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SurfPhase.h
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1/**
2 * @file SurfPhase.h
3 * Header for a simple thermodynamics model of a surface phase
4 * derived from ThermoPhase,
5 * assuming an ideal solution model
6 * (see @ref thermoprops and class @link Cantera::SurfPhase SurfPhase@endlink).
7 */
8
9// This file is part of Cantera. See License.txt in the top-level directory or
10// at https://cantera.org/license.txt for license and copyright information.
11
12#ifndef CT_SURFPHASE_H
13#define CT_SURFPHASE_H
14
15#include "ThermoPhase.h"
16
17 namespace Cantera
18{
19
20//! A simple thermodynamic model for a surface phase, assuming an ideal solution
21//! model.
22/*!
23 * The surface consists of a grid of equivalent sites. Surface species may be
24 * defined to occupy one or more sites. The surface species are assumed to be
25 * independent, and thus the species form an ideal solution.
26 *
27 * The density of surface sites is given by the variable @f$ n_0 @f$,
28 * which has SI units of kmol m-2.
29 *
30 * ## Specification of Species Standard State Properties
31 *
32 * It is assumed that the reference state thermodynamics may be obtained by a
33 * pointer to a populated species thermodynamic property manager class (see
34 * ThermoPhase::m_spthermo). How to relate pressure changes to the reference
35 * state thermodynamics is resolved at this level.
36 *
37 * Pressure is defined as an independent variable in this phase. However, it has
38 * no effect on any quantities, as the molar concentration is a constant.
39 *
40 * Therefore, The standard state internal energy for species *k* is equal to the
41 * enthalpy for species *k*.
42 *
43 * @f[
44 * u^o_k = h^o_k
45 * @f]
46 *
47 * Also, the standard state chemical potentials, entropy, and heat capacities
48 * are independent of pressure. The standard state Gibbs free energy is obtained
49 * from the enthalpy and entropy functions.
50 *
51 * ## Specification of Solution Thermodynamic Properties
52 *
53 * The activity of species defined in the phase is given by
54 * @f[
55 * a_k = \theta_k
56 * @f]
57 *
58 * The chemical potential for species *k* is equal to
59 * @f[
60 * \mu_k(T,P) = \mu^o_k(T) + R T \ln \theta_k
61 * @f]
62 *
63 * Pressure is defined as an independent variable in this phase. However, it has
64 * no effect on any quantities, as the molar concentration is a constant.
65 *
66 * The internal energy for species k is equal to the enthalpy for species *k*
67 * @f[
68 * u_k = h_k
69 * @f]
70 *
71 * The entropy for the phase is given by the following relation, which is
72 * independent of the pressure:
73 *
74 * @f[
75 * s_k(T,P) = s^o_k(T) - R \ln \theta_k
76 * @f]
77 *
78 * ## Application within Kinetics Managers
79 *
80 * The activity concentration,@f$ C^a_k @f$, used by the kinetics manager, is equal to
81 * the actual concentration, @f$ C^s_k @f$, and is given by the following
82 * expression.
83 * @f[
84 * C^a_k = C^s_k = \frac{\theta_k n_0}{s_k}
85 * @f]
86 *
87 * The standard concentration for species *k* is:
88 * @f[
89 * C^0_k = \frac{n_0}{s_k}
90 * @f]
91 *
92 * An example phase definition is given in the
93 * <a href="../../sphinx/html/yaml/phases.html#ideal-surface"> YAML API Reference</a>.
94 *
95 * @ingroup thermoprops
96 */
97 class SurfPhase : public ThermoPhase
98{
99 public:
100 //! Construct and initialize a SurfPhase ThermoPhase object directly from an
101 //! input file
102 /*!
103 * @param infile name of the input file. If blank, an empty phase will be created.
104 * @param id name of the phase id in the file.
105 * If this is blank, the first phase in the file is used.
106 */
107 explicit SurfPhase(const string& infile="", const string& id="");
108
109 string type() const override {
110 return "ideal-surface";
111 }
112
113 bool isCompressible() const override {
114 return false;
115 }
116
117 //! Return the Molar Enthalpy. Units: J/kmol.
118 /*!
119 * For an ideal solution,
120 * @f[
121 * \hat h(T,P) = \sum_k X_k \hat h^0_k(T),
122 * @f]
123 * and is a function only of temperature. The standard-state pure-species
124 * Enthalpies @f$ \hat h^0_k(T) @f$ are computed by the species
125 * thermodynamic property manager.
