Uncoupled redox database

[dlparkhurst]

Sometimes it is useful to consider kinetic redox reactions, as in example 9 of the Version 3 manual. In the ultimate case, all redox reactions are considered to be kinetic, in which case, it is necessary to define as separate "elements" each redox state of each redox element.

Here is a database based on phreeqc.dat that makes separate definitions for each redox state. You can either use this database directly and define all redox transformations kinetically, or you can select specific redox states to treat kinetically (as in example 9).

Code: [Select]

SOLUTION_MASTER_SPECIES
    H             H+              -1     H               1.008
    H(0)          H2               0     H             
    H(1)          H+              -1     0             
    Hzero         Hzero2           0     Hzero           1
    E             e-               0     0               1
    O             H2O              0     O               16
    O(0)          O2               0     O             
    O(-2)         H2O              0     0             
    Ozero         Ozero2           0     Ozero           16
    Ca            Ca+2             0     Ca              40.08
    Mg            Mg+2             0     Mg              24.312
    Na            Na+              0     Na              22.9898
    K             K+               0     K               39.102
    Ferrous       Ferrous+2        0     Ferrous         55.847
    Ferric        Ferric+3        -2     Ferric          55.847
    Manganous     Manganous+2      0     Manganous       54.938
    Manganic      Manganic+3       0     Manganic        54.938
    Al            Al+3             0     Al              26.9815
    Ba            Ba+2             0     Ba              137.34
    Sr            Sr+2             0     Sr              87.62
    Si            H4SiO4           0     SiO2            28.0843
    Cl            Cl-              0     Cl              35.453
    C             CO3-2            2     HCO3            12.0111
    C(4)          CO3-2            2     HCO3            12.0111
    Methane       MethaneH4        0     MethaneH4       16.0143
    Alkalinity    CO3-2            1     Ca0.5(CO3)0.5 50.05
    Sulfate       SulfateO4-2      0     SulfateO4       32.064
    Sulfide       HSulfide-        1     Sulfide         32.064
    Nitrate       NitrateO3-       0     Nitrate         14.0067
    Nitrite       NitriteO2-       0     Nitrite         14.0067
    Nzero         Nzero2           0     Nzero           14.0067
    Amm           AmmH4+           0     Amm             14.0067
    B             H3BO3            0     B               10.81
    P             PO4-3            2     P               30.9738
    F             F-               0     F               18.9984
    Li            Li+              0     Li              6.939
    Br            Br-              0     Br              79.904
    Zn            Zn+2             0     Zn              65.37
    Cd            Cd+2             0     Cd              112.4
    Pb            Pb+2             0     Pb              207.19
    Cupric        Cupric+2         0     Cupric          63.546
    Cuprous       Cuprous+         0     Cuprous         63.546
SOLUTION_SPECIES
H+ = H+
    log_k     0
    -gamma    9 0
    -dw       9.31e-009
e- = e-
    log_k     0
H2O = H2O
    log_k     0
Ca+2 = Ca+2
    log_k     0
    -gamma    5 0.165
