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Work on VPStandardStateTP. Started to formalize what it actually

Browse source 
does, putting in doxygen documentation. Tried to fix some holes
in DebyeHuckel wherein calculations may be returned without
updating the underlying water standard state.
This commit is contained in:
Harry Moffat 2007-03-08 18:23:52 +00:00
parent aa7e70a2ad
commit ca4f9cc31d
10 changed files with 481 additions and 274 deletions
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123
Cantera/src/thermo/DebyeHuckel.cpp
View file

@ -32,7 +32,6 @@ namespace Cantera {
MolalityVPSSTP(),
m_formDH(DHFORM_DILUTE_LIMIT),
m_formGC(2),
m_Pcurrent(OneAtm),
m_IionicMolality(0.0),
m_maxIionicStrength(30.0),
m_useHelgesonFixedForm(false),
@ -62,7 +61,6 @@ namespace Cantera {
MolalityVPSSTP(),
m_formDH(DHFORM_DILUTE_LIMIT),
m_formGC(2),
m_Pcurrent(OneAtm),
m_IionicMolality(0.0),
m_maxIionicStrength(30.0),
m_useHelgesonFixedForm(false),
@ -85,7 +83,6 @@ namespace Cantera {
MolalityVPSSTP(),
m_formDH(DHFORM_DILUTE_LIMIT),
m_formGC(2),
m_Pcurrent(OneAtm),
m_IionicMolality(0.0),
m_maxIionicStrength(3.0),
m_useHelgesonFixedForm(false),
@ -132,7 +129,6 @@ namespace Cantera {
MolalityVPSSTP::operator=(b);
m_formDH = b.m_formDH;
m_formGC = b.m_formGC;
m_Pcurrent = b.m_Pcurrent;
m_Aionic = b.m_Aionic;
m_npActCoeff = b.m_npActCoeff;
m_IionicMolality = b.m_IionicMolality;
@ -172,7 +168,7 @@ namespace Cantera {
}
/**
/*
* ~DebyeHuckel(): (virtual)
*
* Destructor for DebyeHuckel. Release objects that
@ -187,7 +183,7 @@ namespace Cantera {
}
}
/**
/*
* duplMyselfAsThermoPhase():
*
* This routine operates at the ThermoPhase level to
@ -199,7 +195,7 @@ namespace Cantera {
return (ThermoPhase *) mtp;
}
/**
/*
* 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
@ -227,7 +223,7 @@ namespace Cantera {
//
// -------- Molar Thermodynamic Properties of the Solution ---------------
//
/**
/*
* Molar enthalpy of the solution. Units: J/kmol.
*/
doublereal DebyeHuckel::enthalpy_mole() const {
@ -235,7 +231,7 @@ namespace Cantera {
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
@ -249,7 +245,7 @@ namespace Cantera {
return uu;
}
/**
/*
* Molar soln entropy at constant pressure. Units: J/kmol/K.
*
* This is calculated from the partial molar entropies.
@ -259,13 +255,13 @@ namespace Cantera {
return mean_X(DATA_PTR(m_tmpV));
}
/// Molar Gibbs function. Units: J/kmol.
// 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.
@ -289,7 +285,7 @@ namespace Cantera {
// ------- Mechanical Equation of State Properties ------------------------
//
/**
/*
* Pressure. Units: Pa.
* For this incompressible system, we return the internally storred
* independent value of the pressure.
@ -298,22 +294,29 @@ namespace Cantera {
return m_Pcurrent;
}
/**
/*
* 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 DebyeHuckel::setPressure(doublereal p) {
#ifdef DEBUG_MODE
//printf("setPressure: %g\n", p);
#endif
double temp = temperature();
if (m_waterSS) {
/*
* Call the water SS and set it's internal state
*/
m_waterSS->setTempPressure(temp, p);
/*
* Store the current pressure
*/
m_Pcurrent = p;
/*
* update the standard state thermo
* -> This involves calling the water function and setting the pressure
*/
_updateStandardStateThermo();
if (m_waterSS) {
/*
* Store the internal density of the water SS.
* Note, we would have to do this for all other
@ -321,10 +324,6 @@ namespace Cantera {
*/
m_densWaterSS = m_waterSS->density();
}
/*
* Store the current pressure
*/
m_Pcurrent = p;
/*
* Calculate all of the other standard volumes
* -> note these are constant for now
@ -361,7 +360,7 @@ namespace Cantera {
}
/**
/*
* The isothermal compressibility. Units: 1/Pa.
* The isothermal compressibility is defined as
* \f[
@ -377,7 +376,7 @@ namespace Cantera {
return 0.0;
}
/**
/*
* The thermal expansion coefficient. Units: 1/K.
* The thermal expansion coefficient is defined as
*
@ -418,7 +417,7 @@ namespace Cantera {
}
}
/**
/*
* Overwritten setMolarDensity() function is necessary because the
* density is not an indendent variable.
*
@ -441,9 +440,7 @@ namespace Cantera {
* the value propagates to underlying objects.
*/
void DebyeHuckel::setTemperature(doublereal temp) {
if (m_waterSS) {
m_waterSS->setTemperature(temp);
}
_updateStandardStateThermo();
State::setTemperature(temp);
}
@ -452,7 +449,7 @@ namespace Cantera {
