cantera/src/kinetics/GasKinetics.cpp

850 lines
26 KiB
C++

/**
* @file GasKinetics.cpp
*
* Homogeneous kinetics in ideal gases
*
*/
// Copyright 2001 California Institute of Technology
#include "cantera/kinetics/GasKinetics.h"
#include "cantera/kinetics/ReactionData.h"
#include "cantera/kinetics/Enhanced3BConc.h"
#include "cantera/kinetics/ThirdBodyMgr.h"
#include "cantera/kinetics/RateCoeffMgr.h"
#include <iostream>
using namespace std;
namespace Cantera
{
//====================================================================================================================
/*
* Construct an empty reaction mechanism.
*/
GasKinetics::
GasKinetics(thermo_t* thermo) :
Kinetics(),
m_nfall(0),
m_nirrev(0),
m_nrev(0),
m_logp_ref(0.0),
m_logc_ref(0.0),
m_logStandConc(0.0),
m_ROP_ok(false),
m_temp(0.0),
m_finalized(false)
{
if (thermo != 0) {
addPhase(*thermo);
}
m_temp = 0.0;
}
//====================================================================================================================
GasKinetics::GasKinetics(const GasKinetics& right) :
Kinetics(),
m_nfall(0),
m_nirrev(0),
m_nrev(0),
m_logp_ref(0.0),
m_logc_ref(0.0),
m_logStandConc(0.0),
m_ROP_ok(false),
m_temp(0.0),
m_finalized(false)
{
m_temp = 0.0;
*this = right;
}
//====================================================================================================================
GasKinetics::~GasKinetics()
{
}
//====================================================================================================================
GasKinetics& GasKinetics::operator=(const GasKinetics& right)
{
if (this == &right) {
return *this;
}
Kinetics::operator=(right);
m_nfall = right.m_nfall;
m_fallindx = right.m_fallindx;
m_falloff_low_rates = right.m_falloff_low_rates;
m_falloff_high_rates = right.m_falloff_high_rates;
m_rates = right.m_rates;
m_index = right.m_index;
m_falloffn = right.m_falloffn;
m_3b_concm = right.m_3b_concm;
m_falloff_concm = right.m_falloff_concm;
m_irrev = right.m_irrev;
m_plog_rates = right.m_plog_rates;
m_cheb_rates = right.m_cheb_rates;
m_rxnstoich = right.m_rxnstoich;
m_fwdOrder = right.m_fwdOrder;
m_nirrev = right.m_nirrev;
m_nrev = right.m_nrev;
m_rgroups = right.m_rgroups;
m_pgroups = right.m_pgroups;
m_rxntype = right.m_rxntype;
m_rrxn = right.m_rrxn;
m_prxn = right.m_prxn;
m_dn = right.m_dn;
m_revindex = right.m_revindex;
m_rxneqn = right.m_rxneqn;
m_logp_ref = right.m_logp_ref;
m_logc_ref = right.m_logc_ref;
m_logStandConc = right.m_logStandConc;
m_ropf = right.m_ropf;
m_ropr = right.m_ropr;
m_ropnet = right.m_ropnet;
m_rfn_low = right.m_rfn_low;
m_rfn_high = right.m_rfn_high;
m_ROP_ok = right.m_ROP_ok;
m_temp = right.m_temp;
m_rfn = right.m_rfn;
falloff_work = right.falloff_work;
concm_3b_values = right.concm_3b_values;
concm_falloff_values = right.concm_falloff_values;
m_rkcn = right.m_rkcn;
m_conc = right.m_conc;
m_grt = right.m_grt;
m_finalized = right.m_finalized;
throw CanteraError("GasKinetics::operator=()",
"Unfinished implementation");
return *this;
}
//====================================================================================================================
// Duplication routine for objects which inherit from Kinetics
/*
* This virtual routine can be used to duplicate %Kinetics objects
* inherited from %Kinetics even if the application only has
* a pointer to %Kinetics to work with.
*
* These routines are basically wrappers around the derived copy
* constructor.
