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

Worked on doxygen updates. Focussed on adding LatticePhase. Added

Browse source 
and refined functionality of that routine at the same time.
This commit is contained in:
Harry Moffat 2008-10-08 22:11:08 +00:00
parent a561e85775
commit fcb9bcb5d3
10 changed files with 1062 additions and 330 deletions
Show stats Download patch file Download diff file Expand all files Collapse all files

3
Cantera/src/thermo/EdgePhase.h
View file

@ -93,6 +93,3 @@ namespace Cantera {
#endif

10
Cantera/src/thermo/HMWSoln.h
View file

@ -1416,6 +1416,7 @@ namespace Cantera {
*/
virtual void setPressure(doublereal p);
private:
/**
* Calculate the density of the mixture using the partial
* molar volumes and mole fractions as input
@ -1441,9 +1442,14 @@ namespace Cantera {
*/
void calcDensity();
public:
//! Returns the current value of the density
/*!
* @return value of the density. Units: kg/m^3
*/
virtual doublereal density() const;
//! Set the internally storred density (gm/m^3) of the phase.
//! Set the internally storred density (kg/m^3) of the phase.
/*!
* Overwritten setDensity() function is necessary because of
* the underlying water model.
@ -1459,7 +1465,6 @@ namespace Cantera {
*/
void setDensity(doublereal rho);
//! Set the internally storred molar density (kmol/m^3) for the phase.
/**
* Overwritten setMolarDensity() function is necessary because of the
@ -1623,7 +1628,6 @@ namespace Cantera {
*/
virtual void getActivities(doublereal* ac) const;
//! Get the array of non-dimensional molality-based
//! activity coefficients at
//! the current solution temperature, pressure, and solution concentration.

13
Cantera/src/thermo/IdealGasPhase.h
View file

@ -834,16 +834,13 @@ namespace Cantera {
/*!
* @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
* This method performs any initialization required after all
* species have been added. For example, it is 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 from ThermoPhase::initThermoXML(),
* each species.
* This method is called from ThermoPhase::initThermoXML(),
* which is called from importPhase(),
* just prior to returning from function importPhase().
* just prior to returning from the function, importPhase().
*
* @see importCTML.cpp
*/

4
Cantera/src/thermo/IdealSolidSolnPhase.h
View file

@ -207,12 +207,12 @@ namespace Cantera {
* For an ideal, constant partial molar volume solution mixture with
* pure species phases which exhibit zero volume expansivity:
* \f[
* \hat s(T, P, X_k) = \sum_k X_k \hat s^0_k(T) - \hat R \sum_k X_k log(X_k)
* \hat s(T, P, X_k) = \sum_k X_k \hat s^0_k(T) - \hat R \sum_k X_k log(X_k)
* \f]
* The reference-state pure-species entropies
* \f$ \hat s^0_k(T,p_{ref}) \f$ are computed by the species thermodynamic
* property manager. The pure species entropies are independent of
* temperature since the volume expansivities are equal to zero.
* pressure since the volume expansivities are equal to zero.
* @see SpeciesThermo
*/
virtual doublereal entropy_mole() const;