// ------- 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$
@ -495,7 +492,7 @@ namespace Cantera {
return 1.0 / mvSolvent;
}
/**
/*
* Returns the natural logarithm of the standard
* concentration of the kth species
*/
@ -504,7 +501,7 @@ namespace Cantera {
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
@ -538,7 +535,7 @@ namespace Cantera {
}
/**
/*
* Get the array of non-dimensional activities at
* the current solution temperature, pressure, and
* solution concentration.
@ -546,6 +543,7 @@ namespace Cantera {
*
*/
void DebyeHuckel::getActivities(doublereal* ac) const {
_updateStandardStateThermo();
/*
* Update the molality array, m_molalities()
* This requires an update due to mole fractions
@ -561,7 +559,7 @@ namespace Cantera {
exp(m_lnActCoeffMolal[m_indexSolvent]) * xmolSolvent;
}
/**
/*
* getMolalityActivityCoefficients() (virtual, const)
*
* Get the array of non-dimensional Molality based
@ -574,7 +572,7 @@ namespace Cantera {
*/
void DebyeHuckel::
getMolalityActivityCoefficients(doublereal* acMolality) const {
_updateStandardStateThermo();
A_Debye_TP(-1.0, -1.0);
s_update_lnMolalityActCoeff();
copy(m_lnActCoeffMolal.begin(), m_lnActCoeffMolal.end(), acMolality);
@ -586,7 +584,7 @@ namespace Cantera {
//
// ------ Partial Molar Properties of the Solution -----------------
//
/**
/*
* Get the species chemical potentials. Units: J/kmol.
*
* This function returns a vector of chemical potentials of the
@ -633,7 +631,7 @@ namespace Cantera {
}
/**
/*
* Returns an array of partial molar enthalpies for the species
* in the mixture.
* Units (J/kmol)
@ -756,7 +754,7 @@ namespace Cantera {
}
}
/**
/*
* getPartialMolarVolumes() (virtual, const)
*
* returns an array of partial molar volumes of the species
@ -838,7 +836,7 @@ namespace Cantera {
* in the Solution ------------------
*/
/**
/*
* getStandardChemPotentials() (virtual, const)
*
*
@ -855,6 +853,7 @@ namespace Cantera {
* units = J / kmol
*/
void DebyeHuckel::getStandardChemPotentials(doublereal* mu) const {
_updateStandardStateThermo();
getGibbs_ref(mu);
doublereal pref;
doublereal delta_p;
@ -868,7 +867,7 @@ namespace Cantera {
}
}
/**
/*
* Get the nondimensional gibbs function for the species
* standard states at the current T and P of the solution.
*
@ -884,6 +883,7 @@ namespace Cantera {
* standard state gibbs function for species k.
*/
void DebyeHuckel::getGibbs_RT(doublereal* grt) const {
_updateStandardStateThermo();
getPureGibbs(grt);
doublereal invRT = 1.0 / _RT();
for (int k = 0; k < m_kk; k++) {
@ -891,7 +891,7 @@ namespace Cantera {
}
}
/**
/*
*
* getPureGibbs()
*
@ -924,6 +924,7 @@ namespace Cantera {
*/
void DebyeHuckel::
getEnthalpy_RT(doublereal* hrt) const {
_updateStandardStateThermo();
getEnthalpy_RT_ref(hrt);
doublereal pref;
doublereal delta_p;
@ -956,6 +957,7 @@ namespace Cantera {
*/
void DebyeHuckel::
getEntropy_R(doublereal* sr) const {
_updateStandardStateThermo();
getEntropy_R_ref(sr);
if (m_waterSS) {
sr[0] = m_waterSS->entropy_mole();
@ -982,6 +984,7 @@ namespace Cantera {
* constant pressure heat capacity for species k.
*/
void DebyeHuckel::getCp_R(doublereal* cpr) const {
_updateStandardStateThermo();
getCp_R_ref(cpr);
if (m_waterSS) {
cpr[0] = m_waterSS->cp_mole();
@ -996,6 +999,7 @@ namespace Cantera {
* units = m^3 / kmol
*/
void DebyeHuckel::getStandardVolumes(doublereal *vol) const {
_updateStandardStateThermo();
copy(m_speciesSize.begin(),
m_speciesSize.end(), vol);
if (m_waterSS) {
@ -1003,7 +1007,6 @@ namespace Cantera {
vol[0] = molecularWeight(0)/dd;
}
}
/*
* ------ Thermodynamic Values for the Species Reference States ---
@ -1815,7 +1818,7 @@ namespace Cantera {
return dAdT;
}
/**
/*
* d2A_DebyedT2_TP() (virtual)
*
* Returns the 2nd derivative of the A_Debye parameter with
@ -1849,7 +1852,7 @@ namespace Cantera {
return d2AdT2;
}
/**
/*
* dA_DebyedP_TP() (virtual)
*
* Returns the derivative of the A_Debye parameter with
@ -2692,6 +2695,32 @@ namespace Cantera {
}
}
/*
* 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.
*
*
* Note, this will throw an error. It must be reimplemented in derived classes.
*/
void DebyeHuckel::_updateStandardStateThermo(doublereal pnow) const {
_updateRefStateThermo();
doublereal tnow = temperature();
if (pnow == -1.0) {
pnow = m_Pcurrent;
}
if (m_tlast != tnow || m_plast != pnow) {
if (m_waterSS) {
m_waterSS->setTempPressure(tnow, pnow);
}
m_tlast = tnow;
m_plast = pnow;
}
}
}

