengths()
{
m_kk = nSpecies();
dlnActCoeffdlnN_.resize(m_kk, m_kk);
}
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void MixedSolventElectrolyte::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
string subname = "MixedSolventElectrolyte::initThermoXML";
@ -618,15 +456,7 @@ void MixedSolventElectrolyte::initThermoXML(XML_Node& phaseNode, const std::stri
}
//===================================================================================================================
// Update the activity coefficients
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*/
void MixedSolventElectrolyte::s_update_lnActCoeff() const
{
int delAK, delBK;
@ -653,14 +483,7 @@ void MixedSolventElectrolyte::s_update_lnActCoeff() const
}
}
}
//===================================================================================================================
// Update the derivative of the log of the activity coefficients wrt T
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*/
void MixedSolventElectrolyte::s_update_dlnActCoeff_dT() const
{
int delAK, delBK;
@ -690,7 +513,7 @@ void MixedSolventElectrolyte::s_update_dlnActCoeff_dT() const
}
}
}
//====================================================================================================================
void MixedSolventElectrolyte::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
{
s_update_dlnActCoeff_dT();
@ -698,7 +521,7 @@ void MixedSolventElectrolyte::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
dlnActCoeffdT[k] = dlnActCoeffdT_Scaled_[k];
}
}
//====================================================================================================================
void MixedSolventElectrolyte::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const
{
s_update_dlnActCoeff_dT();
@ -706,19 +529,7 @@ void MixedSolventElectrolyte::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) co
d2lnActCoeffdT2[k] = d2lnActCoeffdT2_Scaled_[k];
}
}
//====================================================================================================================
// Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
// a line in parameter space or along a line in physical space
/*
*
* @param dTds Input of temperature change along the path
* @param dXds Input vector of changes in mole fraction along the path. length = m_kk
* Along the path length it must be the case that the mole fractions sum to one.
* @param dlnActCoeffds Output vector of the directional derivatives of the
* log Activity Coefficients along the path. length = m_kk
* units are 1/units(s). if s is a physical coordinate then the units are 1/m.
*/
void MixedSolventElectrolyte::getdlnActCoeffds(const doublereal dTds, const doublereal* const dXds,
doublereal* dlnActCoeffds) const
{
@ -760,15 +571,7 @@ void MixedSolventElectrolyte::getdlnActCoeffds(const doublereal dTds, const dou
}
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt dlnN
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
* he = X_A X_B(B + C X_B)
*/
void MixedSolventElectrolyte::s_update_dlnActCoeff_dlnN_diag() const
{
int delAK, delBK;
@ -824,14 +627,6 @@ void MixedSolventElectrolyte::s_update_dlnActCoeff_dlnN_diag() const
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt dlnN
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
*/
void MixedSolventElectrolyte::s_update_dlnActCoeff_dlnN() const
{
doublereal delAK, delBK;
@ -897,7 +692,7 @@ void MixedSolventElectrolyte::s_update_dlnActCoeff_dlnN() const
}
}
}
//====================================================================================================================
void MixedSolventElectrolyte::s_update_dlnActCoeff_dlnX_diag() const
{
doublereal XA, XB, g0 , g1;
@ -922,7 +717,7 @@ void MixedSolventElectrolyte::s_update_dlnActCoeff_dlnX_diag() const
}
}
//====================================================================================================================
void MixedSolventElectrolyte::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const
{
s_update_dlnActCoeff_dlnN_diag();
@ -930,7 +725,7 @@ void MixedSolventElectrolyte::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdln
dlnActCoeffdlnN_diag[k] = dlnActCoeffdlnN_diag_[k];
}
}
//====================================================================================================================
void MixedSolventElectrolyte::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_diag) const
{
s_update_dlnActCoeff_dlnX_diag();
@ -938,7 +733,7 @@ void MixedSolventElectrolyte::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdln
dlnActCoeffdlnX_diag[k] = dlnActCoeffdlnX_diag_[k];
}
}
//====================================================================================================================
void MixedSolventElectrolyte::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnActCoeffdlnN)
{
s_update_dlnActCoeff_dlnN();
@ -949,7 +744,7 @@ void MixedSolventElectrolyte::getdlnActCoeffdlnN(const size_t ld, doublereal* dl
}
}
}
//====================================================================================================================
void MixedSolventElectrolyte::resizeNumInteractions(const size_t num)
{
numBinaryInteractions_ = num;
@ -970,15 +765,7 @@ void MixedSolventElectrolyte::resizeNumInteractions(const size_t num)
m_pSpecies_B_ij.resize(num, npos);
}
//====================================================================================================================
/*
* Process an XML node called "binaryNeutralSpeciesParameters"
* This node contains all of the parameters necessary to describe
* the Margules Interaction for a single binary interaction
* This function reads the XML file and writes the coefficients
* it finds to an internal data structures.
*/
void MixedSolventElectrolyte::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
{
string xname = xmLBinarySpecies.name();
@ -1095,11 +882,7 @@ void MixedSolventElectrolyte::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
m_VSE_b_ij[iSpot] = vParams[0];
m_VSE_c_ij[iSpot] = vParams[1];
}
}
}
}

304
src/thermo/MolalityVPSSTP.cpp
View file

@ -28,16 +28,6 @@ using namespace std;
namespace Cantera
{
/*
* Default constructor.
*
* This doesn't do much more than initialize constants with
* default values for water at 25C. Water molecular weight
* comes from the default elements.xml file. It actually
* differs slightly from the IAPWS95 value of 18.015268. However,
* density conservation and therefore element conservation
* is the more important principle to follow.
*/
MolalityVPSSTP::MolalityVPSSTP() :
VPStandardStateTP(),
m_indexSolvent(0),
@ -55,12 +45,6 @@ MolalityVPSSTP::MolalityVPSSTP() :
m_chargeNeutralityNecessary = true;
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
MolalityVPSSTP::MolalityVPSSTP(const MolalityVPSSTP& b) :
VPStandardStateTP(),
m_indexSolvent(b.m_indexSolvent),
@ -73,12 +57,6 @@ MolalityVPSSTP::MolalityVPSSTP(const MolalityVPSSTP& b) :
*this = operator=(b);
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
MolalityVPSSTP& MolalityVPSSTP::
operator=(const MolalityVPSSTP& b)
{
@ -95,21 +73,10 @@ operator=(const MolalityVPSSTP& b)
return *this;
}
/**
*
* ~MolalityVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
MolalityVPSSTP::~MolalityVPSSTP()
{
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
MolalityVPSSTP::duplMyselfAsThermoPhase() const
{
@ -120,25 +87,11 @@ MolalityVPSSTP::duplMyselfAsThermoPhase() const
* -------------- Utilities -------------------------------
*/
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The MolalityVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int MolalityVPSSTP::eosType() const
{
return 0;
}
// Set the pH scale, which determines the scale for single-ion activity
// coefficients.
/*
* Single ion activity coefficients are not unique in terms of the
* representing actual measurable quantities.
*/
void MolalityVPSSTP::setpHScale(const int pHscaleType)
{
m_pHScalingType = pHscaleType;
@ -148,24 +101,11 @@ void MolalityVPSSTP::setpHScale(const int pHscaleType)
}
}
// Reports the pH scale, which determines the scale for single-ion activity
// coefficients.
/*
* Single ion activity coefficients are not unique in terms of the
* representing actual measurable quantities.
*/
int MolalityVPSSTP::pHScale() const
{
return m_pHScalingType;
}
/*
* setSolvent():
* Utilities for Solvent ID and Molality
* Here we also calculate and store the molecular weight
* of the solvent and the m_Mnaught parameter.