267
Cantera/src/thermo/LatticePhase.cpp
View file

@ -1,7 +1,13 @@
/**
*
* @file LatticePhase.cpp
* Definitions for a simple thermodynamics model of a bulk phase
* derived from ThermoPhase,
* assuming a lattice of solid atoms
* (see \ref thermoprops and class \link Cantera::LatticePhase LatticePhase\endlink).
*
*/
/*
* $Id$
*/
@ -17,18 +23,19 @@
#include "mix_defs.h"
#include "LatticePhase.h"
#include "SpeciesThermo.h"
#include <math.h>
namespace Cantera {
//! Base Empty constructor
// Base Empty constructor
LatticePhase::LatticePhase() :
m_tlast(0.0)
{
}
//! Copy Constructor
/*!
// Copy Constructor
/*
* @param right Object to be copied
*/
LatticePhase::LatticePhase(const LatticePhase &right) :
@ -37,8 +44,8 @@ namespace Cantera {
*this = operator=(right);
}
//! Assignment operator
/*!
// Assignment operator
/*
* @param right Object to be copied
*/
LatticePhase& LatticePhase::operator=(const LatticePhase& right) {
@ -60,12 +67,12 @@ namespace Cantera {
return *this;
}
//! Destructor
// Destructor
LatticePhase::~LatticePhase() {
}
//! Duplication function
/*!
// Duplication function
/*
* This virtual function is used to create a duplicate of the
* current phase. It's used to duplicate the phase when given
* a ThermoPhase pointer to the phase.
@ -78,110 +85,172 @@ namespace Cantera {
}
doublereal LatticePhase::
enthalpy_mole() const {
doublereal p0 = m_spthermo->refPressure();
return GasConstant * temperature() *
mean_X(&enthalpy_RT()[0])
+ (pressure() - p0)/molarDensity();
doublereal LatticePhase::
enthalpy_mole() const {
doublereal p0 = m_spthermo->refPressure();
return GasConstant * temperature() *
mean_X(&enthalpy_RT_ref()[0])
+ (pressure() - p0)/molarDensity();
}
doublereal LatticePhase::intEnergy_mole() const {
doublereal p0 = m_spthermo->refPressure();
return GasConstant * temperature() *
mean_X(&enthalpy_RT_ref()[0])
- p0/molarDensity();
}
doublereal LatticePhase::entropy_mole() const {
return GasConstant * (mean_X(&entropy_R_ref()[0]) -
sum_xlogx());
}
doublereal LatticePhase::gibbs_mole() const {
return enthalpy_mole() - temperature() * entropy_mole();
}
doublereal LatticePhase::cp_mole() const {
return GasConstant * mean_X(&cp_R_ref()[0]);
}
doublereal LatticePhase::cv_mole() const {
return cp_mole();
}
void LatticePhase::setPressure(doublereal p) {
m_press = p;
setMolarDensity(m_molar_density);
}
void LatticePhase::getActivityConcentrations(doublereal* c) const {
getMoleFractions(c);
}
void LatticePhase::getActivityCoefficients(doublereal* ac) const {
for (int k = 0; k < m_kk; k++) {
ac[k] = 1.0;
}
}
doublereal LatticePhase::intEnergy_mole() const {
doublereal p0 = m_spthermo->refPressure();
return GasConstant * temperature() *
mean_X(&enthalpy_RT()[0])
- p0/molarDensity();
doublereal LatticePhase::standardConcentration(int k) const {
return 1.0;
}
doublereal LatticePhase::logStandardConc(int k) const {
return 0.0;
}
void LatticePhase::getChemPotentials(doublereal* mu) const {
doublereal vdp = ((pressure() - m_spthermo->refPressure())/
molarDensity());
doublereal xx;
doublereal rt = temperature() * GasConstant;
const array_fp& g_RT = gibbs_RT_ref();
for (int k = 0; k < m_kk; k++) {
xx = fmaxx(SmallNumber, moleFraction(k));
mu[k] = rt*(g_RT[k] + log(xx)) + vdp;
}
}
doublereal LatticePhase::entropy_mole() const {
return GasConstant * (mean_X(&entropy_R()[0]) -
sum_xlogx());
void LatticePhase::getPartialMolarVolumes(doublereal* vbar) const {
getStandardVolumes(vbar);
}
void LatticePhase::getStandardChemPotentials(doublereal* mu0) const {
const array_fp& gibbsrt = gibbs_RT_ref();
scale(gibbsrt.begin(), gibbsrt.end(), mu0, _RT());
}
void LatticePhase::getPureGibbs(doublereal* gpure) const {
const array_fp& gibbsrt = gibbs_RT_ref();
scale(gibbsrt.begin(), gibbsrt.end(), gpure, _RT());
}
void LatticePhase::getEnthalpy_RT(doublereal* hrt) const {
const array_fp& _h = enthalpy_RT_ref();
std::copy(_h.begin(), _h.end(), hrt);
doublereal tmp = (pressure() - m_p0) / (molarDensity() * GasConstant * temperature());
for (int k = 0; k < m_kk; k++) {