153
Cantera/src/thermo/DebyeHuckel.h
View file

@ -21,65 +21,6 @@
namespace Cantera {
/*!
*
* Major Parameters:
*
* m_formDH = Form of the Debye-Huckel expression
*
* DHFORM_DILUTE_LIMIT = 0
*
* This form assumes a dilute limit to DH, and is mainly
* for informational purposes:
*
* ln(gamma_k) = -z_k**2 * alpha * sqrt(I)
*
* where I = 1/2 sum_k( molality_k * z_k**2)
*
* DHFORM_BDOT_AK = 1
*
* This form assumes Bethke's format for the DH coefficient
*
* ln(gamma_k) = -z_k**2 * alpha * sqrt(I) / (1 + B * a_k * sqrt(I))
* + bdot_k * I
*
* (note, this particular form where a_k can differ in
* multielectrolyte
* solutions has problems wrt a gibbs-duhem analysis. However
* we include it here because there is a lot of data fit to it)
*
* DHFORM_BDOT_AUNIFORM = 2
*
* This form assumes Bethke's format for the DH coefficient
*
* ln(gamma_k) = -z_k**2 * alpha * sqrt(I) / (1 + B * a * sqrt(I))
* + bdot_k * I
*
* The value of a is determined at the beginning of the
* calculation, and not changed.
*
* DHFORM_BETAIJ = 3
*
* This form assumes a linear expansion in a virial coefficient form
* It is used extensively in Newmann's book, and is the beginning of
* more complex treatments for stronger electrolytes, like Pitzer
* and HMW treatments.
*
* ln(gamma_k) = -z_k**2 * alpha * sqrt(I) / (1 + B * a * sqrt(I))
* + 2* sum_j (beta_jk m_j)
*
* DHFORM_PITZER_BETAIJ = 4
*
* This form assumes an activity coefficient formulation consistent
* with a truncated form of Pitzer's formulation.
*
* ln(gamma_k) = -z_k**2 * alpha * sqrt(I) / (1 + B * a * sqrt(I))
* -2 * z_k**2 * alpha * ln(1 + B * a * sqrt(I)) / (B * a)
* + 2 * sum_j (beta_jk m_j)
*
*/
/*!
* @name Formats for the Activity Coefficients
*
@ -318,25 +259,57 @@ namespace Cantera {
* <HR>
* <b> %Application within %Kinetics Managers </b>
* <HR>
* The standard concentration is equal to 1.0. This means that the
* kinetics operator works on an (activities basis). Since this
* is a stoichiometric substance, this means that the concentration
* of this phase drops out of kinetics expressions.
* For the time being, we have set the standard concentration for all species in
* this phase equal to the default concentration of the solvent at 298 K and 1 atm.
* This means that the
* kinetics operator essentially works on an activities basis, with units specified
* as if it were on a concentration basis.
*
* For example, a bulk-phase binary reaction between liquid species j and k, producing
* a new liquid species l would have the
* following equation for its rate of progress variable, \f$ R^1 \f$, which has
* units of kmol m-3 s-1.
*
* An example of a reaction using this is a sticking coefficient
* reaction of a substance in an ideal gas phase on a surface with a bulk phase
* species in this phase. In this case, the rate of progress for this
* reaction, \f$ R_s \f$, may be expressed via the following equation:
* \f[
* R_s = k_s C_{gas}
* R^1 = k^1 C_j^a C_k^a = k^1 (C_o a_j) (C_o a_k)
* \f]
* where the units for \f$ R_s \f$ are kmol m-2 s-1. \f$ C_{gas} \f$ has units
* of kmol m-3. Therefore, the kinetic rate constant, \f$ k_s \f$, has
* units of m s-1. Nowhere does the concentration of the bulk phase
* appear in the rate constant expression, since it's a stoichiometric
* phase and the activity is always equal to 1.0.
* where
* \f[
* C_j^a = C_o a_j \quad and \quad C_k^a = C_o a_k
* \f]
*
* \f$ 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_o \f$
* is the concentration of water at 298 K and 1 atm. \f$ a_j \f$ is
* the activity of species j at the current temperature and pressure
* and concentration of the liquid phase. \f$k^1 \f$ has units of m3 kmol-1 s-1.
*
* The reverse rate constant can then be obtained from the law of microscopic reversibility
* and the equilibrium expression for the system.
*
* \f[
* \frac{a_j a_k}{ a_l} = K^{o,1} = \exp(\frac{\mu^o_l - \mu^o_j - \mu^o_k}{R T} )
* \f]
*
* \f$ K^{o,1} \f$ is the dimensionless form of the equilibrium constant.
*
* \f[
* R^{-1} = k^{-1} C_l^a = k^{-1} (C_o a_l)
* \f]
*
* where
*
* \f[
* k^{-1} = k^1 K^{o,1} C_o
* \f]
*
* \f$k^{-1} \f$ has units of s-1.
*
* Note, this treatment may be modified in the future, as events dictate.
*
* <HR>
* <b> Instantiation of the Class </b>
* <HR>
*
* The constructor for this phase is NOT located in the default ThermoFactory
* for %Cantera. However, a new %StoichSubstanceSSTP may be created by
@ -397,8 +370,8 @@ namespace Cantera {
</species>
</speciesData> @endverbatim
*
* The model attribute, "StoichSubstanceSSTP", on the thermo element identifies the phase as being
* a StoichSubstanceSSTP object.
* The model attribute, "StoichSubstanceSSTP", on the thermo element identifies the phase as
* being a StoichSubstanceSSTP object.
*
*/
class DebyeHuckel : public MolalityVPSSTP {
@ -662,8 +635,8 @@ namespace Cantera {
* @{
*/
/**
* This method returns an array of generalized 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
@ -698,7 +671,8 @@ namespace Cantera {
* @param k Optional parameter indicating the species. The default
* is to assume this refers to species 0.
* @return
* Returns the standard Concentration in units of m3 kmol-1.
* Returns the standard Concentration in units of
* m<SUP>3</SUP> kmol<SUP>-1</SUP>.
*/
virtual doublereal standardConcentration(int k=0) const;
@ -1357,6 +1331,24 @@ namespace Cantera {
double _osmoticCoeffHelgesonFixedForm() const;
double _lnactivityWaterHelgesonFixedForm() const;
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 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.
*
*
* Note, this will throw an error. It must be reimplemented in derived classes.
*/
virtual void _updateStandardStateThermo(doublereal pres = -1.0) const;
//@}
@ -1408,11 +1400,6 @@ namespace Cantera {
*/
int m_formGC;
/**
* Current pressure in Pascal
*/
double m_Pcurrent;
//! Vector containing the electrolyte species type
/*!
* The possible types are:

5
Cantera/src/thermo/HMWSoln.cpp
View file

@ -31,7 +31,6 @@ namespace Cantera {
m_formPitzer(PITZERFORM_BASE),
m_formPitzerTemp(PITZER_TEMP_CONSTANT),
m_formGC(2),
m_Pcurrent(OneAtm),
m_IionicMolality(0.0),
m_maxIionicStrength(100.0),
m_TempPitzerRef(298.15),
@ -61,7 +60,6 @@ namespace Cantera {
m_formPitzer(PITZERFORM_BASE),
m_formPitzerTemp(PITZER_TEMP_CONSTANT),
m_formGC(2),
m_Pcurrent(OneAtm),
m_IionicMolality(0.0),
m_maxIionicStrength(100.0),
m_TempPitzerRef(298.15),
@ -85,7 +83,6 @@ namespace Cantera {
m_formPitzer(PITZERFORM_BASE),
m_formPitzerTemp(PITZER_TEMP_CONSTANT),
m_formGC(2),
m_Pcurrent(OneAtm),
m_IionicMolality(0.0),
m_maxIionicStrength(100.0),
m_TempPitzerRef(298.15),
@ -133,7 +130,6 @@ namespace Cantera {
m_formPitzer = b.m_formPitzer;
m_formPitzerTemp = b.m_formPitzerTemp;
m_formGC = b.m_formGC;
m_Pcurrent = b.m_Pcurrent;
m_Aionic = b.m_Aionic;
m_IionicMolality = b.m_IionicMolality;
m_maxIionicStrength = b.m_maxIionicStrength;
@ -265,7 +261,6 @@ namespace Cantera {
m_formPitzer(PITZERFORM_BASE),
m_formPitzerTemp(PITZER_TEMP_CONSTANT),
m_formGC(2),
m_Pcurrent(OneAtm),
m_IionicMolality(0.0),
m_maxIionicStrength(30.0),
m_TempPitzerRef(298.15),

7
Cantera/src/thermo/HMWSoln.h
View file

@ -996,13 +996,6 @@ namespace Cantera {
* bimolecular rxns which have units of m-3 kmol-1 s-1.)
*/
int m_formGC;
/**
* Current pressure in Pascal. This is now the independent variable
* as it must be for multicomponent solutions.
*/
double m_Pcurrent;
vector_int m_electrolyteSpeciesType;

2
Cantera/src/thermo/IdealMolalSoln.cpp
View file

@ -23,7 +23,6 @@ namespace Cantera {
*/
IdealMolalSoln::IdealMolalSoln() :
MolalityVPSSTP(),
m_Pcurrent(OneAtm),
m_formGC(2)
{
}
@ -55,7 +54,6 @@ namespace Cantera {
if (&b != this) {
MolalityVPSSTP::operator=(b);
m_speciesMolarVolume = b.m_speciesMolarVolume;
m_Pcurrent = b.m_Pcurrent;
m_formGC = b.m_formGC;
m_expg0_RT = b.m_expg0_RT;
m_pe = b.m_pe;

7
Cantera/src/thermo/IdealMolalSoln.h
View file

@ -1003,13 +1003,6 @@ namespace Cantera {
*/
array_fp m_speciesMolarVolume;
/*!
* Current pressure in Pascal.
*
* This is an independent variable in the problem.
*/
double m_Pcurrent;
/**
* The standard concentrations can have three different forms
* depending on the value of the member attribute m_formGC, which

12
Cantera/src/thermo/SingleSpeciesTP.h
View file

@ -670,9 +670,17 @@ namespace Cantera {
doublereal m_tmin;
//! Upper value of the temperature for which reference thermo is valid
doublereal m_tmax;
//! Current value of the pressure (Pascals)
//! The current pressure of the solution (Pa)
/*!
* It gets initialized to 1 atm.
*/
doublereal m_press;
//! Value of the reference pressure (Pascals)
/*!
* Reference pressure (Pa) must be the same for all species
* - defaults to 1 atm.
*/
doublereal m_p0;
//! Last temperature used to evaluate the thermodynamic polynomial.