* @param k index of the solvent.
*/
void MolalityVPSSTP::setSolvent(size_t k)
{
if (k >= m_kk) {
@ -179,18 +119,11 @@ void MolalityVPSSTP::setSolvent(size_t k)
m_Mnaught = m_weightSolvent / 1000.;
}
/*
* return the solvent id index number.
*/
size_t MolalityVPSSTP::solventIndex() const
{
return m_indexSolvent;
}
/*
* Sets the minimum mole fraction in the molality formulation. The
* minimum mole fraction must be in the range 0 to 0.9.
*/
void MolalityVPSSTP::
setMoleFSolventMin(doublereal xmolSolventMIN)
{
@ -202,29 +135,11 @@ setMoleFSolventMin(doublereal xmolSolventMIN)
m_xmolSolventMIN = xmolSolventMIN;
}
/**
* Returns the minimum mole fraction in the molality formulation.
*/
doublereal MolalityVPSSTP::moleFSolventMin() const
{
return m_xmolSolventMIN;
}
/*
* calcMolalities():
* We calculate the vector of molalities of the species
* in the phase and store the result internally:
* \f[
* m_i = (n_i) / (1000 * M_o * n_{o,p})
* \f]
* where
* - \f$ M_o \f$ is the molecular weight of the solvent
* - \f$ n_o \f$ is the mole fraction of the solvent
* - \f$ n_i \f$ is the mole fraction of the solute.
* - \f$ n_{o,p} = max (n_{o, min}, n_o) \f$
* - \f$ n_{o,min} \f$ = minimum mole fraction of solvent allowed
* in the denominator.
*/
void MolalityVPSSTP::calcMolalities() const
{
getMoleFractions(DATA_PTR(m_molalities));
@ -238,21 +153,6 @@ void MolalityVPSSTP::calcMolalities() const
}
}
/*
* getMolalities():
* We calculate the vector of molalities of the species
* in the phase
* \f[
* m_i = (n_i) / (1000 * M_o * n_{o,p})
* \f]
* where
* - \f$ M_o \f$ is the molecular weight of the solvent
* - \f$ n_o \f$ is the mole fraction of the solvent
* - \f$ n_i \f$ is the mole fraction of the solute.
* - \f$ n_{o,p} = max (n_{o, min}, n_o) \f$
* - \f$ n_{o,min} \f$ = minimum mole fraction of solvent allowed
* in the denominator.
*/
void MolalityVPSSTP::getMolalities(doublereal* const molal) const
{
calcMolalities();
@ -261,24 +161,8 @@ void MolalityVPSSTP::getMolalities(doublereal* const molal) const
}
}
/*
* setMolalities():
* We are supplied with the molalities of all of the
* solute species. We then calculate the mole fractions of all
* species and update the ThermoPhase object.
*
* m_i = (n_i) / (W_o/1000 * n_o_p)
*
* where M_o is the molecular weight of the solvent
* n_o is the mole fraction of the solvent
* n_i is the mole fraction of the solute.
* n_o_p = max (n_o_min, n_o)
* n_o_min = minimum mole fraction of solvent allowed
* in the denominator.
*/
void MolalityVPSSTP::setMolalities(const doublereal* const molal)
{
double Lsum = 1.0 / m_Mnaught;
for (size_t k = 1; k < m_kk; k++) {
m_molalities[k] = molal[k];
@ -306,16 +190,13 @@ void MolalityVPSSTP::setMolalities(const doublereal* const molal)
calcMolalities();
}
/*
* setMolalitiesByName()
*
* This routine sets the molalities by name
* HKM -> Might need to be more complicated here, setting
* neutrals so that the existing mole fractions are
* preserved.
*/
void MolalityVPSSTP::setMolalitiesByName(compositionMap& mMap)
{
/*
* HKM -> Might need to be more complicated here, setting
* neutrals so that the existing mole fractions are
* preserved.
*/
size_t kk = nSpecies();
doublereal x;
/*
@ -396,46 +277,16 @@ void MolalityVPSSTP::setMolalitiesByName(compositionMap& mMap)
calcMolalities();
}
/*
* setMolalitiesByNames()
*
* Set the molalities of the solutes by name
*/
void MolalityVPSSTP::setMolalitiesByName(const std::string& x)
{
compositionMap xx = parseCompString(x, speciesNames());
setMolalitiesByName(xx);
}
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
/*
* This method returns the activity convention.
* Currently, there are two activity conventions
* Molar-based activities
* Unit activity of species at either a hypothetical pure
* solution of the species or at a hypothetical
* pure ideal solution at infinite dilution
* cAC_CONVENTION_MOLAR 0
* - default
*
* Molality based activities
* (unit activity of solutes at a hypothetical 1 molal
* solution referenced to infinite dilution at all
* pressures and temperatures).
* (solvent is still on molar basis).
* cAC_CONVENTION_MOLALITY 1
*
* We set the convention to molality here.
*/
int MolalityVPSSTP::activityConvention() const
{
return cAC_CONVENTION_MOLALITY;
@ -463,19 +314,6 @@ void MolalityVPSSTP::getActivities(doublereal* ac) const
err("getActivities");
}
/*
* Get the array of non-dimensional activity coefficients at
* the current solution temperature, pressure, and
* solution concentration.
* These are mole fraction based activity coefficients. In this
* object, their calculation is based on translating the values
* of Molality based activity coefficients.
* See Denbigh p. 278 for a thorough discussion.
*
* Note, the solvent is treated differently. getMolalityActivityCoeff()
* returns the molar based solvent activity coefficient already.
* Therefore, we do not have to divide by x_s here.
*/
void MolalityVPSSTP::getActivityCoefficients(doublereal* ac) const
{
getMolalityActivityCoefficients(ac);
@ -489,38 +327,12 @@ void MolalityVPSSTP::getActivityCoefficients(doublereal* ac) const
}
}
// Get the array of non-dimensional molality based
// activity coefficients at the current solution temperature,
// pressure, and solution concentration.
/*
* See Denbigh p. 278 for a thorough discussion. This class must be overwritten in
* classes which derive from %MolalityVPSSTP. This function takes over from the
* molar-based activity coefficient calculation, getActivityCoefficients(), in
* derived classes.
*
* Note these activity coefficients have the current pH scale applied to them.
*
* @param acMolality Output vector containing the molality based activity coefficients.
* length: m_kk.
*/
void MolalityVPSSTP::getMolalityActivityCoefficients(doublereal* acMolality) const
{
getUnscaledMolalityActivityCoefficients(acMolality);
applyphScale(acMolality);
}
/*
* osmotic coefficient:
*
* Calculate the osmotic coefficient of the solvent. Note there
* are lots of definitions of the osmotic coefficient floating
* around. We use the one defined in the Pitzer's book:
* (Activity Coeff in Electrolyte Solutions, K. S. Pitzer
* CRC Press, Boca Raton, 1991, p. 85, Eqn. 28).
*
* Definition:
* - sum(m_i) * Mnaught * oc = ln(activity_solvent)
*/
doublereal MolalityVPSSTP::osmoticCoefficient() const
{
/*
@ -543,7 +355,6 @@ doublereal MolalityVPSSTP::osmoticCoefficient() const
return oc;
}
void MolalityVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
getChemPotentials(mu);
@ -553,11 +364,6 @@ void MolalityVPSSTP::getElectrochemPotentials(doublereal* mu) const
}
}
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
doublereal MolalityVPSSTP::err(const std::string& msg) const
{
throw CanteraError("MolalityVPSSTP","Base class method "
@ -565,28 +371,6 @@ doublereal MolalityVPSSTP::err(const std::string& msg) const
return 0;
}
/*
* Returns the units of the standard and general concentrations
* Note they have the same units, as their divisor 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.