*
* @param tpVector Vector of shallow pointers to ThermoPhase objects. this is the
* m_thermo vector within this object
*/
Kinetics* GasKinetics::duplMyselfAsKinetics(const std::vector<thermo_t*> & tpVector) const
{
GasKinetics* gK = new GasKinetics(*this);
gK->assignShallowPointers(tpVector);
return dynamic_cast<Kinetics*>(gK);
}
//====================================================================================================================
/**
* Update temperature-dependent portions of reaction rates and
* falloff functions.
*/
void GasKinetics::update_T()
{
}
//====================================================================================================================
void GasKinetics::
update_C() {}
//====================================================================================================================
void GasKinetics::
_update_rates_T()
{
doublereal T = thermo().temperature();
m_logStandConc = log(thermo().standardConcentration());
doublereal logT = log(T);
if (!m_rfn.empty()) {
m_rates.update(T, logT, &m_rfn[0]);
}
if (!m_rfn_low.empty()) {
m_falloff_low_rates.update(T, logT, &m_rfn_low[0]);
m_falloff_high_rates.update(T, logT, &m_rfn_high[0]);
}
if (!falloff_work.empty()) {
m_falloffn.updateTemp(T, &falloff_work[0]);
}
if (m_plog_rates.nReactions()) {
m_plog_rates.update(T, logT, &m_rfn[0]);
}
if (m_cheb_rates.nReactions()) {
m_cheb_rates.update(T, logT, &m_rfn[0]);
}
m_temp = T;
updateKc();
m_ROP_ok = false;
};
//====================================================================================================================
void GasKinetics::
_update_rates_C()
{
thermo().getActivityConcentrations(&m_conc[0]);
doublereal ctot = thermo().molarDensity();
// 3-body reactions
if (!concm_3b_values.empty()) {
m_3b_concm.update(m_conc, ctot, &concm_3b_values[0]);
}
// Falloff reactions
if (!concm_falloff_values.empty()) {
m_falloff_concm.update(m_conc, ctot, &concm_falloff_values[0]);
}
// 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;
}
//====================================================================================================================
/**
* Update the equilibrium constants in molar units.
*/
void GasKinetics::updateKc()
{
thermo().getStandardChemPotentials(&m_grt[0]);
fill(m_rkcn.begin(), m_rkcn.end(), 0.0);
// compute Delta G^0 for all reversible reactions
m_rxnstoich.getRevReactionDelta(m_ii, &m_grt[0], &m_rkcn[0]);
doublereal rrt = 1.0/(GasConstant * thermo().temperature());
for (size_t i = 0; i < m_nrev; i++) {
size_t irxn = m_revindex[i];
m_rkcn[irxn] = exp(m_rkcn[irxn]*rrt - m_dn[irxn]*m_logStandConc);
}
for (size_t i = 0; i != m_nirrev; ++i) {
m_rkcn[ m_irrev[i] ] = 0.0;
}
}
//====================================================================================================================
/**
* Get the equilibrium constants of all reactions, whether
* reversible or not.
*/
void GasKinetics::getEquilibriumConstants(doublereal* kc)
{
_update_rates_T();
thermo().getStandardChemPotentials(&m_grt[0]);
fill(m_rkcn.begin(), m_rkcn.end(), 0.0);
// compute Delta G^0 for all reactions
m_rxnstoich.getReactionDelta(m_ii, &m_grt[0], &m_rkcn[0]);
doublereal rrt = 1.0/(GasConstant * thermo().temperature());
for (size_t i = 0; i < m_ii; 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;
}
//====================================================================================================================
/**
*
* getDeltaGibbs():
*
* Return the vector of values for the reaction gibbs free energy
* change
* These values depend upon the concentration
* of the ideal gas.
*
* units = J kmol-1
*/
void GasKinetics::getDeltaGibbs(doublereal* deltaG)
{
/*
* Get the chemical potentials of the species in the
* ideal gas solution.
*/
thermo().getChemPotentials(&m_grt[0]);
/*
* Use the stoichiometric manager to find deltaG for each
* reaction.
*/
m_rxnstoich.getReactionDelta(m_ii, &m_grt[0], deltaG);
}
//====================================================================================================================
/**
*
* getDeltaEnthalpy():
*
* Return the vector of values for the reactions change in
* enthalpy.
