[Kinetics] Fix issue 717, Add check for sticking coefficient more than 1

include/cantera/kinetics/Reaction.h

@@ -384,6 +384,7 @@ class InterfaceReaction : public ElementaryReaction2
                       const Arrhenius& rate, bool isStick=false);
     virtual void calculateRateCoeffUnits(const Kinetics& kin);
     virtual void getParameters(AnyMap& reactionNode) const;
+    virtual void validate();
 
     virtual std::string type() const {
         return "interface";
@@ -457,6 +458,7 @@ class BlowersMaselInterfaceReaction : public BlowersMaselReaction
                       const BlowersMasel& rate, bool isStick=false);
     virtual void getParameters(AnyMap& reactionNode) const;
     virtual void calculateRateCoeffUnits(const Kinetics& kin);
+    virtual void validate();
 
     virtual std::string type() const {
         return "surface-Blowers-Masel";

include/cantera/kinetics/RxnRates.h

@@ -102,6 +102,10 @@ class Arrhenius
         return m_E;
     }
 
+    //! Check to make sure that the sticking coefficient is
+    //! less than 1 over a range of temperatures
+    void validate(const std::string& equation);
+
 protected:
     doublereal m_logA, m_b, m_E, m_A;
 };
@@ -212,6 +216,10 @@ class BlowersMasel
         return m_w;
     }
 
+    //! Check to make sure that the sticking coefficient is
+    //! less than 1 over a range of temperatures
+    void validate(const std::string& equation);
+
 protected:
     doublereal m_logA, m_b, m_A, m_w, m_E0;
 };

interfaces/cython/cantera/test/test_kinetics.py

@@ -422,6 +422,24 @@ def test_pdep_err(self):
             for msg in err_msg:
                 self.assertIn(msg, err_msg_list)
 
+    def test_sticking_coeff_err(self):
+        err_msg = (" Sticking coefficient is more than 1 for reaction 'O2 + 2 PT(S) => 2 O(S)'",
+                   " at T = 200.0",
+                   " at T = 500.0",
+                   " at T = 1000.0",
+                   " at T = 2000.0",
+                   " at T = 5000.0",
+                   " at T = 10000.0",
+                   " Sticking coefficient is more than 1 for reaction 'OH + PT(S) => OH(S)'"
+                   )
+        try:
+            gas = ct.Solution('sticking_coeff_check.yaml')
+            surface = ct.Interface('sticking_coeff_check.yaml', 'Pt_surf', [gas])
+            self.fail('CanteraError not raised')
+        except ct.CanteraError as e:
+            err_msg_list = str(e).splitlines()
+            for msg in err_msg:
+                self.assertIn(msg, err_msg_list)
 
 class TestUndeclared(utilities.CanteraTest):
 

src/kinetics/Reaction.cpp

@@ -745,6 +745,14 @@ void InterfaceReaction::getParameters(AnyMap& reactionNode) const
     }
 }
 
+void InterfaceReaction::validate() {
+    ElementaryReaction::validate();
+    if (is_sticking_coefficient != false) {
+        rate.validate(equation());
+    }
+
+}
+
 ElectrochemicalReaction::ElectrochemicalReaction()
     : beta(0.5)
     , exchange_current_density_formulation(false)
@@ -1099,6 +1107,14 @@ CustomFunc1Reaction::CustomFunc1Reaction(const AnyMap& node, const Kinetics& kin
     setRate(std::make_shared<CustomFunc1Rate>(node, rate_units));
 }
 
+void BlowersMaselInterfaceReaction::validate()
+{
+    BlowersMaselReaction::validate();
+    if (is_sticking_coefficient != false) {
+        rate.validate(equation());
+    }
+}
+
 Arrhenius readArrhenius(const XML_Node& arrhenius_node)
 {
     return Arrhenius(getFloat(arrhenius_node, "A", "toSI"),

src/kinetics/RxnRates.cpp

@@ -7,6 +7,7 @@
 #include "cantera/base/Array.h"
 #include "cantera/base/AnyMap.h"
 #include "cantera/base/global.h"
+#include <math.h>
 
 namespace Cantera
 {
@@ -83,6 +84,23 @@ void Arrhenius::getParameters(AnyMap& rateNode, const Units& rate_units) const
     rateNode.setFlowStyle();
 }
 