*
* On return uA contains the powers of the units (MKS assumed)
* of the standard concentrations and generalized concentrations
* for the kth species.
*
* 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
*/
void MolalityVPSSTP::getUnitsStandardConc(double* uA, int k, int sizeUA) const
{
for (int i = 0; i < sizeUA; i++) {
@ -617,9 +401,6 @@ void MolalityVPSSTP::setToEquilState(const doublereal* lambda_RT)
err("setToEquilState");
}
/*
* Set the thermodynamic state.
*/
void MolalityVPSSTP::setStateFromXML(const XML_Node& state)
{
VPStandardStateTP::setStateFromXML(state);
@ -633,10 +414,6 @@ void MolalityVPSSTP::setStateFromXML(const XML_Node& state)
}
}
/*
* Set the temperature (K), pressure (Pa), and molalities
* (gmol kg-1) of the solutes
*/
void MolalityVPSSTP::setState_TPM(doublereal t, doublereal p,
const doublereal* const molalities)
{
@ -644,18 +421,12 @@ void MolalityVPSSTP::setState_TPM(doublereal t, doublereal p,
setState_TP(t, p);
}
/*
* Set the temperature (K), pressure (Pa), and molalities.
*/
void MolalityVPSSTP::setState_TPM(doublereal t, doublereal p, compositionMap& m)
{
setMolalitiesByName(m);
setState_TP(t, p);
}
/*
* Set the temperature (K), pressure (Pa), and molality.
*/
void MolalityVPSSTP::setState_TPM(doublereal t, doublereal p, const std::string& m)
{
setMolalitiesByName(m);
@ -663,19 +434,6 @@ void MolalityVPSSTP::setState_TPM(doublereal t, doublereal p, const std::string&
}
/*
* @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.
*
* @see importCTML.cpp
*/
void MolalityVPSSTP::initThermo()
{
initLengths();
@ -691,48 +449,16 @@ void MolalityVPSSTP::initThermo()
m_indexCLM = findCLMIndex();
}
// Get the array of unscaled non-dimensional molality based
// activity coefficients at the current solution temperature,
// pressure, and solution concentration.
/*
* See Denbigh p. 278 for a thorough discussion. This class must be overwritten in
* classes which derive from %MolalityVPSSTP. This function takes over from the
* molar-based activity coefficient calculation, getActivityCoefficients(), in
* derived classes.
*
* @param acMolality Output vector containing the molality based activity coefficients.
* length: m_kk.
*/
void MolalityVPSSTP::getUnscaledMolalityActivityCoefficients(doublereal* acMolality) const
{
err("getUnscaledMolalityActivityCoefficients");
}
// Apply the current phScale to a set of activity Coefficients or activities
/*
* See the Eq3/6 Manual for a thorough discussion.
*
* @param acMolality input/Output vector containing the molality based
* activity coefficients. length: m_kk.
*/
void MolalityVPSSTP::applyphScale(doublereal* acMolality) const
{
err("applyphScale");
}
// Returns the index of the Cl- species.
/*
* The Cl- species is special in the sense that its single ion
* molality-based activity coefficient is used in the specification
* of the pH scale for single ions. Therefore, we need to know
* what species index Cl- is. If the species isn't in the species
* list then this routine returns -1, and we can't use the NBS
* pH scale.
*
* Right now we use a restrictive interpretation. The species
* must be named "Cl-". It must consist of exactly one Cl and one E
* atom.
*/
size_t MolalityVPSSTP::findCLMIndex() const
{
size_t indexCLM = npos;
@ -798,21 +524,6 @@ void MolalityVPSSTP::initLengths()
m_molalities.resize(m_kk);
}
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void MolalityVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
@ -830,8 +541,6 @@ void MolalityVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
*/
std::string MolalityVPSSTP::report(bool show_thermo) const
{
char p[800];
string s = "";
try {
@ -947,9 +656,6 @@ std::string MolalityVPSSTP::report(bool show_thermo) const
return s;
}
/*
* Format a summary of the mixture state for output.
*/
void MolalityVPSSTP::getCsvReportData(std::vector<std::string>& names,
std::vector<vector_fp>& data) const
{

200
src/thermo/MolarityIonicVPSSTP.cpp
View file

@ -27,11 +27,7 @@ using namespace std;
namespace Cantera
{
//====================================================================================================================
/*
* Default constructor.
*
*/
MolarityIonicVPSSTP::MolarityIonicVPSSTP() :
GibbsExcessVPSSTP(),
PBType_(PBTYPE_PASSTHROUGH),
@ -43,15 +39,7 @@ MolarityIonicVPSSTP::MolarityIonicVPSSTP() :
neutralPBindexStart(0)
{
}
//====================================================================================================================
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*/
MolarityIonicVPSSTP::MolarityIonicVPSSTP(const std::string& inputFile,
const std::string& id) :
GibbsExcessVPSSTP(),
@ -65,7 +53,7 @@ MolarityIonicVPSSTP::MolarityIonicVPSSTP(const std::string& inputFile,
{
initThermoFile(inputFile, id);
}
//====================================================================================================================
MolarityIonicVPSSTP::MolarityIonicVPSSTP(XML_Node& phaseRoot,
const std::string& id) :
GibbsExcessVPSSTP(),
@ -79,13 +67,7 @@ MolarityIonicVPSSTP::MolarityIonicVPSSTP(XML_Node& phaseRoot,
{
importPhase(*findXMLPhase(&phaseRoot, id), this);
}
//====================================================================================================================
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
MolarityIonicVPSSTP::MolarityIonicVPSSTP(const MolarityIonicVPSSTP& b) :
GibbsExcessVPSSTP(),
PBType_(PBTYPE_PASSTHROUGH),
@ -98,13 +80,7 @@ MolarityIonicVPSSTP::MolarityIonicVPSSTP(const MolarityIonicVPSSTP& b) :
{
*this = operator=(b);
}
//====================================================================================================================
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
MolarityIonicVPSSTP& MolarityIonicVPSSTP::
operator=(const MolarityIonicVPSSTP& b)
{
@ -127,22 +103,11 @@ operator=(const MolarityIonicVPSSTP& b)
return *this;
}
//====================================================================================================================
/**
*
* ~MolarityIonicVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
MolarityIonicVPSSTP::~MolarityIonicVPSSTP()
{
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
MolarityIonicVPSSTP::duplMyselfAsThermoPhase() const
{
@ -152,30 +117,15 @@ MolarityIonicVPSSTP::duplMyselfAsThermoPhase() const
/*
* -------------- Utilities -------------------------------
*/
//====================================================================================================================
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The MolarityIonicVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int MolarityIonicVPSSTP::eosType() const
{
return 0;
}
//====================================================================================================================
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
//====================================================================================================================
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
//====================================================================================================================
void MolarityIonicVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
{
@ -191,7 +141,7 @@ void MolarityIonicVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
lnac[k] = lnActCoeff_Scaled_[k];
}
}
//====================================================================================================================
void MolarityIonicVPSSTP::getChemPotentials(doublereal* mu) const
{
doublereal xx;
@ -215,7 +165,6 @@ void MolarityIonicVPSSTP::getChemPotentials(doublereal* mu) const
mu[k] += RT * (log(xx) + lnActCoeff_Scaled_[k]);
}
}
//====================================================================================================================
void MolarityIonicVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
@ -226,21 +175,6 @@ void MolarityIonicVPSSTP::getElectrochemPotentials(doublereal* mu) const
}
}
//====================================================================================================================
// Returns an array of partial molar enthalpies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* molality-based activity coefficient wrt temperature
*
* \f[
* \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MolarityIonicVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
@ -266,21 +200,7 @@ void MolarityIonicVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
hbar[k] -= RTT * dlnActCoeffdT_Scaled_[k];
}
}
//====================================================================================================================
// Returns an array of partial molar heat capacities for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* ??????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MolarityIonicVPSSTP::getPartialMolarCp(doublereal* cpbar) const
{
/*
@ -305,21 +225,7 @@ void MolarityIonicVPSSTP::getPartialMolarCp(doublereal* cpbar) const
cpbar[k] *= GasConstant;
}
}
//====================================================================================================================
// Returns an array of partial molar entropies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MolarityIonicVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
{
double xx;
@ -346,16 +252,7 @@ void MolarityIonicVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
sbar[k] *= GasConstant;
}
}
// Return an array of partial molar volumes for the
// species in the mixture. Units: m^3/kmol.