288
Cantera/src/thermo/VPStandardStateTP.cpp
View file

@ -30,8 +30,13 @@ namespace Cantera {
*/
VPStandardStateTP::VPStandardStateTP() :
ThermoPhase(),
m_Pcurrent(OneAtm),
m_tlast(-1.0),
m_plast(-1.0)
m_tlast_ref(-1.0),
m_plast(-1.0),
m_p0(OneAtm),
m_useTmpRefStateStorage(true),
m_useTmpStandardStateStorage(false)
{
}
@ -46,8 +51,13 @@ namespace Cantera {
*/
VPStandardStateTP::VPStandardStateTP(const VPStandardStateTP &b) :
ThermoPhase(),
m_Pcurrent(OneAtm),
m_tlast(-1.0),
m_plast(-1.0)
m_tlast_ref(-1.0),
m_plast(-1.0),
m_p0(OneAtm),
m_useTmpRefStateStorage(true),
m_useTmpStandardStateStorage(false)
{
*this = b;
}
@ -69,13 +79,17 @@ namespace Cantera {
/*
* However, we have to handle data that we own.
*/
m_Pcurrent = b.m_Pcurrent;
m_tlast = b.m_tlast;
m_tlast_ref = b.m_tlast_ref;
m_plast = b.m_plast;
m_p0 = b.m_p0;
m_useTmpRefStateStorage = b.m_useTmpRefStateStorage;
m_h0_RT = b.m_h0_RT;
m_cp0_R = b.m_cp0_R;
m_g0_RT = b.m_g0_RT;
m_s0_R = b.m_s0_R;
m_V0 = b.m_V0;
m_useTmpStandardStateStorage = b.m_useTmpStandardStateStorage;
m_hss_RT = b.m_hss_RT;
m_cpss_R = b.m_cpss_R;
m_gss_RT = b.m_gss_RT;
@ -148,18 +162,33 @@ namespace Cantera {
}
void VPStandardStateTP::getEnthalpy_RT(doublereal* hrt) const {
_updateStandardStateThermo();
copy(m_hss_RT.begin(), m_hss_RT.end(), hrt);
if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo();
copy(m_hss_RT.begin(), m_hss_RT.end(), hrt);
} else {
err("getEnthalpy_RT ERROR: Must be overwritten in child classes");
_updateStandardStateThermo();
}
}
void VPStandardStateTP::getEntropy_R(doublereal* srt) const {
_updateStandardStateThermo();
copy(m_sss_R.begin(), m_sss_R.end(), srt);
if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo();
copy(m_sss_R.begin(), m_sss_R.end(), srt);
} else {
err("getEntropy_R ERROR: Must be overwritten in child classes");
_updateStandardStateThermo();
}
}
void VPStandardStateTP::getGibbs_RT(doublereal* grt) const {
_updateStandardStateThermo();
copy(m_gss_RT.begin(), m_gss_RT.end(), grt);
if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo();
copy(m_gss_RT.begin(), m_gss_RT.end(), grt);
} else {
err("getGibbs_RT ERROR: Must be overwritten in child classes");
_updateStandardStateThermo();
}
}
void VPStandardStateTP::getPureGibbs(doublereal* g) const {
@ -171,23 +200,38 @@ namespace Cantera {
}
void VPStandardStateTP::getIntEnergy_RT(doublereal* urt) const {
_updateStandardStateThermo();
copy(m_hss_RT.begin(), m_hss_RT.end(), urt);
doublereal RT = _RT();
doublereal tmp = pressure() / RT;
for (int k = 0; k < m_kk; k++) {
urt[k] -= tmp * m_Vss[k];
if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo();
copy(m_hss_RT.begin(), m_hss_RT.end(), urt);
doublereal RT = _RT();
doublereal tmp = pressure() / RT;
for (int k = 0; k < m_kk; k++) {
urt[k] -= tmp * m_Vss[k];
}
} else {
err("getIntEnergy_RT ERROR: Must be overwritten in child classes");
_updateStandardStateThermo();
}
}
void VPStandardStateTP::getCp_R(doublereal* cpr) const {
_updateStandardStateThermo();
copy(m_cpss_R.begin(), m_cpss_R.end(), cpr);
if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo();
copy(m_cpss_R.begin(), m_cpss_R.end(), cpr);
} else {
err("getCp_R ERROR: Must be overwritten in child classes");
_updateStandardStateThermo();
}
}
void VPStandardStateTP::getStandardVolumes(doublereal *vol) const {
_updateStandardStateThermo();
copy(m_Vss.begin(), m_Vss.end(), vol);
if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo();
copy(m_Vss.begin(), m_Vss.end(), vol);
} else {
err("getStandardVolumes ERROR: Must be overwritten in child classes");
_updateStandardStateThermo();
}
}
/*
@ -200,16 +244,23 @@ namespace Cantera {
* the reference pressure for the species.
*/
void VPStandardStateTP::getEnthalpy_RT_ref(doublereal *hrt) const {
/*
* Call the function that makes sure the local copy of the
* species reference thermo functions are up to date for the
* current temperature.
*/
_updateRefStateThermo();
/*
* Copy the enthalpy function into return vector.
*/
copy(m_h0_RT.begin(), m_h0_RT.end(), hrt);
if (m_useTmpRefStateStorage) {
/*
* Call the function that makes sure the local copy of the
* species reference thermo functions are up to date for the
* current temperature.
*/
_updateRefStateThermo();
/*
* Copy the enthalpy function into return vector.
*/
copy(m_h0_RT.begin(), m_h0_RT.end(), hrt);
} else if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo(m_p0);
copy(m_hss_RT.begin(), m_hss_RT.end(), hrt);
} else {
err("getEnthalpy_RT_ref() ERROR: not handled");
}
}
/*
@ -218,16 +269,23 @@ namespace Cantera {
* of the solution and the reference pressure for the species.
*/
void VPStandardStateTP::getGibbs_RT_ref(doublereal *grt) const {
/*
* Call the function that makes sure the local copy of
* the species reference thermo functions are up to date
* for the current temperature.
*/
_updateRefStateThermo();
/*
* Copy the gibbs function into return vector.
*/
copy(m_g0_RT.begin(), m_g0_RT.end(), grt);
if (m_useTmpRefStateStorage) {
/*
* Call the function that makes sure the local copy of
* the species reference thermo functions are up to date
* for the current temperature.
*/
_updateRefStateThermo();
/*
* Copy the gibbs function into return vector.
*/
copy(m_g0_RT.begin(), m_g0_RT.end(), grt);
