-
-
Notifications
You must be signed in to change notification settings - Fork 346
/
GasKinetics.cpp
389 lines (329 loc) · 11.3 KB
/
GasKinetics.cpp
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
/**
* @file GasKinetics.cpp Homogeneous kinetics in ideal gases
*/
// This file is part of Cantera. See License.txt in the top-level directory or
// at https://cantera.org/license.txt for license and copyright information.
#include "cantera/kinetics/GasKinetics.h"
using namespace std;
namespace Cantera
{
GasKinetics::GasKinetics(thermo_t* thermo) :
BulkKinetics(thermo),
m_logp_ref(0.0),
m_logc_ref(0.0),
m_logStandConc(0.0),
m_pres(0.0)
{
}
void GasKinetics::update_rates_T()
{
doublereal T = thermo().temperature();
doublereal P = thermo().pressure();
m_logStandConc = log(thermo().standardConcentration());
doublereal logT = log(T);
if (T != m_temp) {
if (!m_rfn.empty()) {
m_rates.update(T, logT, m_rfn.data());
}
if (!m_rfn_low.empty()) {
m_falloff_low_rates.update(T, logT, m_rfn_low.data());
m_falloff_high_rates.update(T, logT, m_rfn_high.data());
}
if (!falloff_work.empty()) {
m_falloffn.updateTemp(T, falloff_work.data());
}
updateKc();
m_ROP_ok = false;
}
if (T != m_temp || P != m_pres) {
if (m_plog_rates.nReactions()) {
m_plog_rates.update(T, logT, m_rfn.data());
m_ROP_ok = false;
}
if (m_cheb_rates.nReactions()) {
m_cheb_rates.update(T, logT, m_rfn.data());
m_ROP_ok = false;
}
}
m_pres = P;
m_temp = T;
}
void GasKinetics::update_rates_C()
{
thermo().getActivityConcentrations(m_conc.data());
doublereal ctot = thermo().molarDensity();
// 3-body reactions
if (!concm_3b_values.empty()) {
m_3b_concm.update(m_conc, ctot, concm_3b_values.data());
}
// Falloff reactions
if (!concm_falloff_values.empty()) {
m_falloff_concm.update(m_conc, ctot, concm_falloff_values.data());
}
// P-log reactions
if (m_plog_rates.nReactions()) {
double logP = log(thermo().pressure());
m_plog_rates.update_C(&logP);
}
// Chebyshev reactions
if (m_cheb_rates.nReactions()) {
double log10P = log10(thermo().pressure());
m_cheb_rates.update_C(&log10P);
}
m_ROP_ok = false;
}
void GasKinetics::updateKc()
{
thermo().getStandardChemPotentials(m_grt.data());
fill(m_rkcn.begin(), m_rkcn.end(), 0.0);
// compute Delta G^0 for all reversible reactions
getRevReactionDelta(m_grt.data(), m_rkcn.data());
doublereal rrt = 1.0 / thermo().RT();
for (size_t i = 0; i < m_revindex.size(); i++) {
size_t irxn = m_revindex[i];
m_rkcn[irxn] = std::min(exp(m_rkcn[irxn]*rrt - m_dn[irxn]*m_logStandConc),
BigNumber);
}
for (size_t i = 0; i != m_irrev.size(); ++i) {
m_rkcn[ m_irrev[i] ] = 0.0;
}
}
void GasKinetics::getEquilibriumConstants(doublereal* kc)
{
update_rates_T();
thermo().getStandardChemPotentials(m_grt.data());
fill(m_rkcn.begin(), m_rkcn.end(), 0.0);
// compute Delta G^0 for all reactions
getReactionDelta(m_grt.data(), m_rkcn.data());
doublereal rrt = 1.0 / thermo().RT();
for (size_t i = 0; i < nReactions(); i++) {
kc[i] = exp(-m_rkcn[i]*rrt + m_dn[i]*m_logStandConc);
}
// force an update of T-dependent properties, so that m_rkcn will
// be updated before it is used next.