hrt[k] += tmp;
}
}
doublereal LatticePhase::gibbs_mole() const {
return enthalpy_mole() - temperature() * entropy_mole();
void LatticePhase::getEntropy_R(doublereal* sr) const {
const array_fp& _s = entropy_R_ref();
std::copy(_s.begin(), _s.end(), sr);
}
void LatticePhase::getGibbs_RT(doublereal* grt) const {
const array_fp& gibbsrt = gibbs_RT_ref();
std::copy(gibbsrt.begin(), gibbsrt.end(), grt);
}
void LatticePhase::getCp_R(doublereal* cpr) const {
const array_fp& _cpr = cp_R_ref();
std::copy(_cpr.begin(), _cpr.end(), cpr);
}
void LatticePhase::getStandardVolumes(doublereal* vbar) const {
doublereal vv = 1.0/m_molar_density;
for (int k = 0; k < m_kk; k++) {
vbar[k] = vv;
}
}
doublereal LatticePhase::cp_mole() const {
return GasConstant * mean_X(&cp_R()[0]);
void LatticePhase::initThermo() {
m_kk = nSpecies();
m_mm = nElements();
doublereal tmin = m_spthermo->minTemp();
doublereal tmax = m_spthermo->maxTemp();
if (tmin > 0.0) m_tmin = tmin;
if (tmax > 0.0) m_tmax = tmax;
m_p0 = refPressure();
int leng = m_kk;
m_h0_RT.resize(leng);
m_g0_RT.resize(leng);
m_cp0_R.resize(leng);
m_s0_R.resize(leng);
setMolarDensity(m_molar_density);
}
void LatticePhase::_updateThermo() const {
doublereal tnow = temperature();
if (fabs(molarDensity() - m_molar_density)/m_molar_density > 0.0001) {
throw CanteraError("_updateThermo","molar density changed from "
+fp2str(m_molar_density)+" to "+fp2str(molarDensity()));
}
void LatticePhase::getActivityConcentrations(doublereal* c) const {
getMoleFractions(c);
if (m_tlast != tnow) {
m_spthermo->update(tnow, &m_cp0_R[0], &m_h0_RT[0],
&m_s0_R[0]);
m_tlast = tnow;
int k;
for (k = 0; k < m_kk; k++) {
m_g0_RT[k] = m_h0_RT[k] - m_s0_R[k];
}
m_tlast = tnow;
}
}
void LatticePhase::getActivityCoefficients(doublereal* ac) const {
for (int k = 0; k < m_kk; k++) {
ac[k] = 1.0;
}
}
void LatticePhase::setParameters(int n, doublereal* c) {
m_molar_density = c[0];
setMolarDensity(m_molar_density);
}
doublereal LatticePhase::standardConcentration(int k) const {
return 1.0;
}
void LatticePhase::getParameters(int &n, doublereal * const c) const {
double d = molarDensity();
c[0] = d;
n = 1;
}
doublereal LatticePhase::logStandardConc(int k) const {
return 0.0;
}
void LatticePhase::getChemPotentials(doublereal* mu) const {
doublereal vdp = (pressure() - m_spthermo->refPressure())/
molarDensity();
doublereal xx;
doublereal rt = temperature() * GasConstant;
const array_fp& g_RT = gibbs_RT();
for (int k = 0; k < m_kk; k++) {
xx = fmaxx(SmallNumber, moleFraction(k));
mu[k] = rt*(g_RT[k] + log(xx)) + vdp;
}
}
void LatticePhase::getStandardChemPotentials(doublereal* mu0) const {
const array_fp& gibbsrt = gibbs_RT();
scale(gibbsrt.begin(), gibbsrt.end(), mu0, _RT());
}
void LatticePhase::initThermo() {
m_kk = nSpecies();
m_mm = nElements();
doublereal tmin = m_spthermo->minTemp();
doublereal tmax = m_spthermo->maxTemp();
if (tmin > 0.0) m_tmin = tmin;
if (tmax > 0.0) m_tmax = tmax;
m_p0 = refPressure();
int leng = m_kk;
m_h0_RT.resize(leng);
m_g0_RT.resize(leng);
m_cp0_R.resize(leng);
m_s0_R.resize(leng);
setMolarDensity(m_molar_density);
}
void LatticePhase::_updateThermo() const {
doublereal tnow = temperature();
if (fabs(molarDensity() - m_molar_density)/m_molar_density > 0.0001) {
throw CanteraError("_updateThermo","molar density changed from "
+fp2str(m_molar_density)+" to "+fp2str(molarDensity()));
}
if (m_tlast != tnow) {
m_spthermo->update(tnow, &m_cp0_R[0], &m_h0_RT[0],
&m_s0_R[0]);
m_tlast = tnow;
int k;
for (k = 0; k < m_kk; k++) {
m_g0_RT[k] = m_h0_RT[k] - m_s0_R[k];
}
m_tlast = tnow;
}
}
void LatticePhase::setParametersFromXML(const XML_Node& eosdata) {
eosdata._require("model","Lattice");
m_molar_density = getFloat(eosdata, "site_density", "-");
m_vacancy = getString(eosdata, "vacancy_species");
}
void LatticePhase::setParametersFromXML(const XML_Node& eosdata) {
eosdata._require("model","Lattice");
m_molar_density = getFloat(eosdata, "site_density", "-");
m_vacancy = getString(eosdata, "vacancy_species");
}
}
#endif