+void Arrhenius::validate(const std::string& equation) {
+    fmt::memory_buffer err_reactions;
+    double T[] = {200.0, 500.0, 1000.0, 2000.0, 5000.0, 10000.0};
+    for (size_t i=0; i < 6; i++) {
+        double gamma = m_A * std::exp(m_b*log(T[i]) - m_E*(1/T[i]));
+        if (gamma > 1) {
+             format_to(err_reactions,
+                       "\n Sticking coefficient is more than 1 for reaction '{}'\n"
+                       " at T = {:.1f}\n",
+                       equation, T[i]);
+        }
+    }
+    if (err_reactions.size()) {
+        throw CanteraError("Arrhenius::validate", to_string(err_reactions));
+    }
+}
+
 BlowersMasel::BlowersMasel()
     : m_logA(-1.0E300)
     , m_b(0.0)
@@ -123,6 +141,23 @@ void BlowersMasel::getParameters(AnyMap& rateNode, const Units& rate_units) cons
     rateNode.setFlowStyle();
 }
 
+void BlowersMasel::validate(const std::string& equation) {
+    fmt::memory_buffer err_reactions;
+    double T[] = {200.0, 500.0, 1000.0, 2000.0, 5000.0, 10000.0};
+    for (size_t i=0; i < 6; i++) {
+        double gamma = m_A * std::exp(m_b*log(T[i]) - m_E0*(1/T[i]));
+        if (gamma > 1) {
+             format_to(err_reactions,
+                       "\n Sticking coefficient is more than 1 for reaction '{}'\n"
+                       " at T = {:.1f}\n",
+                       equation, T[i]);
+        }
+    }
+    if (err_reactions.size()) {
+        throw CanteraError("BlowersMasel::validate", to_string(err_reactions));
+    }
+}
+
 SurfaceArrhenius::SurfaceArrhenius()
     : m_b(0.0)
     , m_E(0.0)

test/data/sticking_coeff_check.yaml

@@ -0,0 +1,56 @@
+units: {length: cm, quantity: mol, activation-energy: J/mol}
+
+phases:
+- name: gas
+  thermo: ideal-gas
+  elements: [O, H, C, N, Ar]
+  species:
+  - gri30.yaml/species: [ O2, OH]
+  skip-undeclared-elements: true
+  kinetics: gas
+  reactions:
+  - gri30.yaml/reactions: declared-species
+  transport: mixture-averaged
+- name: Pt_surf
+  thermo: ideal-surface
+  elements: [Pt, H, O, C]
+  species: [{Pt-surf-species: all}]
+  kinetics: surface
+  reactions: [Pt-reactions]
+
+Pt-surf-species:
+- name: PT(S)
+  composition: {Pt: 1}
+  thermo:
+    model: NASA7
+    temperature-ranges: [300.0, 1000.0, 3000.0]
+    data:
+    - [0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0]
+    - [0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0]
+- name: OH(S)
+  composition: {O: 1, H: 1, Pt: 1}
+  thermo:
+    model: NASA7
+    temperature-ranges: [300.0, 1000.0, 3000.0]
+    data:
+    - [-2.0340881, 9.3662683e-03, 6.6275214e-07, -5.2074887e-09, 1.7088735e-12,
+      -2.5319949e+04, 8.9863186]
+    - [1.8249973, 3.2501565e-03, -3.1197541e-07, -3.4603206e-10, 7.9171472e-14,
+      -2.6685492e+04, -12.280891]
+- name: O(S)
+  composition: {O: 1, Pt: 1}
+  thermo:
+    model: NASA7
+    temperature-ranges: [300.0, 1000.0, 3000.0]
+    data:
+    - [-0.94986904, 7.4042305e-03, -1.0451424e-06, -6.112042e-09, 3.3787992e-12,
+      -1.3209912e+04, 3.6137905]
+    - [1.945418, 9.1761647e-04, -1.1226719e-07, -9.9099624e-11, 2.4307699e-14,
+      -1.4005187e+04, -11.531663]
+
+Pt-reactions:
+- equation: O2 + 2 PT(S) => 2 O(S)  # Reaction 4
+  sticking-coefficient: {A: 2.0, b: 0, Ea: 0}
+- equation: OH + PT(S) => OH(S)  # Reaction 5
+  type: Blowers-Masel
+  sticking-coefficient: {A: 2.0, b: 0, Ea0: 0, w: 100000}