126 *
127 * \see MultiSpeciesThermo
128 */
129 double enthalpy_mole() const override;
130
131 //! Return the Molar Internal Energy. Units: J/kmol
132 /**
133 * For a surface phase, the pressure is not a relevant thermodynamic
134 * variable, and so the Enthalpy is equal to the Internal Energy.
135 */
136 double intEnergy_mole() const override;
137
138 //! Return the Molar Entropy. Units: J/kmol-K
139 /**
140 * @f[
141 * \hat s(T,P) = \sum_k X_k (\hat s^0_k(T) - R \ln \theta_k)
142 * @f]
143 */
144 double entropy_mole() const override;
145
146 double cp_mole() const override;
147 double cv_mole() const override;
148
149 void getChemPotentials(double* mu) const override;
150 void getPartialMolarEnthalpies(double* hbar) const override;
151 void getPartialMolarEntropies(double* sbar) const override;
152 void getPartialMolarCp(double* cpbar) const override;
153 void getPartialMolarVolumes(double* vbar) const override;
154 void getStandardChemPotentials(double* mu0) const override;
155
156 //! Return a vector of activity concentrations for each species
157 /*!
158 * For this phase the activity concentrations,@f$ C^a_k @f$, are defined to
159 * be equal to the actual concentrations, @f$ C^s_k @f$. Activity
160 * concentrations are
161 *
162 * @f[
163 * C^a_k = C^s_k = \frac{\theta_k n_0}{s_k}
164 * @f]
165 *
166 * where @f$ \theta_k @f$ is the surface site fraction for species k,
167 * @f$ n_0 @f$ is the surface site density for the phase, and
168 * @f$ s_k @f$ is the surface size of species k.
169 *
170 * @f$ C^a_k @f$ that are defined such that @f$ a_k = C^a_k / C^0_k, @f$
171 * where @f$ C^0_k @f$ is a standard concentration defined below and @f$ a_k
172 * @f$ are activities used in the thermodynamic functions. These activity
173 * concentrations are used by kinetics manager classes to compute the
174 * forward and reverse rates of elementary reactions. Note that they may or
175 * may not have units of concentration --- they might be partial pressures,
176 * mole fractions, or surface coverages,
177 *
178 * @param c vector of activity concentration (kmol m-2).
179 */
180 void getActivityConcentrations(double* c) const override;
181
182 //! Return the standard concentration for the kth species
183 /*!
184 * The standard concentration @f$ C^0_k @f$ used to normalize the activity
185 * (that is, generalized) concentration. For this phase, the standard
186 * concentration is species- specific
187 *
188 * @f[
189 * C^0_k = \frac{n_0}{s_k}
190 * @f]
191 *
192 * This definition implies that the activity is equal to @f$ \theta_k @f$.
193 *
194 * @param k Optional parameter indicating the species. The default
195 * is to assume this refers to species 0.
196 * @return the standard concentration in units of kmol/m^2 for surface phases or
197 * kmol/m for edge phases.
198 */
199 double standardConcentration(size_t k=0) const override;
200 double logStandardConc(size_t k=0) const override;
201
202 void initThermo() override;
203 void getParameters(AnyMap& phaseNode) const override;
204
205 bool addSpecies(shared_ptr<Species> spec) override;
206
207 //! Since interface phases have no volume, this returns 0.0.
208 double molarVolume() const override {
209 return 0.0;
210 }
211
212 //! Since interface phases have no volume, setting this to a value other than 0.0
213 //! raises an exception.
214 //! @deprecated Unused. To be removed after %Cantera 3.0
215 void setMolarDensity(const double vm) override;
216
217 //! Returns the site density
218 /*!
219 * Site density kmol m-2
220 */
221 double siteDensity() const {
222 return m_n0;
223 }
224
225 //! Returns the number of sites occupied by one molecule of species *k*.
226 double size(size_t k) const {
227 return m_speciesSize[k];
228 }
229
230 //! Set the site density of the surface phase (kmol m-2)
231 /*!
232 * @param n0 Site density of the surface phase (kmol m-2)
233 */
234 void setSiteDensity(double n0);
235
236 void getGibbs_RT(double* grt) const override;
237 void getEnthalpy_RT(double* hrt) const override;
238 void getEntropy_R(double* sr) const override;
239 void getCp_R(double* cpr) const override;
240 void getStandardVolumes(double* vol) const override;
241
242 //! Return the thermodynamic pressure (Pa).
243 double pressure() const override {
244 return m_press;
245 }
246
247 //! Set the internally stored pressure (Pa) at constant temperature and
248 //! composition
249 /*!