* These values depend upon the concentration
* of the solution.
*
* units = J kmol-1
*/
void GasKinetics::getDeltaEnthalpy(doublereal* deltaH)
{
/*
* Get the partial molar enthalpy of all species in the
* ideal gas.
*/
thermo().getPartialMolarEnthalpies(&m_grt[0]);
/*
* Use the stoichiometric manager to find deltaG for each
* reaction.
*/
m_rxnstoich.getReactionDelta(m_ii, &m_grt[0], deltaH);
}
//====================================================================================================================
/*
*
* getDeltaEntropy():
*
* Return the vector of values for the reactions change in
* entropy.
* These values depend upon the concentration
* of the solution.
*
* units = J kmol-1 Kelvin-1
*/
void GasKinetics::getDeltaEntropy(doublereal* deltaS)
{
/*
* Get the partial molar entropy of all species in the
* solid solution.
*/
thermo().getPartialMolarEntropies(&m_grt[0]);
/*
* Use the stoichiometric manager to find deltaS for each
* reaction.
*/
m_rxnstoich.getReactionDelta(m_ii, &m_grt[0], deltaS);
}
//====================================================================================================================
/**
*
* getDeltaSSGibbs():
*
* Return the vector of values for the reaction
* standard state gibbs free energy change.
* These values don't depend upon the concentration
* of the solution.
*
* units = J kmol-1
*/
void GasKinetics::getDeltaSSGibbs(doublereal* deltaG)
{
/*
* Get the standard state chemical potentials of the species.
* This is the array of chemical potentials at unit activity
* We define these here as the chemical potentials of the pure
* species at the temperature and pressure of the solution.
*/
thermo().getStandardChemPotentials(&m_grt[0]);
/*
* Use the stoichiometric manager to find deltaG for each
* reaction.
*/
m_rxnstoich.getReactionDelta(m_ii, &m_grt[0], deltaG);
}
//====================================================================================================================
/**
*
* getDeltaSSEnthalpy():
*
* Return the vector of values for the change in the
* standard state enthalpies of reaction.
* These values don't depend upon the concentration
* of the solution.
*
* units = J kmol-1
*/
void GasKinetics::getDeltaSSEnthalpy(doublereal* deltaH)
{
/*
* Get the standard state enthalpies of the species.
* This is the array of chemical potentials at unit activity
* We define these here as the enthalpies of the pure
* species at the temperature and pressure of the solution.
*/
thermo().getEnthalpy_RT(&m_grt[0]);
doublereal RT = thermo().temperature() * GasConstant;
for (size_t k = 0; k < m_kk; k++) {
m_grt[k] *= RT;
}
/*
* Use the stoichiometric manager to find deltaG for each
* reaction.
*/
m_rxnstoich.getReactionDelta(m_ii, &m_grt[0], deltaH);
}
//====================================================================================================================
/*********************************************************************
*
* getDeltaSSEntropy():
*
* Return the vector of values for the change in the
* standard state entropies for each reaction.
* These values don't depend upon the concentration
* of the solution.
*
* units = J kmol-1 Kelvin-1
*/
void GasKinetics::getDeltaSSEntropy(doublereal* deltaS)
{
/*
* Get the standard state entropy of the species.
* We define these here as the entropies of the pure
* species at the temperature and pressure of the solution.
*/
thermo().getEntropy_R(&m_grt[0]);
doublereal R = GasConstant;
for (size_t k = 0; k < m_kk; k++) {
m_grt[k] *= R;
}
/*
* Use the stoichiometric manager to find deltaS for each
* reaction.
*/
m_rxnstoich.getReactionDelta(m_ii, &m_grt[0], deltaS);
}
//====================================================================================================================
// Return the species net production rates
/*
* Species net production rates [kmol/m^3/s]. Return the species
* net production rates (creation - destruction) in array
* wdot, which must be dimensioned at least as large as the
* total number of species.
*
* @param net Array of species production rates.