902
Cantera/src/thermo/LatticePhase.h
View file

@ -1,8 +1,11 @@
/**
*
* @file LatticePhase.h
* Header for a simple thermodynamics model of a bulk phase
* derived from ThermoPhase,
* assuming a lattice of solid atoms
* (see \ref thermoprops and class \link Cantera::LatticePhase LatticePhase\endlink).
*
*/
/* $Author$
* $Date$
* $Revision$
@ -15,6 +18,7 @@
#define CT_LATTICE_H
#include "config.h"
#ifdef WITH_LATTICE_SOLID
#include "ct_defs.h"
@ -25,155 +29,789 @@
namespace Cantera {
/**
//! A simple thermoydnamics model for a bulk phase,
//! assuming a lattice of solid atoms
/*!
* The bulk consists of a matrix of equivalent sites whose molar density
* does not vary with temperature or pressure. The thermodynamics
* obeys the ideal solution laws. The phase and the pure species phases which
* comprise the standard states of the species are assumed to have
* zero volume expansivity and zero isothermal compressibility.
*
* The density of matrix sites is given by the variable \f$ C_o \f$,
* which has SI units of kmol m-3.
*
*
* <b> Specification of Species Standard %State Properties </b>
*
* It is assumed that the reference state thermodynamics may be
* obtained by a pointer to a populated species thermodynamic property
* manager class (see ThermoPhase::m_spthermo). However, how to relate pressure
* changes to the reference state thermodynamics is within this class.
*
* Pressure is defined as an independent variable in this phase. However, it has
* no effect on any quantities, as the molar concentration is a constant.
*
* The standard state enthalpy function is given by the following relation,
* which has a weak dependence on the system pressure, \f$P\f$.
*
* \f[
* \raggedright h^o_k(T,P) =
* h^{ref}_k(T) + \left( \frac{P - P_{ref}}{C_o} \right)
* \f]
*
* For an incompressible substance, the molar internal energy is
* independent of pressure. Since the thermodynamic properties
* are specified by giving the standard-state enthalpy, the
* term \f$ \frac{P_{ref}}{C_o} \f$ is subtracted from the specified reference molar
* enthalpy to compute the standard state molar internal energy:
*
* \f[
* u^o_k(T,P) = h^{ref}_k(T) - \frac{P_{ref}}{C_o}
* \f]
*
* The standard state heat capacity, internal energy, and entropy are independent
* of pressure. The standard state gibbs free energy is obtained
* from the enthalpy and entropy functions.
*
* The standard state molar volume is independent of temperature, pressure,
* and species identity:
*
* \f[
* V^o_k(T,P) = \frac{1.0}{C_o}
* \f]
*
*
* <HR>
* <H2> Specification of Solution Thermodynamic Properties </H2>
* <HR>
*
* The activity of species \f$ k \f$ defined in the phase, \f$ a_k \f$, is
* given by the ideal solution law:
*
* \f[
* a_k = X_k ,
* \f]
*
* where \f$ X_k \f$ is the mole fraction of species <I>k</I>.
* The chemical potential for species <I>k</I> is equal to
*
* \f[
* \mu_k(T,P) = \mu^o_k(T, P) + R T \log(X_k)
* \f]
*
* The partial molar entropy for species <I>k</I> is given by the following relation,
*
* \f[
* \tilde{s}_k(T,P) = s^o_k(T,P) - R \log(X_k) = s^{ref}_k(T) - R \log(X_k)
* \f]
*
* The partial molar enthalpy for species <I>k</I> is
*
* \f[
* \tilde{h}_k(T,P) = h^o_k(T,P) = h^{ref}_k(T) + \left( \frac{P - P_{ref}}{C_o} \right)
* \f]
*
* The partial molar Internal Energy for species <I>k</I> is
*
* \f[
* \tilde{u}_k(T,P) = u^o_k(T,P) = u^{ref}_k(T)
* \f]
*
* The partial molar Heat Capacity for species <I>k</I> is
*
* \f[
* \tilde{Cp}_k(T,P) = Cp^o_k(T,P) = Cp^{ref}_k(T)
* \f]
*
* The partial molar volume is independent of temperature, pressure,
* and species identity:
*
* \f[
* \tilde{V}_k(T,P) = V^o_k(T,P) = \frac{1.0}{C_o}
* \f]
*
* It is assumed that the reference state thermodynamics may be
* obtained by a pointer to a populated species thermodynamic property
* manager class (see ThermoPhase::m_spthermo). How to relate pressure
* changes to the reference state thermodynamics is resolved at this level.
*
* Pressure is defined as an independent variable in this phase. However, it only
* has a weak dependence on the enthalpy, and doesn't effect the molar
* concentration.
*
* <HR>
* <H2> %Application within %Kinetics Managers </H2>
* <HR>
*
* \f$ C^a_k\f$ are defined such that \f$ C^a_k = a_k = X_k \f$
* \f$ C^s_k \f$, the standard concentration, is
* defined to be equal to one. \f$ a_k \f$ are activities used in the
* thermodynamic functions. These activity (or generalized)
* concentrations are used
* by kinetics manager classes to compute the forward and
* reverse rates of elementary reactions.
* The activity concentration,\f$ C^a_k \f$, is given by the following expression.
*
* \f[
* C^a_k = C^s_k X_k = X_k
* \f]
*
* The standard concentration for species <I>k</I> is identically one
*
* \f[
* C^s_k = C^s = 1.0
* \f]
*
* For example, a bulk-phase binary gas reaction between species j and k, producing
* a new species l would have the
* following equation for its rate of progress variable, \f$ R^1 \f$, which has
* units of kmol m-3 s-1.
*
* \f[
* R^1 = k^1 C_j^a C_k^a = k^1 X_j X_k
* \f]
*
* The reverse rate constant can then be obtained from the law of microscopic reversibility
* and the equilibrium expression for the system.
*
* \f[
* \frac{X_j X_k}{ X_l} = K_a^{o,1} = \exp(\frac{\mu^o_l - \mu^o_j - \mu^o_k}{R T} )
* \f]
*
* \f$ K_a^{o,1} \f$ is the dimensionless form of the equilibrium constant, associated with
* the pressure dependent standard states \f$ \mu^o_l(T,P) \f$ and their associated activities,
* \f$ a_l \f$, repeated here:
*
* \f[
* \mu_l(T,P) = \mu^o_l(T, P) + R T \log(a_l)
* \f]
*
* The concentration equilibrium constant, \f$ K_c \f$, may be obtained by changing over
* to activity concentrations. When this is done:
*
* \f[
* \frac{C^a_j C^a_k}{ C^a_l} = C^o K_a^{o,1} = K_c^1 =
* \exp(\frac{\mu^{o}_l - \mu^{o}_j - \mu^{o}_k}{R T} )
* \f]
*
*
* %Kinetics managers will calculate the concentration equilibrium constant, \f$ K_c \f$,
* using the second and third part of the above expression as a definition for the concentration
* equilibrium constant.
*
* <HR>
* <H2> Instantiation of the Class </H2>
* <HR>
*
*
* The constructor for this phase is located in the default ThermoFactory
* for %Cantera. A new %LatticePhase object may be created by the following code snippet:
*
* @code