250 * @param p input Pressure (Pa)
251 */
252 void setPressure(double p) override {
253 m_press = p;
254 }
255
256 void getPureGibbs(double* g) const override;
257 void getGibbs_RT_ref(double* grt) const override;
258 void getEnthalpy_RT_ref(double* hrt) const override;
259 void getEntropy_R_ref(double* er) const override;
260 void getCp_R_ref(double* cprt) const override;
261
262 //! Set the surface site fractions to a specified state.
263 /*!
264 * This routine converts to concentrations in kmol/m2, using m_n0, the
265 * surface site density, and size(k), which is defined to be the number of
266 * surface sites occupied by the kth molecule. It then calls
267 * Phase::setConcentrations to set the internal concentration in the object.
268 *
269 * @param theta This is the surface site fraction for the kth species in
270 * the surface phase. This is a dimensionless quantity.
271 *
272 * This routine normalizes the theta's to 1, before application
273 */
274 void setCoverages(const double* theta);
275
276 //! Set the surface site fractions to a specified state.
277 /*!
278 * This routine converts to concentrations in kmol/m2, using m_n0, the
279 * surface site density, and size(k), which is defined to be the number of
280 * surface sites occupied by the kth molecule. It then calls
281 * Phase::setConcentrations to set the internal concentration in the object.
282 *
283 * @param theta This is the surface site fraction for the kth species in
284 * the surface phase. This is a dimensionless quantity.
285 */
286 void setCoveragesNoNorm(const double* theta);
287
288 //! Set the coverages from a string of colon-separated name:value pairs.
289 /*!
290 * @param cov String containing colon-separated name:value pairs
291 */
292 void setCoveragesByName(const string& cov);
293
294 //! Set the coverages from a map of name:value pairs
295 void setCoveragesByName(const Composition& cov);
296
297 //! Return a vector of surface coverages
298 /*!
299 * Get the coverages.
300 *
301 * @param theta Array theta must be at least as long as the number of
302 * species.
303 */
304 void getCoverages(double* theta) const;
305
306 //! @copydoc ThermoPhase::setState
307 /*!
308 * Additionally uses the key `coverages` to set the fractional coverages.
309 */
310 void setState(const AnyMap& state) override;
311
312 protected:
313 void compositionChanged() override;
314
315 //! Surface site density (kmol m-2)
316 double m_n0 = 1.0;
317
318 //! Vector of species sizes (number of sites occupied). length m_kk.
319 vector<double> m_speciesSize;
320
321 //! log of the surface site density
322 double m_logn0;
323
324 //! Current value of the pressure (Pa)
325 double m_press = OneAtm;
326
327 //! Temporary storage for the reference state enthalpies
328 mutable vector<double> m_h0;
329
330 //! Temporary storage for the reference state entropies
331 mutable vector<double> m_s0;
332
333 //! Temporary storage for the reference state heat capacities
334 mutable vector<double> m_cp0;
335
336 //! Temporary storage for the reference state Gibbs energies
337 mutable vector<double> m_mu0;
338
339 //! Temporary work array
340 mutable vector<double> m_work;
341
342 //! vector storing the log of the size of each species.
343 /*!
344 * The size of each species is defined as the number of surface sites each
345 * species occupies.
346 */
347 mutable vector<double> m_logsize;
348
349 //! Update the species reference state thermodynamic functions
350 /*!
351 * The polynomials for the standard state functions are only reevaluated if
352 * the temperature has changed.
353 *
354 * @param force Boolean, which if true, forces a reevaluation of the thermo
355 * polynomials. default = false.
356 */
357 void _updateThermo(bool force=false) const;
358};
359
360}
361
362#endif
ThermoPhase.h
Header file for class ThermoPhase, the base class for phases with thermodynamic properties,...
Cantera::AnyMap
A map of string keys to values whose type can vary at runtime.
Definition AnyMap.h:427
Cantera::SurfPhase
A simple thermodynamic model for a surface phase, assuming an ideal solution model.
Definition SurfPhase.h:98
Cantera::SurfPhase::molarVolume
double molarVolume() const override
Since interface phases have no volume, this returns 0.0.
Definition SurfPhase.h:208
Cantera::SurfPhase::setMolarDensity
void setMolarDensity(const double vm) override
Since interface phases have no volume, setting this to a value other than 0.0 raises an exception.
Definition SurfPhase.cpp:204
Cantera::SurfPhase::getStandardChemPotentials
void getStandardChemPotentials(double *mu0) const override
Get the array of chemical potentials at unit activity for the species at their standard states at the...
Definition SurfPhase.cpp:97
Cantera::SurfPhase::getPureGibbs
void getPureGibbs(double *g) const override
Get the Gibbs functions for the standard state of the species at the current T and P of the solution.