} else if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo(m_p0);
copy(m_gss_RT.begin(), m_gss_RT.end(), grt);
} else {
err("getGibbs_RT_ref() ERROR: not handled");
}
}
/*
@ -253,16 +311,23 @@ namespace Cantera {
* of the solution and the reference pressure for the species.
*/
void VPStandardStateTP::getEntropy_R_ref(doublereal *er) const {
/*
* Call the function that makes sure the local copy of
* the species reference thermo functions are up to date
* for the current temperature.
*/
_updateRefStateThermo();
/*
* Copy the gibbs function into return vector.
*/
copy(m_s0_R.begin(), m_s0_R.end(), er);
if (m_useTmpRefStateStorage) {
/*
* Call the function that makes sure the local copy of
* the species reference thermo functions are up to date
* for the current temperature.
*/
_updateRefStateThermo();
/*
* Copy the gibbs function into return vector.
*/
copy(m_s0_R.begin(), m_s0_R.end(), er);
} else if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo(m_p0);
copy(m_sss_R.begin(), m_sss_R.end(), er);
} else {
err("getEntropy_R_ref() ERROR: not handled");
}
}
/*
@ -272,17 +337,39 @@ namespace Cantera {
* and reference pressure for the species.
*/
void VPStandardStateTP::getCp_R_ref(doublereal *cpr) const {
/*
* Call the function that makes sure the local copy of
* the species reference thermo functions are up to date
* for the current temperature.
*/
_updateRefStateThermo();
/*
* Copy the gibbs function into return vector.
*/
copy(m_cp0_R.begin(), m_cp0_R.end(), cpr);
if (m_useTmpRefStateStorage) {
/*
* Call the function that makes sure the local copy of
* the species reference thermo functions are up to date
* for the current temperature.
*/
_updateRefStateThermo();
/*
* Copy the gibbs function into return vector.
*/
copy(m_cp0_R.begin(), m_cp0_R.end(), cpr);
} else if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo(m_p0);
copy(m_cpss_R.begin(), m_cpss_R.end(), cpr);
} else {
err("getCp_R_ref() ERROR: not handled");
}
}
/*
* 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 {
if (m_useTmpStandardStateStorage) {
_updateStandardStateThermo(m_p0);
copy(m_Vss.begin(), m_Vss.end(), vol);
} else {
err("getStandardVolumes_ref() ERROR: not handled");
}
}
/*
* Perform initializations after all species have been
@ -300,16 +387,19 @@ namespace Cantera {
void VPStandardStateTP::initLengths() {
m_kk = nSpecies();
int leng = m_kk;
m_h0_RT.resize(leng);
m_g0_RT.resize(leng);
m_cp0_R.resize(leng);
m_s0_R.resize(leng);
m_V0.resize(leng);
m_hss_RT.resize(leng);
m_gss_RT.resize(leng);
m_cpss_R.resize(leng);
m_sss_R.resize(leng);
m_Vss.resize(leng);
if (m_useTmpRefStateStorage){
m_h0_RT.resize(leng);
m_g0_RT.resize(leng);
m_cp0_R.resize(leng);
m_s0_R.resize(leng);
}
if (m_useTmpStandardStateStorage) {
m_hss_RT.resize(leng);
m_gss_RT.resize(leng);
m_cpss_R.resize(leng);
m_sss_R.resize(leng);
m_Vss.resize(leng);
}
}
/*
@ -337,21 +427,34 @@ namespace Cantera {
/*
* void _updateRefStateThermo() (protected, virtual, const)
*
* This function gets called for every call to functions in this
* class. It checks to see whether the temperature has changed and
* This function checks to see whether the temperature has changed and
* thus the reference thermodynamics functions for all of the species
* must be recalculated.
* It must be called for every reference state function evaluation,
* if m_useTmpRefStateStorage is set to true.
* If the temperature has changed, the species thermo manager is called
* to recalculate G, Cp, H, and S at the current temperature.
* to recalculate the following internal arrays at the current temperature and at
* the reference pressure:
*
* - m_h0_RT
* - m_g0_RT
* - m_s0_R
* - m_cp0_R
*
* This function may be reimplemented in child objects. However, it doesn't
* necessarily have to be, if the species thermo manager can carry
* out the full calculation.
*/
void VPStandardStateTP::_updateRefStateThermo() const {
doublereal tnow = temperature();
if (m_tlast != tnow) {
m_spthermo->update(tnow, DATA_PTR(m_cp0_R), DATA_PTR(m_h0_RT),
DATA_PTR(m_s0_R));
m_tlast = tnow;
for (int k = 0; k < m_kk; k++) {
m_g0_RT[k] = m_h0_RT[k] - m_s0_R[k];
if (m_spthermo) {
doublereal tnow = temperature();
if (m_tlast_ref != tnow) {
m_spthermo->update(tnow, DATA_PTR(m_cp0_R), DATA_PTR(m_h0_RT),
DATA_PTR(m_s0_R));
m_tlast_ref = tnow;
for (int k = 0; k < m_kk; k++) {
m_g0_RT[k] = m_h0_RT[k] - m_s0_R[k];
}
}
}
}
@ -359,16 +462,31 @@ namespace Cantera {
/*
* void _updateStandardStateThermo() (protected, virtual, const)
*
* This function gets called for every call to functions in this
* class. It checks to see whether the temperature has changed and
* 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 {
void VPStandardStateTP::_updateStandardStateThermo(doublereal pnow) const {
_updateRefStateThermo();
doublereal tnow = temperature();
doublereal pnow = pressure();
if (pnow == -1.0) {
pnow = pressure();
}
if (m_tlast != tnow || m_plast != pnow) {
err("getStandardVolumes");
err("_updateStandardStateThermo ERROR: Must be overwritten in child classes");
/*
* Redo objects that need reevaluation.
*/
for (int k = 0; k < m_kk; k++) {
m_g0_RT[k] = m_g0_RT[k];
}
m_tlast = tnow;
m_plast = pnow;
}
@ -376,5 +494,3 @@ namespace Cantera {
}