* XML_Node *xc = get_XML_File("O_lattice_SiO2.xml");
* XML_Node * const xs = xc->findNameID("phase", "O_lattice_SiO2");
* ThermoPhase *tp = newPhase(*xs);
* LatticePhase *o_lattice = dynamic_cast <LatticPhase *>(tp);
* @endcode
*
* or by the following constructor:
*
* @code
* XML_Node *xc = get_XML_File("O_lattice_SiO2.xml");
* XML_Node * const xs = xc->findNameID("phase", "O_lattice_SiO2");
* LatticePhase *o_lattice = new LatticePhase(*xs);
* @endcode
*
* The XML file used in this example is listed in the next section
*
* <HR>
* <H2> XML Example </H2>
* <HR>
*
* An example of an XML Element named phase setting up a LatticePhase object named "O_lattice_SiO2"
* is given below.
*
* @verbatim
<!-- phase O_lattice_SiO2 -->
<phase dim="3" id="O_lattice_SiO2">
<elementArray datasrc="elements.xml"> Si H He </elementArray>
<speciesArray datasrc="#species_data">
O_O Vac_O
</speciesArray>
<reactionArray datasrc="#reaction_data"/>
<thermo model="Lattice">
<site_density> 73.159 </site_density>
<vacancy_species> Vac_O </vacancy_species>
</thermo>
<kinetics model="BulkKinetics"/>
<transport model="None"/>
</phase>
@endverbatim
*
* The model attribute "Lattice" of the thermo XML element identifies the phase as
* being of the type handled by the LatticePhase object.
*
* @ingroup thermoprops
*
*/
class LatticePhase : public ThermoPhase {
public:
//! Base Empty constructor
LatticePhase();
//! Copy Constructor
/*!
* @param right Object to be copied
*/
class LatticePhase : public ThermoPhase {
LatticePhase(const LatticePhase &right);
public:
//! Assignment operator
/*!
* @param right Object to be copied
*/
LatticePhase& operator=(const LatticePhase& right);
//! Base Empty constructor
LatticePhase();
//! Destructor
virtual ~LatticePhase();
//! Copy Constructor
/*!
* @param right Object to be copied
*/
LatticePhase(const LatticePhase &right);
//! Assignment operator
/*!
* @param right Object to be copied
*/
LatticePhase& operator=(const LatticePhase& right);
//! Destructor
virtual ~LatticePhase();
//! Duplication function
/*!
* This virtual function is used to create a duplicate of the
* current phase. It's used to duplicate the phase when given
* a ThermoPhase pointer to the phase.
*
* @return It returns a ThermoPhase pointer.
*/
ThermoPhase *duplMyselfAsThermoPhase() const;
virtual int eosType() const { return cLattice; }
virtual doublereal enthalpy_mole() const;
virtual doublereal intEnergy_mole() const;
virtual doublereal entropy_mole() const;
virtual doublereal gibbs_mole() const;
virtual doublereal cp_mole() const;
virtual doublereal cv_mole() const {
return cp_mole();
}
virtual doublereal pressure() const {
return m_press;
}
virtual void setPressure(doublereal p) {
m_press = p;
setMolarDensity(m_molar_density);
}
virtual void getActivityConcentrations(doublereal* c) const;
virtual void getActivityCoefficients(doublereal* ac) const;
virtual void getChemPotentials(doublereal* mu) const;
virtual void getStandardChemPotentials(doublereal* mu0) const;
virtual doublereal standardConcentration(int k=0) const;
virtual doublereal logStandardConc(int k=0) const;
virtual void getPureGibbs(doublereal* gpure) const {
const array_fp& gibbsrt = gibbs_RT();
scale(gibbsrt.begin(), gibbsrt.end(), gpure, _RT());
}
void getEnthalpy_RT(doublereal* hrt) const {
const array_fp& _h = enthalpy_RT();
std::copy(_h.begin(), _h.end(), hrt);
}
void getEntropy_R(doublereal* sr) const {
const array_fp& _s = entropy_R();
std::copy(_s.begin(), _s.end(), sr);
}
virtual void getGibbs_RT(doublereal* grt) const {
const array_fp& gibbsrt = gibbs_RT();
std::copy(gibbsrt.begin(), gibbsrt.end(), grt);
}
void getCp_R(doublereal* cpr) const {
const array_fp& _cpr = cp_R();
std::copy(_cpr.begin(), _cpr.end(), cpr);
}
//! Duplication function
/*!
* This virtual function is used to create a duplicate of the
* current phase. It's used to duplicate the phase when given
* a ThermoPhase pointer to the phase.
*
* @return It returns a ThermoPhase pointer.
*/
ThermoPhase *duplMyselfAsThermoPhase() const;
// new methods defined here
//! Equation of state flag. Returns the value cLattice
virtual int eosType() const { return cLattice; }
const array_fp& enthalpy_RT() const {
_updateThermo();
return m_h0_RT;
}
/**
* @name Molar Thermodynamic Properties of the Solution ------------------------
* @{
*/
const array_fp& gibbs_RT() const {
_updateThermo();
return m_g0_RT;
}
//! Return the Molar Enthalpy. Units: J/kmol.
/*!
* For an ideal solution,
*
* \f[
* \hat h(T,P) = \sum_k X_k \hat h^0_k(T,P),
* \f]
*
* The standard-state pure-species Enthalpies
* \f$ \hat h^0_k(T,P) \f$ are computed first by the species reference
* state thermodynamic property manager and then a small pressure dependent term is
* added in.
*
* \see SpeciesThermo
*/
virtual doublereal enthalpy_mole() const;
const array_fp& entropy_R() const {
_updateThermo();
return m_s0_R;
}
//! Molar internal energy of the solution. Units: J/kmol.
/*!
* For an ideal, constant partial molar volume solution mixture with
* pure species phases which exhibit zero volume expansivity and
* zero isothermal compressibility:
*
* \f[
* \hat u(T,X) = \hat h(T,P,X) - p \hat V
* = \sum_k X_k \hat h^0_k(T) - P_{ref} (\sum_k{X_k \hat V^0_k})
* \f]
*
* and is a function only of temperature.
* The reference-state pure-species enthalpies
* \f$ \hat h^0_k(T) \f$ are computed by the species thermodynamic
* property manager.
* @see SpeciesThermo
*/
virtual doublereal intEnergy_mole() const;
const array_fp& cp_R() const {
_updateThermo();
return m_cp0_R;
}
//! 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[
* \hat s(T, P, X_k) = \sum_k X_k \hat s^0_k(T) - \hat R \sum_k X_k log(X_k)
* \f]
* The reference-state pure-species entropies
* \f$ \hat s^0_k(T,p_{ref}) \f$ are computed by the species thermodynamic
* property manager. The pure species entropies are independent of
* pressure since the volume expansivities are equal to zero.
*
* Units: J/kmol/K.
*
* @see SpeciesThermo
*/
virtual doublereal entropy_mole() const;
virtual void initThermo();
//! Molar gibbs free energy of the solution. Units: J/kmol.
/*!
* For an ideal, constant partial molar volume solution mixture with
* pure species phases which exhibit zero volume expansivity:
* \f[
* \hat g(T, P) = \sum_k X_k \hat g^0_k(T,P) + \hat R T \sum_k X_k log(X_k)