* units kmol m-3 s-1
*/
void GasKinetics::getNetProductionRates(doublereal* net)
{
updateROP();
m_rxnstoich.getNetProductionRates(m_kk, &m_ropnet[0], net);
}
//====================================================================================================================
// Return the species creation rates
/*
* Species creation rates [kmol/m^3]. Return the species
* creation rates in array cdot, which must be
* dimensioned at least as large as the total number of
* species.
*
* @param cdot Array of species production rates.
* units kmol m-3 s-1
*/
void GasKinetics::getCreationRates(doublereal* cdot)
{
updateROP();
m_rxnstoich.getCreationRates(m_kk, &m_ropf[0], &m_ropr[0], cdot);
}
//====================================================================================================================
// Return a vector of the species destruction rates
/*
* Species destruction rates [kmol/m^3]. Return the species
* destruction rates in array ddot, which must be
* dimensioned at least as large as the total number of
* species.
*
*
* @param ddot Array of species destruction rates.
* units kmol m-3 s-1
*
*/
void GasKinetics::getDestructionRates(doublereal* ddot)
{
updateROP();
m_rxnstoich.getDestructionRates(m_kk, &m_ropf[0], &m_ropr[0], ddot);
}
//====================================================================================================================
void GasKinetics::processFalloffReactions()
{
// use m_ropr for temporary storage of reduced pressure
vector_fp& pr = m_ropr;
for (size_t i = 0; i < m_nfall; i++) {
pr[i] = concm_falloff_values[i] * m_rfn_low[i] / m_rfn_high[i];
}
double* work = (falloff_work.empty()) ? 0 : &falloff_work[0];
m_falloffn.pr_to_falloff(&pr[0], work);
for (size_t i = 0; i < m_nfall; i++) {
pr[i] *= m_rfn_high[i];
}
scatter_copy(pr.begin(), pr.begin() + m_nfall,
m_ropf.begin(), m_fallindx.begin());
}
//====================================================================================================================
void GasKinetics::updateROP()
{
_update_rates_C();
_update_rates_T();
if (m_ROP_ok) {
return;
}
// copy rate coefficients into ropf
copy(m_rfn.begin(), m_rfn.end(), m_ropf.begin());
// multiply ropf by enhanced 3b conc for all 3b rxns
if (!concm_3b_values.empty()) {
m_3b_concm.multiply(&m_ropf[0], &concm_3b_values[0]);
}
if (m_nfall) {
processFalloffReactions();
}
// multiply by perturbation factor
multiply_each(m_ropf.begin(), m_ropf.end(), m_perturb.begin());
// copy the forward rates to the reverse rates
copy(m_ropf.begin(), m_ropf.end(), m_ropr.begin());
// for reverse rates computed from thermochemistry, multiply
// the forward rates copied into m_ropr by the reciprocals of
// the equilibrium constants
multiply_each(m_ropr.begin(), m_ropr.end(), m_rkcn.begin());
// multiply ropf by concentration products
m_rxnstoich.multiplyReactants(&m_conc[0], &m_ropf[0]);
//m_reactantStoich.multiply(m_conc.begin(), ropf.begin());
// for reversible reactions, multiply ropr by concentration
// products
m_rxnstoich.multiplyRevProducts(&m_conc[0], &m_ropr[0]);
//m_revProductStoich.multiply(m_conc.begin(), ropr.begin());
for (size_t j = 0; j != m_ii; ++j) {
m_ropnet[j] = m_ropf[j] - m_ropr[j];
}
m_ROP_ok = true;
}
//====================================================================================================================
/**
*
* getFwdRateConstants():
*
* Update the rate of progress for the reactions.
* This key routine makes sure that the rate of progress vectors
* located in the solid kinetics data class are up to date.
*/
void GasKinetics::
getFwdRateConstants(doublereal* kfwd)
{
_update_rates_C();
_update_rates_T();
// copy rate coefficients into ropf
copy(m_rfn.begin(), m_rfn.end(), m_ropf.begin());
// multiply ropf by enhanced 3b conc for all 3b rxns
if (!concm_3b_values.empty()) {
m_3b_concm.multiply(&m_ropf[0], &concm_3b_values[0]);
}
/*
* This routine is hardcoded to replace some of the values
* of the ropf vector.