/*
* Frequently, for this class of thermodynamics representations,
* the excess Volume due to mixing is zero. Here, we set it as
* a default. It may be overridden in derived classes.
*
* @param vbar Output vector of species partial molar volumes.
* Length = m_kk. units are m^3/kmol.
*/
void MolarityIonicVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
{
/*
@ -366,7 +263,7 @@ void MolarityIonicVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
vbar[iK] += 0.0;
}
}
//====================================================================================================================
void MolarityIonicVPSSTP::calcPseudoBinaryMoleFractions() const
{
size_t k;
@ -447,65 +344,36 @@ void MolarityIonicVPSSTP::calcPseudoBinaryMoleFractions() const
}
}
//====================================================================================================================
// Update the activity coefficients
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
*/
void MolarityIonicVPSSTP::s_update_lnActCoeff() const
{
for (size_t k = 0; k < m_kk; k++) {
lnActCoeff_Scaled_[k] = 0.0;
}
}
//====================================================================================================================
void MolarityIonicVPSSTP::s_update_dlnActCoeff_dT() const
{
}
//====================================================================================================================
// Internal routine that calculates the derivative of the activity coefficients wrt
// the mole fractions.
/*
* This routine calculates the the derivative of the activity coefficients wrt to mole fraction
* with all other mole fractions held constant. This is strictly not permitted. However, if the
* resulting matrix is multiplied by a permissible deltaX vector then everything is ok.
*
* This is the natural way to handle concentration derivatives in this routine.
*/
void MolarityIonicVPSSTP::s_update_dlnActCoeff_dX_() const
{
}
//====================================================================================================================
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
//====================================================================================================================
doublereal MolarityIonicVPSSTP::err(const std::string& msg) const
{
throw CanteraError("MolarityIonicVPSSTP","Base class method "
+msg+" called. Equation of state type: "+int2str(eosType()));
return 0;
}
//====================================================================================================================
/*
* @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.
*
* @see importCTML.cpp
*/
void MolarityIonicVPSSTP::initThermo()
{
GibbsExcessVPSSTP::initThermo();
@ -543,29 +411,13 @@ void MolarityIonicVPSSTP::initThermo()
PBType_ = PBTYPE_PASSTHROUGH;
}
}
//====================================================================================================================
// Initialize lengths of local variables after all species have been identified.
void MolarityIonicVPSSTP::initLengths()
{
m_kk = nSpecies();
moleFractionsTmp_.resize(m_kk);
}
//====================================================================================================================
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void MolarityIonicVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
std::string subname = "MolarityIonicVPSSTP::initThermoXML";
@ -628,22 +480,13 @@ void MolarityIonicVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string&
*/
GibbsExcessVPSSTP::initThermoXML(phaseNode, id);
}
//====================================================================================================================
// Process an XML node called "binaryNeutralSpeciesParameters"
/*
* This node contains all of the parameters necessary to describe
* a single binary interaction. This function reads the XML file and writes the coefficients
* it finds to an internal data structures.
*/
void MolarityIonicVPSSTP::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
{
std::string xname = xmLBinarySpecies.name();
}
//====================================================================================================================
/*
* Format a summary of the mixture state for output.
*/
std::string MolarityIonicVPSSTP::report(bool show_thermo) const
{
char p[800];
@ -718,6 +561,5 @@ std::string MolarityIonicVPSSTP::report(bool show_thermo) const
}
return s;
}
//====================================================================================================================
}
}

315
src/thermo/PhaseCombo_Interaction.cpp
View file

@ -1,6 +1,5 @@
/**
* @file
*
*/
/*
* Copyright (2009) Sandia Corporation. Under the terms of
@ -19,13 +18,6 @@ using namespace std;
namespace Cantera
{
//====================================================================================================================
/*
* Default constructor.
*
* HKM - Checked for Transition
*/
PhaseCombo_Interaction::PhaseCombo_Interaction() :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -33,17 +25,7 @@ PhaseCombo_Interaction::PhaseCombo_Interaction() :
formTempModel_(0)
{
}
//====================================================================================================================
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call\
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*
* HKM - Checked for Transition
*/
PhaseCombo_Interaction::PhaseCombo_Interaction(const std::string& inputFile,
const std::string& id) :
GibbsExcessVPSSTP(),
@ -53,12 +35,7 @@ PhaseCombo_Interaction::PhaseCombo_Interaction(const std::string& inputFile,
{
initThermoFile(inputFile, id);
}
//====================================================================================================================
//
/*
*
* HKM - Checked for Transition
*/
PhaseCombo_Interaction::PhaseCombo_Interaction(XML_Node& phaseRoot,
const std::string& id) :
GibbsExcessVPSSTP(),
@ -69,29 +46,12 @@ PhaseCombo_Interaction::PhaseCombo_Interaction(XML_Node& phaseRoot,
importPhase(*findXMLPhase(&phaseRoot, id), this);
}
//====================================================================================================================
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*
* HKM - Checked for Transition
*/
PhaseCombo_Interaction::PhaseCombo_Interaction(const PhaseCombo_Interaction& b) :
GibbsExcessVPSSTP()
{
PhaseCombo_Interaction::operator=(b);
}
//====================================================================================================================
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*
* HKM - Checked for Transition
*/
PhaseCombo_Interaction& PhaseCombo_Interaction::
operator=(const PhaseCombo_Interaction& b)
{
@ -121,37 +81,17 @@ operator=(const PhaseCombo_Interaction& b)
return *this;
}
//====================================================================================================================
/**
*
* ~PhaseCombo_Interaction(): (virtual)
*
* Destructor: does nothing:
*
* HKM - Checked for Transition
*/
PhaseCombo_Interaction::~PhaseCombo_Interaction()
{
}
//====================================================================================================================
/*
* This routine duplicates the current object and returnsa pointer to ThermoPhase.
*
* HKM - Checked for Transition
*/
ThermoPhase*
PhaseCombo_Interaction::duplMyselfAsThermoPhase() const
{
return new PhaseCombo_Interaction(*this);
}
//====================================================================================================================
// Special constructor for a hard-coded problem
/*
*
* LiKCl treating the PseudoBinary layer as passthrough.
* -> test to predict the eutectic and liquidus correctly.
*
*/
PhaseCombo_Interaction::PhaseCombo_Interaction(int testProb) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -211,40 +151,20 @@ PhaseCombo_Interaction::PhaseCombo_Interaction(int testProb) :
m_pSpecies_B_ij[0] = iLi2;
throw CanteraError("", "unimplemented");
}
//====================================================================================================================
/*
* -------------- Utilities -------------------------------
*/
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The PhaseCombo_Interaction class also returns
* zero, as it is a non-complete class.