* \f]
* The reference-state pure-species gibbs free energies
* \f$ \hat g^0_k(T) \f$ are computed by the species thermodynamic
* property manager, while the standard state gibbs free energies
* \f$ \hat g^0_k(T,P) \f$ are computed by the member function, gibbs_RT().
*
* @see SpeciesThermo
*/
virtual doublereal gibbs_mole() const;
// set the site density of sublattice n
virtual void setParameters(int n, doublereal* c) {}
//! Molar heat capacity at constant pressure 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[
* \hat c_p(T,P) = \sum_k X_k \hat c^0_{p,k}(T) .
* \f]
* The heat capacity is independent of pressure.
* The reference-state pure-species heat capacities
* \f$ \hat c^0_{p,k}(T) \f$ are computed by the species thermodynamic
* property manager.
*
* @see SpeciesThermo
*/
virtual doublereal cp_mole() const;
//! Molar heat capacity at constant volume 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[
* \hat c_v(T,P) = \hat c_p(T,P)
* \f]
*
* The two heat capacities are equal.
*/
virtual doublereal cv_mole() const;
virtual void getParameters(int &n, doublereal * const c) const {
double d = molarDensity();
c[0] = d;
n = 1;
}
//@}
/// @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
* an independent variable. Instead, the pressure is used as the
* independent variable. Functions which try to set the thermodynamic
* state by calling setDensity() may cause an exception to be
* thrown.
*/
//@{
virtual void setParametersFromXML(const XML_Node& eosdata);
//! Pressure. Units: Pa.
/*!
* For this incompressible system, we return the internally storred
* independent value of the pressure.
*/
virtual doublereal pressure() const {
return m_press;
}
//! Set the internally storred pressure (Pa) at constant
//! temperature and composition
/*!
* This method sets the pressure within the object.
* The mass density is not a function of pressure.
*
* @param p Input Pressure (Pa)
*/
virtual void setPressure(doublereal p);
//@}
/// @name Activities, Standard States, and Activity Concentrations
/**
*
* The activity \f$a_k\f$ of a species in solution is
* related to the chemical potential by \f[ \mu_k = \mu_k^0(T)
* + \hat R T \log a_k. \f] The quantity \f$\mu_k^0(T,P)\f$ is
* the chemical potential at unit activity, which depends only
* on temperature and the pressure.
* Activity is assumed to be molality-based here.
*/
//@{
protected:
/**
* 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.
*/
virtual void getActivityConcentrations(doublereal* c) const;
int m_mm;
doublereal m_tmin;
doublereal m_tmax;
doublereal m_p0;
mutable doublereal m_tlast;
mutable array_fp m_h0_RT;
mutable array_fp m_cp0_R;
mutable array_fp m_g0_RT;
mutable array_fp m_s0_R;
doublereal m_press;
std::string m_vacancy;
doublereal m_molar_density;
//! Return the standard concentration for the kth species
/*!
* The standard concentration \f$ C^0_k \f$ used to normalize
* the activity (i.e., generalized) concentration for use
*
* 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 mass-action reaction rates
* based on the molality of species proportional to the
* molality of the species.
*
* @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
* m<SUP>3</SUP> kmol<SUP>-1</SUP>.
*
* @param k Species index
*/
virtual doublereal standardConcentration(int k=0) const;
private:
//! Returns the natural logarithm of the standard
//! concentration of the kth species
/*!
* @param k Species index
*/
virtual doublereal logStandardConc(int k=0) const;
void _updateThermo() const;
};
//! Get the array of non-dimensional activity coefficients at
//! the current solution temperature, pressure, and solution concentration.
/*!
* For this phase, the activity coefficients are all equal to one.
*
* @param ac Output vector of activity coefficients. Length: m_kk.
*/
virtual void getActivityCoefficients(doublereal* ac) const;
//@}
/// @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 solid solution at the current temperature, pressure
* and mole fraction of the solid solution.
*
* @param mu Output vector of species chemical
* potentials. Length: m_kk. Units: J/kmol
*/
virtual void getChemPotentials(doublereal* mu) const;
//! Get the array of chemical potentials at unit activity for the
//! species standard states at the current <I>T</I> and <I>P</I> of the solution.
/*!
* These are the standard state chemical potentials \f$ \mu^0_k(T,P)
* \f$. The values are evaluated at the current
* temperature and pressure of the solution
*
* @param mu Output vector of chemical potentials.
* Length: m_kk.
*/
virtual void getStandardChemPotentials(doublereal* mu) const;
//! Get the Gibbs functions for the standard
//! state of the species at the current <I>T</I> and <I>P</I> of the solution
/*!
* Units are Joules/kmol
* @param gpure Output vector of standard state gibbs free energies
* Length: m_kk.
*/
virtual void getPureGibbs(doublereal* gpure) const;
//! Return an array of partial molar volumes for the
//! species in the mixture. Units: m^3/kmol.
/*!
* @param vbar Output vector of speciar partial molar volumes.
* 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
//@{
//! Get the nondimensional Enthalpy functions for the species standard states
//! at their standard states at the current <I>T</I> and <I>P</I> of the solution.
/*!
* A small pressure dependent term is added onto the reference state enthalpy
* to get the pressure dependence of this term.
*
* \f[
* h^o_k(T,P) = h^{ref}_k(T) + \left( \frac{P - P_{ref}}{C_o} \right)
* \f]
*
* The reference state thermodynamics is
* obtained by a pointer to a populated species thermodynamic property
* manager class (see ThermoPhase::m_spthermo). How to relate pressure
* changes to the reference state thermodynamics is resolved at this level.
*
* @param hrt Output vector of nondimensional standard state enthalpies.
* Length: m_kk.
*/
virtual void getEnthalpy_RT(doublereal* hrt) const;
//! Get the array of nondimensional Entropy functions for the
//! species standard states at the current <I>T</I> and <I>P</I> of the solution.
/*!
* The entropy of the standard state is defined as independent of
* pressure here.
*
* \f[
* s^o_k(T,P) = s^{ref}_k(T)
* \f]
*
* The reference state thermodynamics is
* obtained by a pointer to a populated species thermodynamic property