Definition SurfPhase.cpp:128
Cantera::SurfPhase::enthalpy_mole
double enthalpy_mole() const override
Return the Molar Enthalpy. Units: J/kmol.
Definition SurfPhase.cpp:28
Cantera::SurfPhase::setSiteDensity
void setSiteDensity(double n0)
Set the site density of the surface phase (kmol m-2)
Definition SurfPhase.cpp:212
Cantera::SurfPhase::logStandardConc
double logStandardConc(size_t k=0) const override
Natural logarithm of the standard concentration of the kth species.
Definition SurfPhase.cpp:123
Cantera::SurfPhase::setState
void setState(const AnyMap &state) override
Set the state using an AnyMap containing any combination of properties supported by the thermodynamic...
Definition SurfPhase.cpp:294
Cantera::SurfPhase::getPartialMolarEnthalpies
void getPartialMolarEnthalpies(double *hbar) const override
Returns an array of partial molar enthalpies for the species in the mixture.
Definition SurfPhase.cpp:64
Cantera::SurfPhase::getChemPotentials
void getChemPotentials(double *mu) const override
Get the species chemical potentials. Units: J/kmol.
Definition SurfPhase.cpp:103
Cantera::SurfPhase::pressure
double pressure() const override
Return the thermodynamic pressure (Pa).
Definition SurfPhase.h:243
Cantera::SurfPhase::isCompressible
bool isCompressible() const override
Return whether phase represents a compressible substance.
Definition SurfPhase.h:113
Cantera::SurfPhase::getEntropy_R
void getEntropy_R(double *sr) const override
Get the array of nondimensional Entropy functions for the standard state species at the current T and...
Definition SurfPhase.cpp:146
Cantera::SurfPhase::m_logsize
vector< double > m_logsize
vector storing the log of the size of each species.
Definition SurfPhase.h:347
Cantera::SurfPhase::m_work
vector< double > m_work
Temporary work array.
Definition SurfPhase.h:340
Cantera::SurfPhase::getCp_R
void getCp_R(double *cpr) const override
Get the nondimensional Heat Capacities at constant pressure for the species standard states at the cu...
Definition SurfPhase.cpp:152
Cantera::SurfPhase::getParameters
void getParameters(AnyMap &phaseNode) const override
Store the parameters of a ThermoPhase object such that an identical one could be reconstructed using ...
Definition SurfPhase.cpp:336
Cantera::SurfPhase::type
string type() const override
String indicating the thermodynamic model implemented.
Definition SurfPhase.h:109
Cantera::SurfPhase::initThermo
void initThermo() override
Initialize the ThermoPhase object after all species have been set up.
Definition SurfPhase.cpp:327
Cantera::SurfPhase::getActivityConcentrations
void getActivityConcentrations(double *c) const override
Return a vector of activity concentrations for each species.
Definition SurfPhase.cpp:113
Cantera::SurfPhase::m_n0
double m_n0
Surface site density (kmol m-2)
Definition SurfPhase.h:316
Cantera::SurfPhase::size
double size(size_t k) const
Returns the number of sites occupied by one molecule of species k.
Definition SurfPhase.h:226
Cantera::SurfPhase::setPressure
void setPressure(double p) override
Set the internally stored pressure (Pa) at constant temperature and composition.
Definition SurfPhase.h:252
Cantera::SurfPhase::m_h0
vector< double > m_h0
Temporary storage for the reference state enthalpies.
Definition SurfPhase.h:328
Cantera::SurfPhase::getPartialMolarVolumes
void getPartialMolarVolumes(double *vbar) const override
Return an array of partial molar volumes for the species in the mixture.
Definition SurfPhase.cpp:92
Cantera::SurfPhase::cv_mole
double cv_mole() const override
Molar heat capacity at constant volume. Units: J/kmol/K.
Definition SurfPhase.cpp:59
Cantera::SurfPhase::m_s0
vector< double > m_s0
Temporary storage for the reference state entropies.
Definition SurfPhase.h:331
Cantera::SurfPhase::setCoverages
void setCoverages(const double *theta)
Set the surface site fractions to a specified state.
Definition SurfPhase.cpp:223
Cantera::SurfPhase::m_cp0
vector< double > m_cp0
Temporary storage for the reference state heat capacities.
Definition SurfPhase.h:334
Cantera::SurfPhase::m_speciesSize
vector< double > m_speciesSize
Vector of species sizes (number of sites occupied). length m_kk.
Definition SurfPhase.h:319
Cantera::SurfPhase::m_press
double m_press
Current value of the pressure (Pa)
Definition SurfPhase.h:325
Cantera::SurfPhase::siteDensity
double siteDensity() const
Returns the site density.