157
Cantera/src/thermo/VPStandardStateTP.h
View file

@ -34,15 +34,53 @@ namespace Cantera {
* a variable pressure standard state for species.
*
* Several concepts are introduced. The first concept is there are temporary
* variables for holding the species standard values of Cp, H, S, and V at the
* variables for holding the species standard state values
* of Cp, H, S, G, and V at the
* last temperature and pressure called. These functions are not recalculated
* if a new call is made using the previous temperature and pressure.
*
* There are also temporary
* variables for holding the species reference-state values of Cp, H, S, and V at the
* variables for holding the species reference-state values of Cp, H, S, and G at the
* last temperature and reference pressure called. These functions are not recalculated
* if a new call is made using the previous temperature.
*
* To support the above functionality, pressure and temperature variables,
* m_plast and m_tlast, are kept which store the last pressure and temperature
* used in the evaluation of standard state properties. An optional utility is provided
* to store the results from the last temperature and pressure standard
* state calculation and use it on subsequent calculations, if the temperature
* and pressure are unchanged.
*
* If #m_useTmpRefStateStorage is set to true, then the following internal
* arrays, containing information about the reference arrays,
* are calculated and kept up to date at every call.
*
* - #m_h0_RT
* - #m_g0_RT
* - #m_s0_R
* - #m_cp0_R
*
* The virtual function #_updateRefStateThermo() is supplied to do this
* and may be reimplemented in child routines. A default implementation
* based on the speciesThermo class is supplied in this base class.
* #_updateStandardStateThermo() is called whenever a reference state property is needed.
*
* When #m_useTmpStandardStateStorage is true, then the following
* internal arrays, containing information on the standard state properties
* are calculated and kept up to date.
*
* - #m_hss_RT;
* - #m_cpss_R;
* - #m_gss_RT;
* - #m_sss_R;
* - #m_Vss
*
* The virtual function #_updateStandardStateThermo() is supplied to do this
* and must be reimplemented in child routines, when #m_useTmpStandardStateStorage is true.
* It may be optionally reimplemented in child routines if
* #m_useTmpStandardStateStorage is false.
* #_updateStandardStateThermo() is called whenever a standard state property is needed.
*
* This class is usually used for nearly incompressible phases. For those phases, it
* makes sense to change the equation of state independent variable from density to pressure.
*
@ -99,19 +137,21 @@ namespace Cantera {
/// @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.
* getChemPotentials() and then dividing by RT. No need for child
* classes to handle.
*
* @param mu Output vector of non-dimensional species chemical potentials
* Length: m_kk.
*/
virtual void getChemPotentials_RT(doublereal* mu) const;
void getChemPotentials_RT(doublereal* mu) const;
//@}
@ -166,15 +206,20 @@ namespace Cantera {
*/
virtual void getGibbs_RT(doublereal* grt) const;
/**
* Get the nondimensional Gibbs functions for the standard
* state of the species at the current T and P.
//! Get the nondimensional Gibbs functions for the standard
//! state of the species at the current T and P.
/*!
* (Note resolved at this level)
*
* @param gpure Output vector of standard state
* Gibbs free energies. length = m_kk.
* units are J/kmol.
*
* @todo This could be eliminated. It doesn't fit into the current
* naming convention.
*/
virtual void getPureGibbs(doublereal* gpure) const;
void getPureGibbs(doublereal* gpure) const;
/**
* Returns the vector of nondimensional
@ -224,24 +269,33 @@ namespace Cantera {
/*!
* @internal
*
* This function gets called for every call to functions in this
* If m_useTmpStandardStateStorage is true,
* this function must be called for every call to functions in this
* class. It checks to see whether the temperature or pressure has changed and
* thus the ss thermodynamics functions for all of the species
* must be recalculated.
*
* This function is responsible for updating the following internal members:
* This function is responsible for updating the following internal members,
* when m_useTmpStandardStateStorage is true.