* manager class (see ThermoPhase::m_spthermo). How to relate pressure
* changes to the reference state thermodynamics is resolved at this level.
*
* @param sr Output vector of nondimensional standard state entropies.
* Length: m_kk.
*/
virtual void getEntropy_R(doublereal* sr) const;
//! Get the nondimensional Gibbs functions for the species
//! standard states at the current <I>T</I> and <I>P</I> of the solution.
/*!
* The standard gibbs free energies are obtained from the enthalpy
* and entropy formulation.
*
* \f[
* g^o_k(T,P) = h^{o}_k(T,P) - T s^{o}_k(T,P)
* \f]
*
* @param grt Output vector of nondimensional standard state gibbs free energies
* Length: m_kk.
*/
virtual void getGibbs_RT(doublereal* grt) const;
//! Get the nondimensional Heat Capacities at constant
//! pressure for the species standard states
//! at the current <I>T</I> and <I>P</I> of the solution
/*!
* The heat capacity of the standard state is independent of pressure
*
* \f[
* Cp^o_k(T,P) = Cp^{ref}_k(T)
* \f]
*
* The reference state thermodynamics is
* obtained by a pointer to a populated species thermodynamic property
* manager class (see ThermoPhase::m_spthermo). How to relate pressure
* changes to the reference state thermodynamics is resolved at this level.
*
* @param cpr Output vector of nondimensional standard state heat capacities
* Length: m_kk.
*/
virtual void getCp_R(doublereal* cpr) const;
//! Get the molar volumes of the species standard states at the current
//! <I>T</I> and <I>P</I> of the solution.
/*!
* units = m^3 / kmol
*
* @param vol Output vector containing the standard state volumes.
* Length: m_kk.
*/
virtual void getStandardVolumes(doublereal *vol) const;
//@}
/// @name 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 phase.
/*!
* @return Output vector of nondimensional reference state
* Enthalpies of the species.
* Length: m_kk
*/
const array_fp& enthalpy_RT_ref() const {
_updateThermo();
return m_h0_RT;
}
//! Returns a reference to the dimensionless reference state Gibbs free energy vector.
/*!
* This function is part of the layer that checks/recalculates the reference
* state thermo functions.
*/
const array_fp& gibbs_RT_ref() const {
_updateThermo();
return m_g0_RT;
}
//! Returns a reference to the dimensionless reference state Entropy vector.
/*!
* This function is part of the layer that checks/recalculates the reference
* state thermo functions.
*/
const array_fp& entropy_R_ref() const {
_updateThermo();
return m_s0_R;
}
//! Returns a reference to the dimensionless reference state Heat Capacity vector.
/*!
* This function is part of the layer that checks/recalculates the reference
* state thermo functions.
*/
const array_fp& cp_R_ref() const {
_updateThermo();
return m_cp0_R;
}
//@}
/// @name Utilities for Initialization of the Object
//@{
//! Initialize the ThermoPhase object after all species have been set up
/*!
* @internal Initialize.
*
* This method performs any initialization required after all
* species have been added. For example, it is used to
* resize internal work arrays that must have an entry for
* each species.
* This method is called from ThermoPhase::initThermoXML(),
* which is called from importPhase(),
* just prior to returning from the function, importPhase().
*
* @see importCTML.cpp
*/
virtual void initThermo();
//! Set the equation of state parameters from the argument list
/*!
* @internal
* Set equation of state parameters.
*
* @param n number of parameters. Must be one
* @param c array of \a n coefficients
* c[0] = The bulk lattice density (kmol m-3)
*/
virtual void setParameters(int n, doublereal* c);
//! Get the equation of state parameters in a vector
/*!
* @internal
*
* @param n number of parameters
* @param c array of \a n coefficients
*
* For this phase:
* - n = 1
* - c[0] = molar density of phase [ kmol/m^3 ]
*/
virtual void getParameters(int &n, doublereal * const c) const;
//! Set equation of state parameter values from XML entries.
/*!
* This method is called by function importPhase() in
* file importCTML.cpp when processing a phase definition in
* an input file. It should be overloaded in subclasses to set
* any parameters that are specific to that particular phase
* model. Note, this method is called before the phase is
* initialzed with elements and/or species.
*
* For this phase, the molar density of the phase is specified in this block,
* and is a required parameter.
*
* @param eosdata An XML_Node object corresponding to
* the "thermo" entry for this phase in the input file.
*
* eosdata points to the thermo block, and looks like this:
*
* @verbatim
<phase id="O_lattice_SiO2" >
<thermo model="Lattice">
<site_density units="kmol/m^3"> 73.159 </site_density>
<vacancy_species> "O_vacancy" </vacancy_species>
</thermo>
</phase> @endverbatim
*
*/
virtual void setParametersFromXML(const XML_Node& eosdata);
//@}
protected:
//! Number of elements
int m_mm;
//! Minimum temperature for valid species standard state thermo props
/*!
* This is the minimum temperature at which all species have valid standard
* state thermo props defined.
*/
doublereal m_tmin;
//! Maximum temperature for valid species standard state thermo props
/*!
* This is the maximum temperature at which all species have valid standard
* state thermo props defined.
*/
doublereal m_tmax;
//! Reference state pressure
doublereal m_p0;
//! Current value of the temperature (Kelvin)
mutable doublereal m_tlast;
//! Reference state enthalpies / RT
mutable array_fp m_h0_RT;
//! Temporary storage for the reference state heat capacities
mutable array_fp m_cp0_R;
//! Temporary storage for the reference state gibbs energies
mutable array_fp m_g0_RT;
//! Temporary storage for the reference state entropies
mutable array_fp m_s0_R;
//! Current value of the pressure (Pa)
doublereal m_press;
//! String name for the species which represents a vacency
//! in the lattice
/*!
* This string is currently unused
*/
std::string m_vacancy;
//! Molar density of the lattice solid
/*!
* units are kmol m-3
*/
doublereal m_molar_density;
private:
//! Update the species reference state thermodynamic functions
/*!
* The polynomials for the standard state functions are only
* reevalulated if the temperature has changed.
*/
void _updateThermo() const;
};
}
#endif