*/
if (m_nfall) {
processFalloffReactions();
}
// multiply by perturbation factor
multiply_each(m_ropf.begin(), m_ropf.end(), m_perturb.begin());
for (size_t i = 0; i < m_ii; i++) {
kfwd[i] = m_ropf[i];
}
}
//====================================================================================================================
/**
*
* getRevRateConstants():
*
* Return a vector of the reverse reaction rate constants
*
* Length is the number of reactions. units depends
* on many issues. Note, this routine will return rate constants
* for irreversible reactions if the default for
* doIrreversible is overridden.
*/
void GasKinetics::
getRevRateConstants(doublereal* krev, bool doIrreversible)
{
/*
* go get the forward rate constants. -> note, we don't
* really care about speed or redundancy in these
* informational routines.
*/
getFwdRateConstants(krev);
if (doIrreversible) {
getEquilibriumConstants(&m_ropnet[0]);
for (size_t i = 0; i < m_ii; i++) {
krev[i] /= m_ropnet[i];
}
} else {
// m_rkcn[] is zero for irreversible reactions
for (size_t i = 0; i < m_ii; i++) {
krev[i] *= m_rkcn[i];
}
}
}
//====================================================================================================================
void GasKinetics::
addReaction(ReactionData& r)
{
switch (r.reactionType) {
case ELEMENTARY_RXN:
addElementaryReaction(r);
break;
case THREE_BODY_RXN:
addThreeBodyReaction(r);
break;
case FALLOFF_RXN:
addFalloffReaction(r);
break;
case PLOG_RXN:
addPlogReaction(r);
break;
case CHEBYSHEV_RXN:
addChebyshevReaction(r);
break;
default:
throw CanteraError("GasKinetics::addReaction", "Invalid reaction type specified");
}
// operations common to all reaction types
installReagents(r);
installGroups(reactionNumber(), r.rgroups, r.pgroups);
incrementRxnCount();
m_rxneqn.push_back(r.equation);
}
//====================================================================================================================
void GasKinetics::
addFalloffReaction(ReactionData& r)
{
// install high and low rate coeff calculators
// and add constant terms to high and low rate coeff value vectors
size_t iloc = m_falloff_high_rates.install(m_nfall, r);
m_rfn_high.push_back(r.rateCoeffParameters[0]);
std::swap(r.rateCoeffParameters, r.auxRateCoeffParameters);
m_falloff_low_rates.install(m_nfall, r);
m_rfn_low.push_back(r.rateCoeffParameters[0]);
// add a dummy entry in m_rf, where computed falloff
// rate coeff will be put
m_rfn.push_back(0.0);
// add this reaction number to the list of
// falloff reactions
m_fallindx.push_back(reactionNumber());
// install the enhanced third-body concentration
// calculator for this reaction
m_falloff_concm.install(m_nfall, r.thirdBodyEfficiencies,
r.default_3b_eff);
// install the falloff function calculator for
// this reaction
m_falloffn.install(m_nfall, r.falloffType, r.falloffParameters);
// forward rxn order equals number of reactants, since rate
// coeff is defined in terms of the high-pressure limit
m_fwdOrder.push_back(r.reactants.size());
// increment the falloff reaction counter
++m_nfall;
registerReaction(reactionNumber(), FALLOFF_RXN, iloc);
}
//====================================================================================================================
void GasKinetics::
addElementaryReaction(ReactionData& r)
{
// install rate coeff calculator
size_t iloc = m_rates.install(reactionNumber(), r);
// add constant term to rate coeff value vector
m_rfn.push_back(r.rateCoeffParameters[0]);
// forward rxn order equals number of reactants
m_fwdOrder.push_back(r.reactants.size());
registerReaction(reactionNumber(), ELEMENTARY_RXN, iloc);
}
//====================================================================================================================
void GasKinetics::
addThreeBodyReaction(ReactionData& r)
{
// install rate coeff calculator
size_t iloc = m_rates.install(reactionNumber(), r);
// add constant term to rate coeff value vector