*/
int PhaseCombo_Interaction::eosType() const
{
return cPhaseCombo_Interaction;
}
//====================================================================================================================
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
//====================================================================================================================
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
//====================================================================================================================
// Get the array of non-dimensional molar-based activity coefficients at
// the current solution temperature, pressure, and solution concentration.
/*
* @param ac Output vector of activity coefficients. Length: m_kk.
*/
void PhaseCombo_Interaction::getActivityCoefficients(doublereal* ac) const
{
/*
@ -264,8 +184,6 @@ void PhaseCombo_Interaction::getActivityCoefficients(doublereal* ac) const
* ------------ Partial Molar Properties of the Solution ------------
*/
//====================================================================================================================
void PhaseCombo_Interaction::getElectrochemPotentials(doublereal* mu) const
{
getChemPotentials(mu);
@ -275,7 +193,6 @@ void PhaseCombo_Interaction::getElectrochemPotentials(doublereal* mu) const
}
}
//====================================================================================================================
void PhaseCombo_Interaction::getChemPotentials(doublereal* mu) const
{
doublereal xx;
@ -299,8 +216,7 @@ void PhaseCombo_Interaction::getChemPotentials(doublereal* mu) const
mu[k] += RT * (log(xx) + lnActCoeff_Scaled_[k]);
}
}
//====================================================================================================================
// Molar enthalpy. Units: J/kmol.
doublereal PhaseCombo_Interaction::enthalpy_mole() const
{
size_t kk = nSpecies();
@ -312,8 +228,7 @@ doublereal PhaseCombo_Interaction::enthalpy_mole() const
}
return h;
}
//====================================================================================================================
// Molar entropy. Units: J/kmol.
doublereal PhaseCombo_Interaction::entropy_mole() const
{
size_t kk = nSpecies();
@ -325,8 +240,7 @@ doublereal PhaseCombo_Interaction::entropy_mole() const
}
return s;
}
//====================================================================================================================
// Molar heat capacity at constant pressure. Units: J/kmol/K.
doublereal PhaseCombo_Interaction::cp_mole() const
{
size_t kk = nSpecies();
@ -338,27 +252,12 @@ doublereal PhaseCombo_Interaction::cp_mole() const
}
return cp;
}
//====================================================================================================================
// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal PhaseCombo_Interaction::cv_mole() const
{
return cp_mole() - GasConstant;
}
//====================================================================================================================
// Returns an array of partial molar enthalpies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* molality-based activity coefficient wrt temperature
*
* \f[
* \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void PhaseCombo_Interaction::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
@ -384,20 +283,7 @@ void PhaseCombo_Interaction::getPartialMolarEnthalpies(doublereal* hbar) const
hbar[k] -= RTT * dlnActCoeffdT_Scaled_[k];
}
}
//====================================================================================================================
// Returns an array of partial molar heat capacities for the species in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* ??????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void PhaseCombo_Interaction::getPartialMolarCp(doublereal* cpbar) const
{
/*
@ -422,21 +308,7 @@ void PhaseCombo_Interaction::getPartialMolarCp(doublereal* cpbar) const
cpbar[k] *= GasConstant;
}
}
//====================================================================================================================
// Returns an array of partial molar entropies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void PhaseCombo_Interaction::getPartialMolarEntropies(doublereal* sbar) const
{
double xx;
@ -463,20 +335,7 @@ void PhaseCombo_Interaction::getPartialMolarEntropies(doublereal* sbar) const
sbar[k] *= GasConstant;
}
}
//====================================================================================================================
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
// Return an array of partial molar volumes for the species in the mixture. Units: m^3/kmol.
/*
* Frequently, for this class of thermodynamics representations,
* the excess Volume due to mixing is zero. Here, we set it as
* a default. It may be overridden in derived classes.
*
* @param vbar Output vector of species partial molar volumes.
* Length = m_kk. units are m^3/kmol.
*/
void PhaseCombo_Interaction::getPartialMolarVolumes(doublereal* vbar) const
{
int delAK, delBK;
@ -512,7 +371,7 @@ void PhaseCombo_Interaction::getPartialMolarVolumes(doublereal* vbar) const
}
}
}
//====================================================================================================================
doublereal PhaseCombo_Interaction::err(const std::string& msg) const
{
throw CanteraError("PhaseCombo_Interaction","Base class method "
@ -520,50 +379,18 @@ doublereal PhaseCombo_Interaction::err(const std::string& msg) const
return 0;
}
//====================================================================================================================
/*
* @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.
*
* @see importCTML.cpp
*/
void PhaseCombo_Interaction::initThermo()
{
initLengths();
GibbsExcessVPSSTP::initThermo();
}
//====================================================================================================================
// Initialize lengths of local variables after all species have
// been identified.
void PhaseCombo_Interaction::initLengths()
{
m_kk = nSpecies();
dlnActCoeffdlnN_.resize(m_kk, m_kk);
}
//====================================================================================================================
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void PhaseCombo_Interaction::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
string subname = "PhaseCombo_Interaction::initThermoXML";
@ -630,16 +457,7 @@ void PhaseCombo_Interaction::initThermoXML(XML_Node& phaseNode, const std::strin
}
//===================================================================================================================
// Update the activity coefficients
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::s_update_lnActCoeff() const
{
int delAK, delBK;
@ -680,16 +498,7 @@ void PhaseCombo_Interaction::s_update_lnActCoeff() const
}
}
}
//===================================================================================================================
// Update the derivative of the log of the activity coefficients wrt T
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::s_update_dlnActCoeff_dT() const
{
int delAK, delBK;
@ -719,11 +528,7 @@ void PhaseCombo_Interaction::s_update_dlnActCoeff_dT() const
}
}
}
//====================================================================================================================
//
/*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
{
s_update_dlnActCoeff_dT();
@ -731,11 +536,7 @@ void PhaseCombo_Interaction::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
dlnActCoeffdT[k] = dlnActCoeffdT_Scaled_[k];
}
}
//====================================================================================================================
//
/*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const
{
s_update_dlnActCoeff_dT();
@ -743,21 +544,7 @@ void PhaseCombo_Interaction::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) con
d2lnActCoeffdT2[k] = d2lnActCoeffdT2_Scaled_[k];
}
}
//====================================================================================================================
// Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
// a line in parameter space or along a line in physical space
/*
*
* @param dTds Input of temperature change along the path
* @param dXds Input vector of changes in mole fraction along the path. length = m_kk
* Along the path length it must be the case that the mole fractions sum to one.
* @param dlnActCoeffds Output vector of the directional derivatives of the
* log Activity Coefficients along the path. length = m_kk
* units are 1/units(s). if s is a physical coordinate then the units are 1/m.