m_temp = 0.0;
}
void GasKinetics::processFalloffReactions()
{
// use m_ropr for temporary storage of reduced pressure
vector_fp& pr = m_ropr;
for (size_t i = 0; i < m_falloff_low_rates.nReactions(); i++) {
pr[i] = concm_falloff_values[i] * m_rfn_low[i] / (m_rfn_high[i] + SmallNumber);
AssertFinite(pr[i], "GasKinetics::processFalloffReactions",
"pr[{}] is not finite.", i);
}
m_falloffn.pr_to_falloff(pr.data(), falloff_work.data());
for (size_t i = 0; i < m_falloff_low_rates.nReactions(); i++) {
if (reactionType(m_fallindx[i]) == FALLOFF_RXN) {
pr[i] *= m_rfn_high[i];
} else { // CHEMACT_RXN
pr[i] *= m_rfn_low[i];
}
m_ropf[m_fallindx[i]] = pr[i];
}
}
void GasKinetics::updateROP()
{
update_rates_C();
update_rates_T();
if (m_ROP_ok) {
return;
}
// copy rate coefficients into ropf
m_ropf = m_rfn;
// multiply ropf by enhanced 3b conc for all 3b rxns
if (!concm_3b_values.empty()) {
m_3b_concm.multiply(m_ropf.data(), concm_3b_values.data());
}
if (m_falloff_high_rates.nReactions()) {
processFalloffReactions();
}
for (size_t i = 0; i < nReactions(); i++) {
// Scale the forward rate coefficient by the perturbation factor
m_ropf[i] *= m_perturb[i];
// For reverse rates computed from thermochemistry, multiply the forward
// rate coefficients by the reciprocals of the equilibrium constants
m_ropr[i] = m_ropf[i] * m_rkcn[i];
}
// multiply ropf by concentration products
m_reactantStoich.multiply(m_conc.data(), m_ropf.data());
// for reversible reactions, multiply ropr by concentration products
m_revProductStoich.multiply(m_conc.data(), m_ropr.data());
for (size_t j = 0; j != nReactions(); ++j) {
m_ropnet[j] = m_ropf[j] - m_ropr[j];
}
for (size_t i = 0; i < m_rfn.size(); i++) {
AssertFinite(m_rfn[i], "GasKinetics::updateROP",
"m_rfn[{}] is not finite.", i);
AssertFinite(m_ropf[i], "GasKinetics::updateROP",
"m_ropf[{}] is not finite.", i);
AssertFinite(m_ropr[i], "GasKinetics::updateROP",
"m_ropr[{}] is not finite.", i);
}
m_ROP_ok = true;
}
void GasKinetics::getFwdRateConstants(doublereal* kfwd)
{
update_rates_C();
update_rates_T();
// copy rate coefficients into ropf
m_ropf = m_rfn;
// multiply ropf by enhanced 3b conc for all 3b rxns
if (!concm_3b_values.empty()) {
m_3b_concm.multiply(m_ropf.data(), concm_3b_values.data());
}
if (m_falloff_high_rates.nReactions()) {
processFalloffReactions();
}
for (size_t i = 0; i < nReactions(); i++) {
// multiply by perturbation factor
kfwd[i] = m_ropf[i] * m_perturb[i];
}
}
bool GasKinetics::addReaction(shared_ptr<Reaction> r)
{
// operations common to all reaction types
bool added = BulkKinetics::addReaction(r);
if (!added) {
return false;
}
switch (r->reaction_type) {
case ELEMENTARY_RXN:
addElementaryReaction(dynamic_cast<ElementaryReaction&>(*r));
break;
case THREE_BODY_RXN:
addThreeBodyReaction(dynamic_cast<ThreeBodyReaction&>(*r));
break;
case FALLOFF_RXN:
case CHEMACT_RXN:
addFalloffReaction(dynamic_cast<FalloffReaction&>(*r));
break;
case PLOG_RXN:
addPlogReaction(dynamic_cast<PlogReaction&>(*r));
break;
case CHEBYSHEV_RXN:
addChebyshevReaction(dynamic_cast<ChebyshevReaction&>(*r));
break;
default:
throw CanteraError("GasKinetics::addReaction",
"Unknown reaction type specified: {}", r->reaction_type);
}
return true;
}
void GasKinetics::addFalloffReaction(FalloffReaction& r)
{
// install high and low rate coeff calculators and extend the high and low
// rate coeff value vectors
size_t nfall = m_falloff_high_rates.nReactions();
m_falloff_high_rates.install(nfall, r.high_rate);
