425 lines
12 KiB
C++
425 lines
12 KiB
C++
/**
|
|
*
|
|
* @file StoichSubstance.h
|
|
*
|
|
* This file contains the class declarations for the StoichSubstance
|
|
* ThermoPhase class.
|
|
*/
|
|
|
|
/* $Author$
|
|
* $Date$
|
|
* $Revision$
|
|
*
|
|
* Copyright 2001 California Institute of Technology
|
|
*
|
|
*/
|
|
|
|
|
|
#ifndef CT_STOICHSUBSTANCE_H
|
|
#define CT_STOICHSUBSTANCE_H
|
|
|
|
#include "mix_defs.h"
|
|
#include "ThermoPhase.h"
|
|
#include "SpeciesThermo.h"
|
|
|
|
namespace Cantera {
|
|
|
|
/**
|
|
* @ingroup thermoprops
|
|
*
|
|
* Class StoichSubstance represents a stoichiometric (fixed composition)
|
|
* incompressible substance.
|
|
* \nosubgrouping
|
|
*
|
|
*/
|
|
class StoichSubstance : public ThermoPhase {
|
|
|
|
public:
|
|
|
|
StoichSubstance():
|
|
m_kk(0),
|
|
m_tmin(0.0),
|
|
m_tmax(0.0),
|
|
m_press(OneAtm),
|
|
m_p0(OneAtm),
|
|
m_tlast(-1.0) {}
|
|
|
|
virtual ~StoichSubstance() {}
|
|
|
|
/**
|
|
*
|
|
* @name Utilities
|
|
* @{
|
|
*/
|
|
|
|
/**
|
|
* Equation of state flag. Returns the value cStoichSubstance,
|
|
* defined in mix_defs.h.
|
|
*/
|
|
virtual int eosType() const { return cStoichSubstance; }
|
|
|
|
|
|
/**
|
|
* @}
|
|
* @name Molar Thermodynamic Properties of the Solution ---------
|
|
* @{
|
|
*/
|
|
|
|
/**
|
|
* Molar enthalpy. Units: J/kmol. For an incompressible,
|
|
* stoichiometric substance, the internal energy is
|
|
* independent of pressure, and therefore the molar enthalpy
|
|
* is \f[ \hat h(T, P) = \hat u(T) + P \hat v \f], where the
|
|
* molar specific volume is constant.
|
|
*/
|
|
virtual doublereal enthalpy_mole() const {
|
|
double hh = intEnergy_mole() + m_press / molarDensity();
|
|
return hh;
|
|
}
|
|
|
|
/**
|
|
* Molar internal energy. J/kmol. For an incompressible,
|
|
* stoichiometric substance, the molar internal energy is
|
|
* independent of pressure. Since the thermodynamic properties
|
|
* are specified by giving the standard-state enthalpy, the
|
|
* term \f$ P_0 \hat v\f$ is subtracted from the specified molar
|
|
* enthalpy to compute the molar internal energy.
|
|
*/
|
|
virtual doublereal intEnergy_mole() const {
|
|
_updateThermo();
|
|
return GasConstant * temperature() * m_h0_RT[0]
|
|
- m_p0 / molarDensity();
|
|
}
|
|
|
|
/**
|
|
* Molar entropy. Units: J/kmol/K. For an incompressible,
|
|
* stoichiometric substance, the molar entropy depends only on
|
|
* the temperature.
|
|
*/
|
|
virtual doublereal entropy_mole() const {
|
|
_updateThermo();
|
|
return GasConstant * m_s0_R[0];
|
|
}
|
|
|
|
|
|
/**
|
|
* Molar gibbs Function. Units: J/kmol. This is determined
|
|
* from the molar enthalpy and entropy functions.
|
|
*/
|
|
virtual doublereal gibbs_mole() const {
|
|
return enthalpy_mole() - temperature() * entropy_mole();
|
|
}
|
|
|
|
|
|
/**
|
|
* Molar heat capacity at constant pressure. Units: J/kmol/K.
|
|
* For an incompressible substance, \f$ \hat c_p = \hat c_v\f$.
|
|
*/
|
|
virtual doublereal cp_mole() const {
|
|
_updateThermo();
|
|
return GasConstant * m_cp0_R[0];
|
|
}
|
|
|
|
/**
|
|
* Molar heat capacity at constant volume. Units: J/kmol/K.
|
|
* For an incompressible substance, \f$ \hat c_p = \hat c_v\f$.
|
|
*/
|
|
virtual doublereal cv_mole() const {
|
|
return cp_mole();
|
|
}
|
|
|
|
//@}
|
|
|
|
|
|
/**
|
|
* @name Mechanical Equation of State
|
|
* @{
|
|
*/
|
|
|
|
/**
|
|
* Pressure. Units: Pa.
|
|
* For an incompressible substance, the density is independent
|
|
* of pressure. This method simply returns the stored
|
|
* pressure value.