*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::getdlnActCoeffds(const doublereal dTds, const doublereal* const dXds,
doublereal* dlnActCoeffds) const
{
@ -809,19 +596,7 @@ void PhaseCombo_Interaction::getdlnActCoeffds(const doublereal dTds, const doub
}
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt the log of the corresponding species number density
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
* he = X_A X_B(B + C X_B)
*
* This function only carries out the diagonal calculation
*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::s_update_dlnActCoeff_dlnN_diag() const
{
int delAK, delBK;
@ -872,15 +647,7 @@ void PhaseCombo_Interaction::s_update_dlnActCoeff_dlnN_diag() const
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt ln N_k
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::s_update_dlnActCoeff_dlnN() const
{
doublereal delAK, delBK;
@ -947,7 +714,7 @@ void PhaseCombo_Interaction::s_update_dlnActCoeff_dlnN() const
}
}
}
//====================================================================================================================
void PhaseCombo_Interaction::s_update_dlnActCoeff_dlnX_diag() const
{
doublereal XA, XB, g0 , g1;
@ -972,11 +739,6 @@ void PhaseCombo_Interaction::s_update_dlnActCoeff_dlnX_diag() const
throw CanteraError("", "unimplemented");
}
//====================================================================================================================
//
/*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const
{
s_update_dlnActCoeff_dlnN_diag();
@ -984,11 +746,7 @@ void PhaseCombo_Interaction::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN
dlnActCoeffdlnN_diag[k] = dlnActCoeffdlnN_diag_[k];
}
}
//====================================================================================================================
//
/*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_diag) const
{
s_update_dlnActCoeff_dlnX_diag();
@ -996,11 +754,7 @@ void PhaseCombo_Interaction::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX
dlnActCoeffdlnX_diag[k] = dlnActCoeffdlnX_diag_[k];
}
}
//====================================================================================================================
//
/*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnActCoeffdlnN)
{
s_update_dlnActCoeff_dlnN();
@ -1011,11 +765,7 @@ void PhaseCombo_Interaction::getdlnActCoeffdlnN(const size_t ld, doublereal* dln
}
}
}
//====================================================================================================================
//
/*
* HKM - Checked for Transition
*/
void PhaseCombo_Interaction::resizeNumInteractions(const size_t num)
{
numBinaryInteractions_ = num;
@ -1035,15 +785,7 @@ void PhaseCombo_Interaction::resizeNumInteractions(const size_t num)
m_pSpecies_A_ij.resize(num, npos);
m_pSpecies_B_ij.resize(num, npos);
}
//====================================================================================================================
/*
* Process an XML node called "binaryNeutralSpeciesParameters"
* This node contains all of the parameters necessary to describe
* the Margules Interaction for a single binary interaction
* This function reads the XML file and writes the coefficients
* it finds to an internal data structures.
*/
void PhaseCombo_Interaction::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
{
string xname = xmLBinarySpecies.name();
@ -1160,10 +902,7 @@ void PhaseCombo_Interaction::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
m_VSE_b_ij[iSpot] = vParams[0];
m_VSE_c_ij[iSpot] = vParams[1];
}
}
}
//====================================================================================================================
}
//======================================================================================================================

101
src/thermo/PseudoBinaryVPSSTP.cpp
View file

@ -26,11 +26,6 @@ using namespace std;
namespace Cantera
{
/*
* Default constructor.
*
*/
PseudoBinaryVPSSTP::PseudoBinaryVPSSTP() :
GibbsExcessVPSSTP(),
PBType_(PBTYPE_PASSTHROUGH),
@ -45,12 +40,6 @@ PseudoBinaryVPSSTP::PseudoBinaryVPSSTP() :
{
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
PseudoBinaryVPSSTP::PseudoBinaryVPSSTP(const PseudoBinaryVPSSTP& b) :
GibbsExcessVPSSTP(),
PBType_(PBTYPE_PASSTHROUGH),
@ -66,12 +55,6 @@ PseudoBinaryVPSSTP::PseudoBinaryVPSSTP(const PseudoBinaryVPSSTP& b) :
*this = operator=(b);
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
PseudoBinaryVPSSTP& PseudoBinaryVPSSTP::
operator=(const PseudoBinaryVPSSTP& b)
{
@ -97,57 +80,21 @@ operator=(const PseudoBinaryVPSSTP& b)
return *this;
}
/**
*
* ~PseudoBinaryVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
PseudoBinaryVPSSTP::~PseudoBinaryVPSSTP()
{
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
PseudoBinaryVPSSTP::duplMyselfAsThermoPhase() const
{
return new PseudoBinaryVPSSTP(*this);
}
/*
* -------------- Utilities -------------------------------
*/
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The PseudoBinaryVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int PseudoBinaryVPSSTP::eosType() const
{
return 0;
}
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
doublereal PseudoBinaryVPSSTP::standardConcentration(size_t k) const
{
err("standardConcentration");
@ -160,8 +107,6 @@ doublereal PseudoBinaryVPSSTP::logStandardConc(size_t k) const
return -1.0;
}
void PseudoBinaryVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
getChemPotentials(mu);
@ -231,11 +176,6 @@ void PseudoBinaryVPSSTP::calcPseudoBinaryMoleFractions() const
}
}
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
doublereal PseudoBinaryVPSSTP::err(const std::string& msg) const
{
throw CanteraError("PseudoBinaryVPSSTP","Base class method "
@ -243,64 +183,25 @@ doublereal PseudoBinaryVPSSTP::err(const std::string& msg) const
return 0;
}
/*
* @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.
*
* @see importCTML.cpp
*/
void PseudoBinaryVPSSTP::initThermo()
{
initLengths();
GibbsExcessVPSSTP::initThermo();
}
// Initialize lengths of local variables after all species have
// been identified.
void PseudoBinaryVPSSTP::initLengths()
{
m_kk = nSpecies();
moleFractions_.resize(m_kk);
}
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void PseudoBinaryVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
GibbsExcessVPSSTP::initThermoXML(phaseNode, id);
}
/**
* Format a summary of the mixture state for output.
*/
std::string PseudoBinaryVPSSTP::report(bool show_thermo) const
{
char p[800];
string s = "";
try {
@ -374,6 +275,4 @@ std::string PseudoBinaryVPSSTP::report(bool show_thermo) const
return s;
}
}

241
src/thermo/RedlichKisterVPSSTP.cpp
View file

@ -23,12 +23,6 @@ using namespace std;
namespace Cantera
{
//====================================================================================================================
/*
* Default constructor.
*
*/
RedlichKisterVPSSTP::RedlichKisterVPSSTP() :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -42,16 +36,7 @@ RedlichKisterVPSSTP::RedlichKisterVPSSTP() :
dlnActCoeff_dX_()
{
}
//====================================================================================================================
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*/
RedlichKisterVPSSTP::RedlichKisterVPSSTP(const std::string& inputFile,
const std::string& id) :
GibbsExcessVPSSTP(),
@ -67,7 +52,7 @@ RedlichKisterVPSSTP::RedlichKisterVPSSTP(const std::string& inputFile,
{
initThermoFile(inputFile, id);
}
//====================================================================================================================
RedlichKisterVPSSTP::RedlichKisterVPSSTP(XML_Node& phaseRoot,
const std::string& id) :
GibbsExcessVPSSTP(),
@ -83,14 +68,7 @@ RedlichKisterVPSSTP::RedlichKisterVPSSTP(XML_Node& phaseRoot,
{
importPhase(*findXMLPhase(&phaseRoot, id), this);
}
//====================================================================================================================
// Special constructor for a hard-coded problem
/*
*
* LiKCl treating the PseudoBinary layer as passthrough.
* -> test to predict the eutectic and liquidus correctly.
*
*/
RedlichKisterVPSSTP::RedlichKisterVPSSTP(int testProb) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -136,16 +114,8 @@ RedlichKisterVPSSTP::RedlichKisterVPSSTP(int testProb) :
"Unable to find VLi");
}
m_pSpecies_B_ij[0] = iVLi;
}
//====================================================================================================================
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
RedlichKisterVPSSTP::RedlichKisterVPSSTP(const RedlichKisterVPSSTP& b) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
@ -160,13 +130,7 @@ RedlichKisterVPSSTP::RedlichKisterVPSSTP(const RedlichKisterVPSSTP& b) :
{
RedlichKisterVPSSTP::operator=(b);
}
//====================================================================================================================
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
RedlichKisterVPSSTP& RedlichKisterVPSSTP::
operator=(const RedlichKisterVPSSTP& b)
{
@ -188,51 +152,25 @@ operator=(const RedlichKisterVPSSTP& b)
return *this;
}
//====================================================================================================================
/*
*
* ~RedlichKisterVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
RedlichKisterVPSSTP::~RedlichKisterVPSSTP()
{
}
//====================================================================================================================
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
RedlichKisterVPSSTP::duplMyselfAsThermoPhase() const
{
return new RedlichKisterVPSSTP(*this);
}
//====================================================================================================================
// Equation of state type flag.