m_rfn.push_back(r.rateCoeffParameters[0]);
// forward rxn order equals number of reactants + 1
m_fwdOrder.push_back(r.reactants.size() + 1);
m_3b_concm.install(reactionNumber(), r.thirdBodyEfficiencies,
r.default_3b_eff);
registerReaction(reactionNumber(), THREE_BODY_RXN, iloc);
}
//====================================================================================================================
void GasKinetics::addPlogReaction(ReactionData& r)
{
// install rate coefficient calculator
size_t iloc = m_plog_rates.install(reactionNumber(), r);
// add a dummy entry in m_rfn, where computed rate coeff will be put
m_rfn.push_back(0.0);
m_fwdOrder.push_back(r.reactants.size());
registerReaction(reactionNumber(), PLOG_RXN, iloc);
}
void GasKinetics::addChebyshevReaction(ReactionData& r)
{
// install rate coefficient calculator
size_t iloc = m_cheb_rates.install(reactionNumber(), r);
// add a dummy entry in m_rfn, where computed rate coeff will be put
m_rfn.push_back(0.0);
m_fwdOrder.push_back(r.reactants.size());
registerReaction(reactionNumber(), CHEBYSHEV_RXN, iloc);
}
void GasKinetics::installReagents(const ReactionData& r)
{
m_ropf.push_back(0.0); // extend by one for new rxn
m_ropr.push_back(0.0);
m_ropnet.push_back(0.0);
size_t n, ns, m;
doublereal nsFlt;
doublereal reactantGlobalOrder = 0.0;
doublereal productGlobalOrder = 0.0;
size_t rnum = reactionNumber();
std::vector<size_t> rk;
size_t nr = r.reactants.size();
for (n = 0; n < nr; n++) {
nsFlt = r.rstoich[n];
reactantGlobalOrder += nsFlt;
ns = (size_t) nsFlt;
if ((doublereal) ns != nsFlt) {
if (ns < 1) {
ns = 1;
}
}
if (r.rstoich[n] != 0.0) {
m_rrxn[r.reactants[n]][rnum] += r.rstoich[n];
}
for (m = 0; m < ns; m++) {
rk.push_back(r.reactants[n]);
}
}
m_reactants.push_back(rk);
std::vector<size_t> pk;
size_t np = r.products.size();
for (n = 0; n < np; n++) {
nsFlt = r.pstoich[n];
productGlobalOrder += nsFlt;
ns = (size_t) nsFlt;
if ((double) ns != nsFlt) {
if (ns < 1) {
ns = 1;
}
}
if (r.pstoich[n] != 0.0) {
m_prxn[r.products[n]][rnum] += r.pstoich[n];
}
for (m = 0; m < ns; m++) {
pk.push_back(r.products[n]);
}
}
m_products.push_back(pk);
m_rkcn.push_back(0.0);
m_rxnstoich.add(reactionNumber(), r);
if (r.reversible) {
m_dn.push_back(productGlobalOrder - reactantGlobalOrder);
m_revindex.push_back(reactionNumber());
m_nrev++;
} else {
m_dn.push_back(productGlobalOrder - reactantGlobalOrder);
m_irrev.push_back(reactionNumber());
m_nirrev++;
}
}
//====================================================================================================================
void GasKinetics::installGroups(size_t irxn,
const vector<grouplist_t>& r, const vector<grouplist_t>& p)
{
if (!r.empty()) {
writelog("installing groups for reaction "+int2str(reactionNumber()));
m_rgroups[reactionNumber()] = r;
m_pgroups[reactionNumber()] = p;
}
}
//====================================================================================================================
void GasKinetics::init()
{
m_kk = thermo().nSpecies();
m_rrxn.resize(m_kk);
m_prxn.resize(m_kk);
m_conc.resize(m_kk);
m_grt.resize(m_kk);
m_logp_ref = log(thermo().refPressure()) - log(GasConstant);
}
//====================================================================================================================
void GasKinetics::finalize()
{
if (!m_finalized) {
falloff_work.resize(m_falloffn.workSize());
concm_3b_values.resize(m_3b_concm.workSize());
concm_falloff_values.resize(m_falloff_concm.workSize());
m_finalized = true;
}
}
//====================================================================================================================
bool GasKinetics::ready() const
{
return (m_finalized);
}
//====================================================================================================================
}
//======================================================================================================================