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fix: corrected rate parameters in carbonate system #9

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fix: corrected rate parameters in carbonate system #9

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d4cbd48
Update carbonate system reaction constants
jkgolla Jul 2, 2025
453dbc6
Update carbonate reaction system
jkgolla Jul 2, 2025
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57 changes: 27 additions & 30 deletions src/reactions/geochemistry/Carbonate.hpp
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Original file line number Diff line number Diff line change
Expand Up @@ -40,52 +40,50 @@ constexpr CArrayWrapper<double, 11, 18> stoichMatrix =
// { 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, -2, 0, 1, 0, 0, 0, 0 } // Ca(OH)2​(s) + 2H+ = Ca2+ + 2H2​O (kinetic)
};

constexpr CArrayWrapper<double, 11, 17> stoichMatrixNosolid =
{ // OH- CO2 CO3-2 H2CO3 CaHCO3+ CaSO4 CaCl+ CaCl2 MgSO4 NaSO4- H+ HCO3- Ca+2 SO4-2 Cl- Mg+2 Na+
{ -1, 0, 0, 0, 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 0, 0 }, // OH- + H+ = H2O
{ 0, -1, 0, 0, 0, 0, 0, 0, 0, 0, 1, 1, 0, 0, 0, 0, 0 }, // CO2 + H2O = H+ + HCO3-
{ 0, 0, -1, 0, 0, 0, 0, 0, 0, 0, -1, 1, 0, 0, 0, 0, 0 }, // CO3-2 + H+ = HCO3-
{ 0, 0, 0, -1, 0, 0, 0, 0, 0, 0, 1, 1, 0, 0, 0, 0, 0 }, // H2CO3 = H+ + HCO3-
{ 0, 0, 0, 0, -1, 0, 0, 0, 0, 0, 0, 1, 1, 0, 0, 0, 0 }, // CaHCO3+ = Ca+2 + HCO3-
{ 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 0, 0, 1, 1, 0, 0, 0 }, // CaSO4 = Ca+2 + SO4-2
{ 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 0, 1, 0, 1, 0, 0 }, // CaCl+ = Ca+2 + Cl-
{ 0, 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 1, 0, 2, 0, 0 }, // CaCl2 = Ca+2 + 2Cl-
{ 0, 0, 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 1, 0, 1, 0 }, // MgSO4 = Mg+2 + SO4-2
{ 0, 0, 0, 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 1, 0, 0, 1 }, // NaSO4- = Na+ + SO4-2
{ 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, -1, 1, 1, 0, 0, 0, 0 } // CaCO3(s) + H+ = Ca+2 + HCO3- (kinetic)
// { 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, -2, 0, 1, 0, 0, 0, 0 } // Ca(OH)2​(s) + 2H+ = Ca2+ + 2H2​O (kinetic)
constexpr CArrayWrapper<double, 11, 16> stoichMatrixNosolid =
{ // OH- CO2 CO3-2 CaHCO3+ CaSO4 CaCl+ CaCl2 MgSO4 NaSO4- H+ HCO3- Ca+2 SO4-2 Cl- Mg+2 Na+
{ -1, 0, 0, 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 0, 0 }, // OH- + H+ = H2O
{ 0, -1, 0, 0, 0, 0, 0, 0, 0, 1, 1, 0, 0, 0, 0, 0 }, // CO2 + H2O = H+ + HCO3-
{ 0, 0, -1, 0, 0, 0, 0, 0, 0, -1, 1, 0, 0, 0, 0, 0 }, // CO3-2 + H+ = HCO3-
{ 0, 0, 0, -1, 0, 0, 0, 0, 0, 0, 1, 1, 0, 0, 0, 0 }, // CaHCO3+ = Ca+2 + HCO3-
{ 0, 0, 0, 0, -1, 0, 0, 0, 0, 0, 0, 1, 1, 0, 0, 0 }, // CaSO4 = Ca+2 + SO4-2
{ 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 0, 1, 0, 1, 0, 0 }, // CaCl+ = Ca+2 + Cl-
{ 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 1, 0, 2, 0, 0 }, // CaCl2 = Ca+2 + 2Cl-
{ 0, 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 0, 1, 0, 1, 0 }, // MgSO4 = Mg+2 + SO4-2
{ 0, 0, 0, 0, 0, 0, 0, 0, -1, 0, 0, 0, 1, 0, 0, 1 }, // NaSO4- = Na+ + SO4-2
{ 0, 0, 0, 0, 0, 0, 0, 0, 0, -1, 1, 1, 0, 0, 0, 0 } // CaCO3(s) + H+ = Ca+2 + HCO3- (kinetic)
// { 0, 0, 0, 0, 0, 0, 0, 0, 0, -2, 0, 1, 0, 0, 0, 0 } // Ca(OH)2​(s) + 2H+ = Ca2+ + 2H2​O (kinetic)
};