/*
* The ThermoPhase base class returns
* zero. Subclasses should define this to return a unique
* non-zero value. Known constants defined for this purpose are
* listed in mix_defs.h. The RedlichKisterVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int RedlichKisterVPSSTP::eosType() const
{
return 0;
}
//====================================================================================================================
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
//====================================================================================================================
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
//====================================================================================================================
void RedlichKisterVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
{
@ -248,11 +186,11 @@ void RedlichKisterVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
lnac[k] = lnActCoeff_Scaled_[k];
}
}
//====================================================================================================================
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
//====================================================================================================================
void RedlichKisterVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
getChemPotentials(mu);
@ -261,7 +199,7 @@ void RedlichKisterVPSSTP::getElectrochemPotentials(doublereal* mu) const
mu[k] += ve*charge(k);
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::getChemPotentials(doublereal* mu) const
{
doublereal xx;
@ -285,8 +223,7 @@ void RedlichKisterVPSSTP::getChemPotentials(doublereal* mu) const
mu[k] += RT * (log(xx) + lnActCoeff_Scaled_[k]);
}
}
//====================================================================================================================
//Molar enthalpy. Units: J/kmol.
doublereal RedlichKisterVPSSTP::enthalpy_mole() const
{
size_t kk = nSpecies();
@ -298,8 +235,7 @@ doublereal RedlichKisterVPSSTP::enthalpy_mole() const
}
return h;
}
//====================================================================================================================
/// Molar entropy. Units: J/kmol.
doublereal RedlichKisterVPSSTP::entropy_mole() const
{
size_t kk = nSpecies();
@ -311,8 +247,7 @@ doublereal RedlichKisterVPSSTP::entropy_mole() const
}
return s;
}
//====================================================================================================================
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
doublereal RedlichKisterVPSSTP::cp_mole() const
{
size_t kk = nSpecies();
@ -324,27 +259,12 @@ doublereal RedlichKisterVPSSTP::cp_mole() const
}
return cp;
}
//====================================================================================================================
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal RedlichKisterVPSSTP::cv_mole() const
{
return cp_mole() - GasConstant;
}
//====================================================================================================================
// Returns an array of partial molar enthalpies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* molality-based activity coefficient wrt temperature
*
* \f[
* \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void RedlichKisterVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
@ -370,21 +290,7 @@ void RedlichKisterVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
hbar[k] -= RTT * dlnActCoeffdT_Scaled_[k];
}
}
//====================================================================================================================
// Returns an array of partial molar heat capacities for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* ??????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void RedlichKisterVPSSTP::getPartialMolarCp(doublereal* cpbar) const
{
/*
@ -409,21 +315,7 @@ void RedlichKisterVPSSTP::getPartialMolarCp(doublereal* cpbar) const
cpbar[k] *= GasConstant;
}
}
//====================================================================================================================
// Returns an array of partial molar entropies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficient wrt temperature
*
* \f[
* \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void RedlichKisterVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
{
double xx;
@ -451,20 +343,6 @@ void RedlichKisterVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
}
}
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
//====================================================================================================================
// Return an array of partial molar volumes for the
// species in the mixture. Units: m^3/kmol.
/*
* Frequently, for this class of thermodynamics representations,
* the excess Volume due to mixing is zero. Here, we set it as
* a default. It may be overridden in derived classes.
*
* @param vbar Output vector of species partial molar volumes.
* Length = m_kk. units are m^3/kmol.
*/
void RedlichKisterVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
{
/*
@ -476,52 +354,26 @@ void RedlichKisterVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
vbar[iK] += 0.0;
}
}
//====================================================================================================================
doublereal RedlichKisterVPSSTP::err(const std::string& msg) const
{
throw CanteraError("RedlichKisterVPSSTP","Base class method "
+msg+" called. Equation of state type: "+int2str(eosType()));
return 0;
}
//====================================================================================================================
/*
* @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.
*
* @see importCTML.cpp
*/
void RedlichKisterVPSSTP::initThermo()
{
initLengths();
GibbsExcessVPSSTP::initThermo();
}
//====================================================================================================================
// Initialize lengths of local variables after all species have
// been identified.
void RedlichKisterVPSSTP::initLengths()
{
m_kk = nSpecies();
dlnActCoeffdlnN_.resize(m_kk, m_kk);
}
//====================================================================================================================
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @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.
*/
void RedlichKisterVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
std::string subname = "RedlichKisterVPSSTP::initThermoXML";
@ -583,13 +435,7 @@ void RedlichKisterVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string&
*/
GibbsExcessVPSSTP::initThermoXML(phaseNode, id);
}
//===================================================================================================================
// Update the activity coefficients
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
*/
void RedlichKisterVPSSTP::s_update_lnActCoeff() const
{
doublereal XA, XB;
@ -660,14 +506,7 @@ void RedlichKisterVPSSTP::s_update_lnActCoeff() const
}
}
//===================================================================================================================
// Update the derivative of the log of the activity coefficients wrt T
/*
* This function will be called to update the internally stored
* natural logarithm of the activity coefficients
*
*/
void RedlichKisterVPSSTP::s_update_dlnActCoeff_dT() const
{
doublereal XA, XB;
@ -713,7 +552,7 @@ void RedlichKisterVPSSTP::s_update_dlnActCoeff_dT() const
}
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
{
s_update_dlnActCoeff_dT();
@ -721,7 +560,7 @@ void RedlichKisterVPSSTP::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
dlnActCoeffdT[k] = dlnActCoeffdT_Scaled_[k];
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const
{
s_update_dlnActCoeff_dT();
@ -729,7 +568,7 @@ void RedlichKisterVPSSTP::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const
d2lnActCoeffdT2[k] = d2lnActCoeffdT2_Scaled_[k];
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::s_update_dlnActCoeff_dX_() const
{
doublereal XA, XB;
@ -800,18 +639,7 @@ void RedlichKisterVPSSTP::s_update_dlnActCoeff_dX_() const
}
}
}
//====================================================================================================================
// Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
// a line in parameter space or along a line in physical space
/*
*
* @param dTds Input of temperature change along the path
* @param dXds Input vector of changes in mole fraction along the path. length = m_kk
* Along the path length it must be the case that the mole fractions sum to one.
* @param dlnActCoeffds Output vector of the directional derivatives of the
* log Activity Coefficients along the path. length = m_kk
* units are 1/units(s). if s is a physical coordinate then the units are 1/m.