*
* m_hss_RT;
* m_cpss_R;
* m_gss_RT;
* m_sss_R;
* m_Vss
* - m_hss_RT;
* - m_cpss_R;
* - m_gss_RT;
* - m_sss_R;
* - m_Vss
*
* If m_useTmpStandardStateStorage is not true, this function may be
* required to be called by child classes to update internal member data.
*
* Note, this will throw an error. It must be reimplemented in derived classes.
*
* @param pres Pressure at which to carry out the calculation.
* The default is to use the current pressure, storred in m_Pcurrent.
*/
virtual void _updateStandardStateThermo() const;
virtual void _updateStandardStateThermo(doublereal pres = -1.0) const;
public:
//@}
/// @name Thermodynamic Values for the Species Reference States (VPStandardStateTP)
/*!
@ -298,7 +352,7 @@ namespace Cantera {
*/
virtual void getEntropy_R_ref(doublereal *er) const;
/**
/*!
* Returns the vector of nondimensional
* constant pressure heat capacities of the reference state
* at the current temperature of the solution
@ -310,15 +364,15 @@ namespace Cantera {
*/
virtual void getCp_R_ref(doublereal *cprt) const;
//! Recalculate the Reference state thermo functions
//! Get the molar volumes of the species reference states at the current
//! <I>T</I> and <I>P_ref</I> of the solution.
/*!
* This function checks to see whether the temperature has changed and
* thus the reference thermodynamics functions for all of the species
* must be recalculated.
* If the temperature has changed, the species thermo manager is called
* to recalculate G, Cp, H, and S at the current temperature and at
* the reference pressure.
* units = m^3 / kmol
*
* @param vol Output vector containing the standard state volumes.
* Length: m_kk.
*/
virtual void getStandardVolumes_ref(doublereal *vol) const;
protected:
@ -327,12 +381,24 @@ namespace Cantera {
* This function checks to see whether the temperature has changed and
* thus the reference thermodynamics functions for all of the species
* must be recalculated.
* It must be called for every reference state function evaluation,
* if m_useTmpRefStateStorage is set to true.
* If the temperature has changed, the species thermo manager is called
* to recalculate G, Cp, H, and S at the current temperature and at
* the reference pressure.
* to recalculate the following internal arrays at the current temperature and at
* the reference pressure:
*
* - m_h0_RT
* - m_g0_RT
* - m_s0_R
* - m_cp0_R
*
* This function may be reimplemented in child objects. However, it doesn't
* necessarily have to be, if the species thermo manager can carry
* out the full calculation.
*/
virtual void _updateRefStateThermo() const;
//@}
@ -416,13 +482,34 @@ namespace Cantera {
//@}
protected:
//! The current pressure of the solution (Pa)
/*!
* It gets initialized to 1 atm.
*/
mutable doublereal m_Pcurrent;
//! The last temperature at which the reference thermodynamic properties were calculated at.
mutable doublereal m_tlast;
//! The last temperature at which the reference thermodynamic properties were calculated at.
mutable doublereal m_tlast_ref;
//! The last pressure at which the Standard State thermodynamic properties were calculated at.
mutable doublereal m_plast;
/*!
* Reference pressure (Pa) must be the same for all species
* - defaults to 1 atm.
*/
doublereal m_p0;
/*!
* boolean indicating whether temporary reference state storage is used
* -> default is true
*/
bool m_useTmpRefStateStorage;
/*!
* Vector containing the species reference enthalpies at T = m_tlast
* and P = p_ref.
@ -447,11 +534,11 @@ namespace Cantera {
*/
mutable vector_fp m_s0_R;
/**
* Vector containing the species reference volumes
* at T = m_tlast and P = p_ref
*/
mutable vector_fp m_V0;
/*!
* boolean indicating whether temporary standard state storage is used
* -> default is false
*/
bool m_useTmpStandardStateStorage;
/**
* Vector containing the species Standard State enthalpies at T = m_tlast
@ -482,6 +569,8 @@ namespace Cantera {
* at T = m_tlast and P = m_plast
*/
mutable vector_fp m_Vss;
private:

1
test_problems/cathermo/DH_graph_1/runtest
View file

@ -51,7 +51,6 @@ fi
/bin/rm -f test.out test.diff DH_NaCl_acommon.csv
echo 'Testing the DH dilute act calculation - act vs I'
/bin/rm DH_NaCl_acommon.csv
$prog DH_NaCl_acommon.xml > DH_NaCl_acommon.csv
retnStat=$?
echo 'Making a comparison with the good saved solution: '