    -dw       7.93e-010
    -millero  -19.69 0.1058 -0.001256 1.617 -0.075 0.0008262
Mg+2 = Mg+2
    log_k     0
    -gamma    5.5 0.2
    -dw       7.05e-010
    -millero  -22.32 0.0868 -0.0016 2.017 -0.125 0.001457
Na+ = Na+
    log_k     0
    -gamma    4 0.075
    -dw       1.33e-009
    -millero  -3.46 0.1092 -0.000768 2.698 -0.106 0.001651
K+ = K+
    log_k     0
    -gamma    3.5 0.015
    -dw       1.96e-009
    -millero  7.26 0.0892 -0.000736 2.722 -0.101 0.00151
Ferrous+2 = Ferrous+2
    log_k     0
    -gamma    6 0
    -dw       7.19e-010
Manganous+2 = Manganous+2
    log_k     0
    -gamma    6 0
    -dw       6.88e-010
Al+3 = Al+3
    log_k     0
    -gamma    9 0
    -dw       5.59e-010
Ba+2 = Ba+2
    log_k     0
    -gamma    5 0
    -dw       8.48e-010
Sr+2 = Sr+2
    log_k     0
    -gamma    5.26 0.121
    -dw       7.94e-010
    -millero  -18.44 0.0082 -0.0006 1.727 -0.067 0.00084
H4SiO4 = H4SiO4
    log_k     0
    -dw       1.1e-009
    -millero  56 0 0 0 0 0
Cl- = Cl-
    log_k     0
    -gamma    3.5 0.015
    -dw       2.03e-009
    -millero  16.37 0.0896 -0.001264 -1.494 0.034 -0.000621
CO3-2 = CO3-2
    log_k     0
    -gamma    5.4 0
    -dw       9.55e-010
    -millero  -8.74 0.3 -0.004064 5.65 0 0
SulfateO4-2 = SulfateO4-2
    log_k     0
    -gamma    5 -0.04
    -dw       1.07e-009
    -millero  9.26 0.284 -0.003808 0.4348 -0.0099143 -8.4762e-005
NitrateO3- = NitrateO3-
    log_k     0
    -dw       1.9e-009
    -millero  25.51 0.1888 -0.001984 -0.654 0 0
H3BO3 = H3BO3
    log_k     0
    -dw       1.1e-009
    -millero  36.56 0.13 -0.00081 0 0 0
PO4-3 = PO4-3
    log_k     0
    -gamma    4 0
    -dw       6.12e-010
F- = F-
    log_k     0
    -gamma    3.5 0
    -dw       1.46e-009
    -millero  -3.05 0.3276 -0.00352 1.271 -0.074 8.857e-005
Li+ = Li+
    log_k     0
    -gamma    6 0
    -dw       1.03e-009
Br- = Br-
    log_k     0
    -gamma    3 0
    -dw       2.01e-009
    -millero  22.98 0.0934 -0.000968 -1.675 0.05 -0.001105
Zn+2 = Zn+2
    log_k     0
    -gamma    5 0
    -dw       7.15e-010
Cd+2 = Cd+2
    log_k     0
    -dw       7.17e-010
Pb+2 = Pb+2
    log_k     0
    -dw       9.45e-010
Cupric+2 = Cupric+2
    log_k     0
    -gamma    6 0
    -dw       7.33e-010
H2O = OH- + H+
    log_k     -14
    delta_h   13.362 kcal
    -analytical_expression -283.971 -0.05069842 13323 102.24447 -1119669 0
    -gamma    3.5 0
    -dw       5.27e-009
2H2O = O2 + 4H+ + 4e-
    log_k     -86.08
    delta_h   134.79 kcal
    -dw       2.35e-009
Ozero2 = Ozero2
    log_k     0
    -dw       2.35e-009
2H+ + 2e- = H2
    log_k     -3.15
    delta_h   -1.759 kcal
    -dw       5.1e-009
Hzero2 = Hzero2
    log_k     0
    -dw       5.1e-009
H+ + CO3-2 = HCO3-
    log_k     10.329
    delta_h   -3.561 kcal
    -analytical_expression 107.8871 0.03252849 -5151.79 -38.92561 563713.9 0
    -gamma    5.4 0
    -dw       1.18e-009
    -millero  21.07 0.185 -0.002248 2.29 -0.006644 -3.667e-006
2H+ + CO3-2 = CO2 + H2O
    log_k     16.681
    delta_h   -5.738 kcal
    -analytical_expression 464.1965 0.09344813 -26986.16 -165.75951 2248628.9 0
    -dw       1.92e-009
MethaneH4 = MethaneH4
    log_k     0
    delta_h   -61.039 kcal
    -dw       1.85e-009
H+ + SulfateO4-2 = HSulfateO4-
    log_k     1.988
    delta_h   3.85 kcal
    -analytical_expression -56.889 0.006473 2307.9 19.8858 0 0
    -dw       1.33e-009
HSulfide- = HSulfide-
    log_k     0
    -gamma    3.5 0