m_rfn_high.push_back(0.0);
m_falloff_low_rates.install(nfall, r.low_rate);
m_rfn_low.push_back(0.0);
// add this reaction number to the list of falloff reactions
m_fallindx.push_back(nReactions()-1);
m_rfallindx[nReactions()-1] = nfall;
// install the enhanced third-body concentration calculator
map<size_t, double> efficiencies;
for (const auto& eff : r.third_body.efficiencies) {
size_t k = kineticsSpeciesIndex(eff.first);
if (k != npos) {
efficiencies[k] = eff.second;
} else if (!m_skipUndeclaredThirdBodies) {
throw CanteraError("GasKinetics::addFalloffReaction", "Found "
"third-body efficiency for undefined species '" + eff.first +
"' while adding reaction '" + r.equation() + "'");
}
}
m_falloff_concm.install(nfall, efficiencies,
r.third_body.default_efficiency);
concm_falloff_values.resize(m_falloff_concm.workSize());
// install the falloff function calculator for this reaction
m_falloffn.install(nfall, r.reaction_type, r.falloff);
falloff_work.resize(m_falloffn.workSize());
}
void GasKinetics::addThreeBodyReaction(ThreeBodyReaction& r)
{
m_rates.install(nReactions()-1, r.rate);
map<size_t, double> efficiencies;
for (const auto& eff : r.third_body.efficiencies) {
size_t k = kineticsSpeciesIndex(eff.first);
if (k != npos) {
efficiencies[k] = eff.second;
} else if (!m_skipUndeclaredThirdBodies) {
throw CanteraError("GasKinetics::addThreeBodyReaction", "Found "
"third-body efficiency for undefined species '" + eff.first +
"' while adding reaction '" + r.equation() + "'");
}
}
m_3b_concm.install(nReactions()-1, efficiencies,
r.third_body.default_efficiency);
concm_3b_values.resize(m_3b_concm.workSize());
}
void GasKinetics::addPlogReaction(PlogReaction& r)
{
m_plog_rates.install(nReactions()-1, r.rate);
}
void GasKinetics::addChebyshevReaction(ChebyshevReaction& r)
{
m_cheb_rates.install(nReactions()-1, r.rate);
}
void GasKinetics::modifyReaction(size_t i, shared_ptr<Reaction> rNew)
{
// operations common to all reaction types
BulkKinetics::modifyReaction(i, rNew);
switch (rNew->reaction_type) {
case ELEMENTARY_RXN:
modifyElementaryReaction(i, dynamic_cast<ElementaryReaction&>(*rNew));
break;
case THREE_BODY_RXN:
modifyThreeBodyReaction(i, dynamic_cast<ThreeBodyReaction&>(*rNew));
break;
case FALLOFF_RXN:
case CHEMACT_RXN:
modifyFalloffReaction(i, dynamic_cast<FalloffReaction&>(*rNew));
break;
case PLOG_RXN:
modifyPlogReaction(i, dynamic_cast<PlogReaction&>(*rNew));
break;
case CHEBYSHEV_RXN:
modifyChebyshevReaction(i, dynamic_cast<ChebyshevReaction&>(*rNew));
break;
default:
throw CanteraError("GasKinetics::modifyReaction",
"Unknown reaction type specified: {}", rNew->reaction_type);
}
// invalidate all cached data
m_ROP_ok = false;
m_temp += 0.1234;
m_pres += 0.1234;
}
void GasKinetics::modifyThreeBodyReaction(size_t i, ThreeBodyReaction& r)
{
m_rates.replace(i, r.rate);
}
void GasKinetics::modifyFalloffReaction(size_t i, FalloffReaction& r)
{
size_t iFall = m_rfallindx[i];
m_falloff_high_rates.replace(iFall, r.high_rate);
m_falloff_low_rates.replace(iFall, r.low_rate);
m_falloffn.replace(iFall, r.falloff);
}
void GasKinetics::modifyPlogReaction(size_t i, PlogReaction& r)
{
m_plog_rates.replace(i, r.rate);
}
void GasKinetics::modifyChebyshevReaction(size_t i, ChebyshevReaction& r)
{
m_cheb_rates.replace(i, r.rate);
}
void GasKinetics::init()
{
BulkKinetics::init();
m_logp_ref = log(thermo().refPressure()) - log(GasConstant);
}
void GasKinetics::invalidateCache()
{
BulkKinetics::invalidateCache();
m_pres += 0.13579;
}
}