|
|
*/
|
|
virtual doublereal pressure() const {
|
|
return m_press;
|
|
}
|
|
|
|
/**
|
|
* Set the pressure at constant temperature. Units: Pa.
|
|
* For an incompressible substance, the density is
|
|
* independent of pressure. Therefore, this method only
|
|
* stores the specified pressure value. It does not
|
|
* modify the density.
|
|
*/
|
|
virtual void setPressure(doublereal p) {
|
|
m_press = p;
|
|
}
|
|
|
|
//@}
|
|
|
|
/**
|
|
* @name Chemical Potentials and Activities
|
|
*@{
|
|
*/
|
|
|
|
/**
|
|
* This method returns the array of generalized
|
|
* concentrations. For a stoichiometric substance, there is
|
|
* only one species, and the generalized concentration is 1.0.
|
|
*/
|
|
virtual void getActivityConcentrations(doublereal* c) const {
|
|
c[0] = 1.0;
|
|
}
|
|
|
|
/**
|
|
* The standard concentration. This is defined as the concentration
|
|
* by which the generalized concentration is normalized to produce
|
|
* the activity.
|
|
*/
|
|
virtual doublereal standardConcentration(int k=0) const {
|
|
return 1.0;
|
|
}
|
|
|
|
/**
|
|
* Returns the natural logarithm of the standard
|
|
* concentration of the kth species
|
|
*/
|
|
virtual doublereal logStandardConc(int k=0) const {
|
|
return 0.0;
|
|
}
|
|
|
|
/**
|
|
* Get the array of chemical potentials at unit activity
|
|
* \f$ \mu^0_k \f$.
|
|
*
|
|
* For a stoichiometric substance, there is no activity term in
|
|
* the chemical potential expression, and therefore the
|
|
* standard chemical potential and the chemical potential
|
|
* are both equal to the molar Gibbs function.
|
|
*/
|
|
virtual void getStandardChemPotentials(doublereal* mu0) const {
|
|
mu0[0] = gibbs_mole();
|
|
}
|
|
|
|
/**
|
|
* Returns the units of the standard and generalized
|
|
* concentrations Note they have the same units, as their
|
|
* ratio is defined to be equal to the activity of the kth
|
|
* species in the solution, which is unitless.
|
|
*
|
|
* This routine is used in print out applications where the
|
|
* units are needed. Usually, MKS units are assumed throughout
|
|
* the program and in the XML input files.
|
|
*
|
|
* uA[0] = kmol units - default = 0
|
|
* uA[1] = m units - default = 0
|
|
* uA[2] = kg units - default = 0;
|
|
* uA[3] = Pa(pressure) units - default = 0;
|
|
* uA[4] = Temperature units - default = 0;
|
|
* uA[5] = time units - default = 0
|
|
*/
|
|
virtual void getUnitsStandardConc(double *uA, int k = 0,
|
|
int sizeUA = 6);
|
|
|
|
|
|
//@}
|
|
/// @name Partial Molar Properties of the Solution ----------------------------------
|
|
//@{
|
|
|
|
|
|
/**
|
|
* Get the array of non-dimensional chemical potentials
|
|
* \f$ \mu_k / \hat R T \f$.
|
|
*/
|
|
virtual void getChemPotentials_RT(doublereal* mu) const {
|
|
mu[0] = gibbs_mole() / (GasConstant * temperature());
|
|
}
|
|
|
|
/**
|
|
* For a stoichiometric substance, there is only one species.
|
|
* This method returns the molar gibbs function in the
|
|
* first element of array \c mu.
|
|
*/
|
|
virtual void getChemPotentials(doublereal* mu) const {
|
|
mu[0] = gibbs_mole();
|
|
}
|
|
|
|
/**
|
|
* Get the species electrochemical potentials. Units: J/kmol.
|
|
* This method adds a term \f$ Fz_k \phi_k \f$ to the
|
|
* to each chemical potential.
|
|
*/
|
|
void getElectrochemPotentials(doublereal* mu) const {
|
|
getChemPotentials(mu);
|
|
}
|
|
|
|
/**
|
|
* Returns an array of partial molar enthalpies for the species
|
|
* in the mixture.
|
|
* Units (J/kmol)
|
|
*/
|
|
virtual void getPartialMolarEnthalpies(doublereal* hbar) const {
|
|
hbar[0] = enthalpy_mole();
|
|
}
|
|
|
|
/**
|
|
* Returns an array of partial molar entropies of the species in the
|
|
* solution. Units: J/kmol/K.
|
|
*/
|
|
virtual void getPartialMolarEntropies(doublereal* sbar) const {
|
|
sbar[0] = entropy_mole();
|
|
}
|
|
|
|
/**
|
|
* returns an array of partial molar volumes of the species
|
|
* in the solution. Units: m^3 kmol-1.