20
Cantera/src/thermo/LatticeSolidPhase.cpp
View file

@ -79,17 +79,17 @@ namespace Cantera {
return (ThermoPhase *) igp;
}
doublereal LatticeSolidPhase::
enthalpy_mole() const {
_updateThermo();
doublereal ndens, sum = 0.0;
int n;
for (n = 0; n < m_nlattice; n++) {
ndens = m_lattice[n]->molarDensity();
sum += ndens * m_lattice[n]->enthalpy_mole();
}
return sum/molarDensity();
doublereal LatticeSolidPhase::
enthalpy_mole() const {
_updateThermo();
doublereal ndens, sum = 0.0;
int n;
for (n = 0; n < m_nlattice; n++) {
ndens = m_lattice[n]->molarDensity();
sum += ndens * m_lattice[n]->enthalpy_mole();
}
return sum/molarDensity();
}
doublereal LatticeSolidPhase::intEnergy_mole() const {
_updateThermo();

156
Cantera/src/thermo/LatticeSolidPhase.h
View file

@ -1,6 +1,10 @@
/**
*
* @file LatticeSolidPhase.h
* Header for a simple thermodynamics model of a bulk solid phase
* derived from ThermoPhase,
* assuming an ideal solution model based on a lattice of solid atoms
* (see \ref thermoprops and class \link Cantera::LatticeSolidPhase LatticeSolidPhase\endlink).
*/
/* $Author$
@ -15,6 +19,7 @@
#define CT_LATTICESOLID_H
#include "config.h"
#ifdef WITH_LATTICE_SOLID
#include "ct_defs.h"
@ -28,95 +33,118 @@
namespace Cantera {
class LatticePhase;
class LatticePhase;
class LatticeSolidPhase : public ThermoPhase {
//! Additive combination of lattice phases
/*!
*
*/
class LatticeSolidPhase : public ThermoPhase {
public:
public:
//! Base empty constructor
LatticeSolidPhase();
//! Base empty constructor
LatticeSolidPhase();
//! Copy Constructor
/*!
* @param right Object to be copied
*/
LatticeSolidPhase(const LatticeSolidPhase &right);
//! Copy Constructor
/*!
* @param right Object to be copied
*/
LatticeSolidPhase(const LatticeSolidPhase &right);
//! Assignment operator
/*!
* @param right Object to be copied
*/
LatticeSolidPhase& operator=(const LatticeSolidPhase& right);
//! Assignment operator
/*!
* @param right Object to be copied
*/
LatticeSolidPhase& operator=(const LatticeSolidPhase& right);
//! Destructor
virtual ~LatticeSolidPhase();
//! Destructor
virtual ~LatticeSolidPhase();
//! Duplication function
/*!
* This virtual function is used to create a duplicate of the
* current phase. It's used to duplicate the phase when given
* a ThermoPhase pointer to the phase.
*
* @return It returns a ThermoPhase pointer.
*/
ThermoPhase *duplMyselfAsThermoPhase() const;
//! Duplication function
/*!
* This virtual function is used to create a duplicate of the
* current phase. It's used to duplicate the phase when given
* a ThermoPhase pointer to the phase.
*
* @return It returns a ThermoPhase pointer.
*/
ThermoPhase *duplMyselfAsThermoPhase() const;
virtual int eosType() const { return cLatticeSolid; }
//! Equation of state type flag.
/*!
* Redefine this to return cLatticeSolid, listed in mix_defs.h.
*/
virtual int eosType() const { return cLatticeSolid; }
virtual doublereal enthalpy_mole() const;
//! Return the Molar Enthalpy. Units: J/kmol.
/*!
* For an ideal solution,
* \f[
* \hat h(T,P) = \sum_k X_k \hat h^0_k(T),
* \f]
* and is a function only of temperature.
* The standard-state pure-species Enthalpies
* \f$ \hat h^0_k(T) \f$ are computed by the species thermodynamic
* property manager.
*
* \see SpeciesThermo
*/
virtual doublereal enthalpy_mole() const;
virtual doublereal intEnergy_mole() const;
virtual doublereal intEnergy_mole() const;
virtual doublereal entropy_mole() const;
virtual doublereal entropy_mole() const;
virtual doublereal gibbs_mole() const;
virtual doublereal gibbs_mole() const;
virtual doublereal cp_mole() const;
virtual doublereal cp_mole() const;
virtual doublereal cv_mole() const {
return cp_mole();
}
virtual doublereal cv_mole() const {
return cp_mole();
}
virtual doublereal pressure() const {
return m_press;
}
virtual doublereal pressure() const {
return m_press;
}
virtual void setPressure(doublereal p) {
m_press = p;
setMolarDensity(m_molar_density);
}
virtual void setPressure(doublereal p) {
m_press = p;
setMolarDensity(m_molar_density);
}
virtual void getActivityConcentrations(doublereal* c) const;
virtual void getActivityConcentrations(doublereal* c) const;
virtual void getActivityCoefficients(doublereal* ac) const;
virtual void getActivityCoefficients(doublereal* ac) const;
virtual void getChemPotentials(doublereal* mu) const;
virtual void getStandardChemPotentials(doublereal* mu0) const;
virtual doublereal standardConcentration(int k=0) const;
virtual doublereal logStandardConc(int k=0) const;
virtual void getChemPotentials(doublereal* mu) const;
virtual void getStandardChemPotentials(doublereal* mu0) const;
virtual doublereal standardConcentration(int k=0) const;
virtual doublereal logStandardConc(int k=0) const;
virtual void initThermo();
virtual void initThermo();
virtual void setParametersFromXML(const XML_Node& eosdata);
virtual void setParametersFromXML(const XML_Node& eosdata);
void setLatticeMoleFractions(int n, std::string x);
void setLatticeMoleFractions(int n, std::string x);
protected:
protected:
int m_mm;
int m_kk;
mutable doublereal m_tlast;
doublereal m_press;
doublereal m_molar_density;
int m_nlattice;
std::vector<LatticePhase*> m_lattice;
mutable vector_fp m_x;
int m_mm;
int m_kk;
mutable doublereal m_tlast;
doublereal m_press;
doublereal m_molar_density;
private:
void _updateThermo() const;
};
int m_nlattice;
std::vector<LatticePhase*> m_lattice;
mutable vector_fp m_x;
private:
void _updateThermo() const;
};
}
#endif

2
Cantera/src/thermo/SurfPhase.h
View file

@ -1,6 +1,6 @@
/**
* @file SurfPhase.h
* Header for a simple thermoydnamics model of a surface phase
* Header for a simple thermodynamics model of a surface phase
* derived from ThermoPhase,
* assuming an ideal solution model
* (see \ref thermoprops and class \link Cantera::SurfPhase SurfPhase\endlink).

15
Cantera/src/thermo/ThermoPhase.h
View file

@ -1372,15 +1372,14 @@ namespace Cantera {
err("getStandardVolumes_ref");
}
///////////////////////////////////////////////////////
//
// The methods below are not virtual, and should not
// be overloaded.
//
//////////////////////////////////////////////////////
//@}
/**
* @}
* @name Specific Properties
* @{
*/
@ -1702,12 +1701,12 @@ namespace Cantera {
}
//@}
//! @name Saturation properties.
/*!
/** @name Saturation Properties.
*
* These methods are only implemented by subclasses that
* implement full liquid-vapor equations of state. They may be
* moved out of ThermoPhase at a later date.
* moved out of %ThermoPhase at a later date.
*/
//@{