// C^{n+1} - C^n - r( C^{n+1} ) * dt = 0
// thermodynamic constants derived from 'llnl.tdat' used by Geochemists' Workbench (originally from EQ36)
constexpr CArrayWrapper<double, 11> equilibriumConstants =
{
9.77E+13, // OH- + H+ = H2O
4.37E-07, // CO2 + H2O = H+ + HCO3-
2.14E+10, // CO3-2 + H+ = HCO3-
1.70E-04, // H2CO3 = H+ + HCO3-
8.13E-02, // CaHCO3+ = Ca+2 + HCO3-
6.92E-03, // CaSO4 = Ca+2 + SO4-2
4.68E+00, // CaCl+ = Ca+2 + Cl-
9.89E+13, // OH- + H+ = H2O
4.42E-07, // CO2 + H2O = H+ + HCO3-
2.21E+10, // CO3-2 + H+ = HCO3-
6.00E-02, // CaHCO3+ = Ca+2 + HCO3-
4.79E-03, // CaSO4 = Ca+2 + SO4-2
2.00E-01, // CaCl+ = Ca+2 + Cl-
3.98E+00, // CaCl2 = Ca+2 + 2Cl-
3.72E-03, // MgSO4 = Mg+2 + SO4-2
1.51E-01, // NaSO4- = Na+ + SO4-2
1.17E+07 // CaCO3 + H+ = Ca+2 + HCO3- (kinetic)
5.92E-03, // MgSO4 = Mg+2 + SO4-2
2.02E-01, // NaSO4- = Na+ + SO4-2
5.16E+01 // CaCO3 + H+ = Ca+2 + HCO3- (kinetic)
// 1
}; // Ca(OH)2​(s) + 2H+ = Ca2+ + 2H2​O (kinetic)

constexpr CArrayWrapper<double, 11> forwardRates =
{
1.4e11, // OH- + H+ = H2O
0.039, // CO2 + H2O = H+ + HCO3-
1.0e10, // CO3-2 + H+ = HCO3-
0.57, // H2CO3 = H+ + HCO3-
1.0e10, // CO3-2 + H+ = HCO3-
1.5e6, // CaHCO3+ = Ca+2 + HCO3-
1.0e5, // CaSO4 = Ca+2 + SO4-2
1.0e8, // CaCl+ = Ca+2 + Cl-
1.0e7, // CaCl2 = Ca+2 + 2Cl-
1.0e5, // MgSO4 = Mg+2 + SO4-2
1.0e7, // NaSO4- = Na+ + SO4-2
1.0e5 // CaCO3 + H+ = Ca+2 + HCO3- (kinetic)
1.55E-06 // CaCO3 + H+ = Ca+2 + HCO3- (kinetic)

// 1
}; // Ca(OH)2​(s) + 2H+ = Ca2+ + 2H2​O (kinetic)
Expand All @@ -94,20 +92,19 @@ constexpr CArrayWrapper<double, 11> reverseRates =
{ 1.43E-03, // OH- + H+ = H2O
8.92E+04, // CO2 + H2O = H+ + HCO3-
4.67E-01, // CO3-2 + H+ = HCO3-
3.35E+03, // H2CO3 = H+ + HCO3-
1.85E+07, // CaHCO3+ = Ca+2 + HCO3-
1.45E+07, // CaSO4 = Ca+2 + SO4-2
2.14E+07, // CaCl+ = Ca+2 + Cl-
2.51E+06, // CaCl2 = Ca+2 + 2Cl-
2.69E+07, // MgSO4 = Mg+2 + SO4-2
6.62E+07, // NaSO4- = Na+ + SO4-2
8.55E-03 // CaCO3 + H+ = Ca+2 + HCO3-
3.00E-08 // CaCO3 + H+ = Ca+2 + HCO3-
// 1 // Ca(OH)2​(s) + 2H+ = Ca2+ + 2H2​O (kinetic)
};
}
using carbonateSystemAllKineticType = reactionsSystems::MixedReactionsParameters< double, int, int, 18, 11, 0 >;
using carbonateSystemAllEquilibriumType = reactionsSystems::MixedReactionsParameters< double, int, int, 18, 11, 11 >;
using carbonateSystemType = reactionsSystems::MixedReactionsParameters< double, int, int, 17, 11, 10 >;
using carbonateSystemType = reactionsSystems::MixedReactionsParameters< double, int, int, 16, 11, 10 >;

constexpr carbonateSystemAllKineticType carbonateSystemAllKinetic( carbonate::stoichMatrix, carbonate::equilibriumConstants, carbonate::forwardRates, carbonate::reverseRates );
constexpr carbonateSystemAllEquilibriumType carbonateSystemAllEquilibrium( carbonate::stoichMatrix, carbonate::equilibriumConstants, carbonate::forwardRates, carbonate::reverseRates );
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