*/
void RedlichKisterVPSSTP::getdlnActCoeffds(const doublereal dTds, const doublereal* const dXds,
doublereal* dlnActCoeffds) const
{
@ -825,7 +653,6 @@ void RedlichKisterVPSSTP::getdlnActCoeffds(const doublereal dTds, const doublere
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const
{
s_update_dlnActCoeff_dX_();
@ -836,7 +663,7 @@ void RedlichKisterVPSSTP::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_di
}
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_diag) const
{
s_update_dlnActCoeff_dX_();
@ -844,7 +671,7 @@ void RedlichKisterVPSSTP::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_di
dlnActCoeffdlnX_diag[k] = dlnActCoeffdlnX_diag_[k];
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnActCoeffdlnN)
{
s_update_dlnActCoeff_dX_();
@ -855,7 +682,7 @@ void RedlichKisterVPSSTP::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnAct
}
}
}
//====================================================================================================================
void RedlichKisterVPSSTP::resizeNumInteractions(const size_t num)
{
numBinaryInteractions_ = num;
@ -866,13 +693,7 @@ void RedlichKisterVPSSTP::resizeNumInteractions(const size_t num)
m_SE_m_ij.resize(num);
dlnActCoeff_dX_.resize(num, num, 0.0);
}
//====================================================================================================================
// Process an XML node called "binaryNeutralSpeciesParameters"
/*
* This node contains all of the parameters necessary to describe the RedlichKister Interaction for
* a single binary interaction. This function reads the XML file and writes the coefficients
* it finds to an internal data structures.
*/
void RedlichKisterVPSSTP::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
{
std::string xname = xmLBinarySpecies.name();
@ -961,7 +782,7 @@ void RedlichKisterVPSSTP::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
m_N_ij.push_back(Npoly);
resizeNumInteractions(numBinaryInteractions_);
}
//====================================================================================================================
#ifdef DEBUG_MODE
void RedlichKisterVPSSTP::Vint(double& VintOut, double& voltsOut)
{
@ -1010,6 +831,4 @@ void RedlichKisterVPSSTP::Vint(double& VintOut, double& voltsOut)
voltsOut = Volts + termp;
}
#endif
//====================================================================================================================
}

137
src/thermo/VPStandardStateTP.cpp
View file

@ -34,15 +34,6 @@ VPStandardStateTP::VPStandardStateTP() :
{
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor.
*
* The copy constructor just calls the assignment operator
* to do the heavy lifting.
*/
VPStandardStateTP::VPStandardStateTP(const VPStandardStateTP& b) :
ThermoPhase(),
m_Pcurrent(OneAtm),
@ -54,12 +45,6 @@ VPStandardStateTP::VPStandardStateTP(const VPStandardStateTP& b) :
VPStandardStateTP::operator=(b);
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
VPStandardStateTP&
VPStandardStateTP::operator=(const VPStandardStateTP& b)
{
@ -126,10 +111,6 @@ VPStandardStateTP::operator=(const VPStandardStateTP& b)
return *this;
}
//====================================================================================================================
/*
* ~VPStandardStateTP(): (virtual)
*
*/
VPStandardStateTP::~VPStandardStateTP()
{
for (int k = 0; k < (int) m_PDSS_storage.size(); k++) {
@ -138,38 +119,16 @@ VPStandardStateTP::~VPStandardStateTP()
delete m_VPSS_ptr;
}
/*
* Duplication function.
* This calls the copy constructor for this object.
*/
ThermoPhase* VPStandardStateTP::duplMyselfAsThermoPhase() const
{
return new VPStandardStateTP(*this);
}
// 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
*/
int VPStandardStateTP::standardStateConvention() const
{
return cSS_CONVENTION_VPSS;
}
/*
* ------------Molar Thermodynamic Properties -------------------------
*/
doublereal VPStandardStateTP::err(const std::string& msg) const
{
throw CanteraError("VPStandardStateTP","Base class method "
@ -177,19 +136,6 @@ doublereal VPStandardStateTP::err(const std::string& msg) const
return 0;
}
/*
* ---- Partial Molar Properties of the Solution -----------------
*/
/*
* Get the array of non-dimensional species chemical potentials
* These are partial molar Gibbs free energies.
* \f$ \mu_k / \hat R T \f$.
* Units: unitless
*
* We close the loop on this function, here, calling
* getChemPotentials() and then dividing by RT.
*/
void VPStandardStateTP::getChemPotentials_RT(doublereal* muRT) const
{
getChemPotentials(muRT);
@ -220,14 +166,6 @@ void VPStandardStateTP::getEnthalpy_RT(doublereal* hrt) const
//================================================================================================
#ifdef H298MODIFY_CAPABILITY
// Modify the value of the 298 K Heat of Formation 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 Species k
* @param Hf298New Specify the new value of the Heat of Formation at 298K and 1 bar
*/
void VPStandardStateTP::modifyOneHf298SS(const size_t& k, const doublereal Hf298New)
{
m_spthermo->modifyOneHf298(k, Hf298New);
@ -282,37 +220,18 @@ const vector_fp& VPStandardStateTP::getStandardVolumes() const
* ----- Thermodynamic Values for the Species Reference States ----
*/
/*
* Returns the vector of nondimensional enthalpies of the
* reference state at the current temperature of the solution and
* the reference pressure for the species.
*/
void VPStandardStateTP::getEnthalpy_RT_ref(doublereal* hrt) const
{
updateStandardStateThermo();
m_VPSS_ptr->getEnthalpy_RT_ref(hrt);
}
/*
* Returns the vector of nondimensional
* enthalpies of the reference state at the current temperature
* of the solution and the reference pressure for the species.
*/
void VPStandardStateTP::getGibbs_RT_ref(doublereal* grt) const
{
updateStandardStateThermo();
m_VPSS_ptr->getGibbs_RT_ref(grt);
}
/*
* 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
*
* This is filled in here so that derived classes don't have to
* take care of it.
*/
void VPStandardStateTP::getGibbs_ref(doublereal* g) const
{
updateStandardStateThermo();
@ -325,45 +244,24 @@ const vector_fp& VPStandardStateTP::Gibbs_RT_ref() const
return m_VPSS_ptr->Gibbs_RT_ref();
}
/*
* Returns the vector of nondimensional
* entropies of the reference state at the current temperature
* of the solution and the reference pressure for the species.
*/
void VPStandardStateTP::getEntropy_R_ref(doublereal* er) const
{
updateStandardStateThermo();
m_VPSS_ptr->getEntropy_R_ref(er);
}
/*
* 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.
*/
void VPStandardStateTP::getCp_R_ref(doublereal* cpr) const
{
updateStandardStateThermo();
m_VPSS_ptr->getCp_R_ref(cpr);
}
/*
* 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
*/
void VPStandardStateTP::getStandardVolumes_ref(doublereal* vol) const
{
updateStandardStateThermo();
m_VPSS_ptr->getStandardVolumes_ref(vol);
}
/*
* Perform initializations after all species have been
* added.
*/
void VPStandardStateTP::initThermo()
{
initLengths();
@ -465,25 +363,10 @@ VPStandardStateTP::providePDSS(size_t k) const
return m_PDSS_storage[k];
}
/*
* Import and initialize a ThermoPhase object
*
* 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.
*
* This routine initializes the lengths in the current object and
* then calls the parent routine.
*/
void VPStandardStateTP::initThermoXML(XML_Node& phaseNode, const std::string& id)
{
// initialize the lengths in the current object and then call the parent
// routine.
VPStandardStateTP::initLengths();
//m_VPSS_ptr->initThermo();
@ -504,20 +387,6 @@ VPSSMgr* VPStandardStateTP::provideVPSSMgr()
return m_VPSS_ptr;
}
/*
* void _updateStandardStateThermo() (protected, virtual, const)
*
* If m_useTmpStandardStateStorage is true,
* This function must be called for every call to functions in this
* class that need standard state properties.
* Child classes may require that it be called even if m_useTmpStandardStateStorage
* is not true.
* It checks to see whether the temperature has changed and
* thus the ss thermodynamics functions for all of the species
* must be recalculated.
*
* This
*/
void VPStandardStateTP::_updateStandardStateThermo() const
{
double Tnow = temperature();
@ -536,5 +405,3 @@ void VPStandardStateTP::updateStandardStateThermo() const
}
}
}