Definition SurfPhase.h:221
Cantera::SurfPhase::getEnthalpy_RT
void getEnthalpy_RT(double *hrt) const override
Get the nondimensional Enthalpy functions for the species at their standard states at the current T a...
Definition SurfPhase.cpp:140
Cantera::SurfPhase::getEntropy_R_ref
void getEntropy_R_ref(double *er) const override
Returns the vector of nondimensional entropies of the reference state at the current temperature of t...
Definition SurfPhase.cpp:175
Cantera::SurfPhase::getGibbs_RT
void getGibbs_RT(double *grt) const override
Get the nondimensional Gibbs functions for the species in their standard states at the current T and ...
Definition SurfPhase.cpp:134
Cantera::SurfPhase::intEnergy_mole
double intEnergy_mole() const override
Return the Molar Internal Energy. Units: J/kmol.
Definition SurfPhase.cpp:37
Cantera::SurfPhase::entropy_mole
double entropy_mole() const override
Return the Molar Entropy. Units: J/kmol-K.
Definition SurfPhase.cpp:42
Cantera::SurfPhase::_updateThermo
void _updateThermo(bool force=false) const
Update the species reference state thermodynamic functions.
Definition SurfPhase.cpp:311
Cantera::SurfPhase::getCp_R_ref
void getCp_R_ref(double *cprt) const override
Returns the vector of nondimensional constant pressure heat capacities of the reference state at the ...
Definition SurfPhase.cpp:180
Cantera::SurfPhase::getStandardVolumes
void getStandardVolumes(double *vol) const override
Get the molar volumes of the species standard states at the current T and P of the solution.
Definition SurfPhase.cpp:158
Cantera::SurfPhase::setCoveragesNoNorm
void setCoveragesNoNorm(const double *theta)
Set the surface site fractions to a specified state.
Definition SurfPhase.cpp:239
Cantera::SurfPhase::getCoverages
void getCoverages(double *theta) const
Return a vector of surface coverages.
Definition SurfPhase.cpp:257
Cantera::SurfPhase::cp_mole
double cp_mole() const override
Molar heat capacity at constant pressure. Units: J/kmol/K.
Definition SurfPhase.cpp:53
Cantera::SurfPhase::getPartialMolarCp
void getPartialMolarCp(double *cpbar) const override
Return an array of partial molar heat capacities for the species in the mixture.
Definition SurfPhase.cpp:82
Cantera::SurfPhase::compositionChanged
void compositionChanged() override
Apply changes to the state which are needed after the composition changes.
Definition SurfPhase.cpp:305
Cantera::SurfPhase::standardConcentration
double standardConcentration(size_t k=0) const override
Return the standard concentration for the kth species.
Definition SurfPhase.cpp:118
Cantera::SurfPhase::m_mu0
vector< double > m_mu0
Temporary storage for the reference state Gibbs energies.
Definition SurfPhase.h:337
Cantera::SurfPhase::addSpecies
bool addSpecies(shared_ptr< Species > spec) override
Add a Species to this Phase.
Definition SurfPhase.cpp:185
Cantera::SurfPhase::setCoveragesByName
void setCoveragesByName(const string &cov)
Set the coverages from a string of colon-separated name:value pairs.
Definition SurfPhase.cpp:271
Cantera::SurfPhase::getGibbs_RT_ref
void getGibbs_RT_ref(double *grt) const override
Returns the vector of nondimensional Gibbs Free Energies of the reference state at the current temper...
Definition SurfPhase.cpp:165
Cantera::SurfPhase::m_logn0
double m_logn0
log of the surface site density
Definition SurfPhase.h:322
Cantera::SurfPhase::getPartialMolarEntropies
void getPartialMolarEntropies(double *sbar) const override
Returns an array of partial molar entropies of the species in the solution.
Definition SurfPhase.cpp:72
Cantera::SurfPhase::getEnthalpy_RT_ref
void getEnthalpy_RT_ref(double *hrt) const override
Returns the vector of nondimensional enthalpies of the reference state at the current temperature of ...
Definition SurfPhase.cpp:170
Cantera::ThermoPhase
Base class for a phase with thermodynamic properties.
Definition ThermoPhase.h:390
Cantera::OneAtm
const double OneAtm
One atmosphere [Pa].
Definition ct_defs.h:96
Cantera
Namespace for the Cantera kernel.
Definition AnyMap.cpp:564
Cantera::Composition
map< string, double > Composition
Map from string names to doubles.
Definition ct_defs.h:184