|
|
*/
|
|
virtual void getPartialMolarVolumes(doublereal* vbar) const {
|
|
vbar[0] = 1.0 / molarDensity();
|
|
}
|
|
|
|
|
|
//@}
|
|
/// @name Properties of the Standard State of the Species in the Solution -------------------------------------
|
|
//@{
|
|
/**
|
|
* Get the nondimensional Enthalpy functions for the species
|
|
* at their standard states at the current
|
|
* <I>T</I> and <I>P</I> of the solution.
|
|
*/
|
|
virtual void getEnthalpy_RT(doublereal* hrt) const {
|
|
hrt[0] = enthalpy_mole() / (GasConstant * temperature());
|
|
}
|
|
|
|
|
|
/**
|
|
* Get the array of nondimensional Enthalpy functions for the
|
|
* standard state species
|
|
* at the current <I>T</I> and <I>P</I> of the solution.
|
|
*/
|
|
virtual void getEntropy_R(doublereal* sr) const {
|
|
sr[0] = entropy_mole() / GasConstant;
|
|
}
|
|
|
|
/**
|
|
* Get the nondimensional Gibbs functions for the species
|
|
* at their standard states of solution at the current T and P
|
|
* of the solution.
|
|
*/
|
|
virtual void getGibbs_RT(doublereal* grt) const {
|
|
grt[0] = gibbs_mole() / (GasConstant * temperature());
|
|
}
|
|
|
|
/**
|
|
* Get the nondimensional Heat Capacities at constant
|
|
* pressure for the standard state of the species
|
|
* at the current T and P.
|
|
*/
|
|
virtual void getCp_R(doublereal* cpr) const {
|
|
cpr[0] = cp_mole() / GasConstant;
|
|
}
|
|
|
|
/**
|
|
* Get the standard volumes for the standard state of the species
|
|
* at the current T and P
|
|
*/
|
|
virtual void getStandardVolumes(doublereal*vol) const {
|
|
vol[0] = 1.0 / molarDensity();
|
|
}
|
|
|
|
//@}
|
|
/// @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 species.
|
|
*
|
|
* This function fills in its one entry in hrt[] by calling
|
|
* the underlying species thermo function for the
|
|
* dimensionless enthalpy.
|
|
*/
|
|
virtual void getEnthalpy_RT_ref(doublereal *hrt) const {
|
|
_updateThermo();
|
|
hrt[0] = m_h0_RT[0];
|
|
}
|
|
|
|
/**
|
|
* Returns the vector of nondimensional
|
|
* enthalpies of the reference state at the current temperature
|
|
* of the solution and the reference pressure for the species.
|
|
*
|
|
* This function fills in its one entry in hrt[] by calling
|
|
* the underlying species thermo function for the
|
|
* dimensionless gibbs free energy, calculated from the
|
|
* dimensionless enthalpy and entropy.
|
|
*/
|
|
virtual void getGibbs_RT_ref(doublereal *grt) const {
|
|
_updateThermo();
|
|
grt[0] = m_h0_RT[0] - m_s0_R[0];
|
|
}
|
|
|
|
/**
|
|
* 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 function fills in its one entry in g[] by calling
|
|
* the underlying species thermo functions for the
|
|
* gibbs free energy, calculated from enthalpy and the
|
|
* entropy, and the multiplying by RT.
|
|
*/
|
|
virtual void getGibbs_ref(doublereal *g) const {
|
|
getGibbs_RT_ref(g);
|
|
g[0] *= GasConstant * temperature();
|
|
}
|
|
|
|
/**
|
|
* Returns the vector of nondimensional
|
|
* entropies of the reference state at the current temperature
|
|
* of the solution and the reference pressure for the species.
|
|
*
|
|
* This function fills in its one entry in hrt[] by calling
|
|
* the underlying species thermo function for the
|
|
* dimensionless entropy.
|
|
*/
|
|
virtual void getEntropy_R_ref(doublereal *er) const {
|
|
_updateThermo();
|
|
er[0] = m_s0_R[0];
|
|
}
|
|
|
|
|
|
virtual void initThermo();
|
|
|
|
virtual void setParameters(int n, double *c);
|
|
virtual void getParameters(int &n, double * const c);
|
|
|
|
virtual void setParametersFromXML(const XML_Node& eosdata);
|
|
|
|
protected:
|
|
|
|
int m_kk;
|
|
doublereal m_tmin, m_tmax, m_press, m_p0;
|
|
|
|
mutable doublereal m_tlast;
|
|
mutable array_fp m_h0_RT;
|
|
mutable array_fp m_cp0_R;
|
|
mutable array_fp m_s0_R;
|
|
|
|
private:
|
|
|
|
void _updateThermo() const;
|
|
};
|
|
|
|
}
|
|
|
|
#endif
|
|
|
|
|
|
|
|
|
|
|