    -dw       1.73e-009
HSulfide- = Sulfide-2 + H+
    log_k     -12.918
    delta_h   12.1 kcal
    -gamma    5 0
    -dw       7.31e-010
H+ + HSulfide- = H2Sulfide
    log_k     6.994
    delta_h   -5.3 kcal
    -analytical_expression -11.17 0.02386 3279 0 0 0
    -dw       2.1e-009
NitriteO2- = NitriteO2-
    log_k     0
    -gamma    3 0
    -dw       1.91e-009
Nzero2 = Nzero2
    log_k     0
    -dw       1.96e-009
AmmH4+ = AmmH3 + H+
    log_k     -9.252
    delta_h   12.48 kcal
    -analytical_expression 0.6322 -0.001225 -2835.76 0 0 0
    -dw       2.28e-009
AmmH4+ = AmmH4+
    log_k     0
    -gamma    2.5 0
    -dw       1.98e-009
    -millero  17.47 -0.0034 0.00076 0 0 0
AmmH4+ + SulfateO4-2 = AmmH4SulfateO4-
    log_k     1.11
H3BO3 = H2BO3- + H+
    log_k     -9.24
    delta_h   3.224 kcal
F- + H3BO3 = BF(OH)3-
    log_k     -0.4
    delta_h   1.85 kcal
2F- + H+ + H3BO3 = BF2(OH)2- + H2O
    log_k     7.63
    delta_h   1.618 kcal
3F- + 2H+ + H3BO3 = BF3OH- + 2H2O
    log_k     13.67
    delta_h   -1.614 kcal
4F- + 3H+ + H3BO3 = BF4- + 3H2O
    log_k     20.28
    delta_h   -1.846 kcal
H+ + PO4-3 = HPO4-2
    log_k     12.346
    delta_h   -3.53 kcal
    -gamma    4 0
    -dw       6.9e-010
2H+ + PO4-3 = H2PO4-
    log_k     19.553
    delta_h   -4.52 kcal
    -gamma    4.5 0
    -dw       8.46e-010
    -millero  33.6 0 0 0 0 0
F- + H+ = HF
    log_k     3.18
    delta_h   3.18 kcal
    -analytical_expression -2.033 0.012645 429.01 0 0 0
2F- + H+ = HF2-
    log_k     3.76
    delta_h   4.55 kcal
Ca+2 + H2O = CaOH+ + H+
    log_k     -12.78
Ca+2 + CO3-2 = CaCO3
    log_k     3.224
    delta_h   3.545 kcal
    -analytical_expression -1228.732 -0.29944 35512.75 485.818 0 0
    -dw       4.46e-010
Ca+2 + H+ + CO3-2 = CaHCO3+
    log_k     11.435
    delta_h   -0.871 kcal
    -analytical_expression 1317.0071 0.34546894 -39916.84 -517.70761 563713.9 0
    -gamma    5.4 0
    -dw       5.06e-010
Ca+2 + SulfateO4-2 = CaSulfateO4
    log_k     2.3
    delta_h   1.65 kcal
    -dw       4.71e-010
Ca+2 + HSulfateO4- = CaHSulfateO4+
    log_k     1.08
Ca+2 + PO4-3 = CaPO4-
    log_k     6.459
    delta_h   3.1 kcal
Ca+2 + HPO4-2 = CaHPO4
    log_k     2.739
    delta_h   3.3 kcal
Ca+2 + H2PO4- = CaH2PO4+
    log_k     1.408
    delta_h   3.4 kcal
Ca+2 + F- = CaF+
    log_k     0.94
    delta_h   4.12 kcal
H2O + Mg+2 = MgOH+ + H+
    log_k     -11.44
    delta_h   15.952 kcal
Mg+2 + CO3-2 = MgCO3
    log_k     2.98
    delta_h   2.713 kcal
    -analytical_expression 0.991 0.00667 0 0 0 0
H+ + Mg+2 + CO3-2 = MgHCO3+
    log_k     11.399
    delta_h   -2.771 kcal
    -analytical_expression 48.6721 0.03252849 -2614.335 -18.00263 563713.9 0
Mg+2 + SulfateO4-2 = MgSulfateO4
    log_k     2.37
    delta_h   4.55 kcal
Mg+2 + PO4-3 = MgPO4-
    log_k     6.589
    delta_h   3.1 kcal
HPO4-2 + Mg+2 = MgHPO4
    log_k     2.87
    delta_h   3.3 kcal
H2PO4- + Mg+2 = MgH2PO4+
    log_k     1.513
    delta_h   3.4 kcal
F- + Mg+2 = MgF+
    log_k     1.82
    delta_h   3.2 kcal
H2O + Na+ = NaOH + H+
    log_k     -14.18
Na+ + CO3-2 = NaCO3-
    log_k     1.27
    delta_h   8.91 kcal
    -dw       5.85e-010
HCO3- + Na+ = NaHCO3
    log_k     -0.25
    -dw       6.73e-010
Na+ + SulfateO4-2 = NaSulfateO4-
    log_k     0.7
    delta_h   1.12 kcal
    -dw       6.18e-010
HPO4-2 + Na+ = NaHPO4-
    log_k     0.29
F- + Na+ = NaF
    log_k     -0.24
H2O + K+ = KOH + H+
    log_k     -14.46
K+ + SulfateO4-2 = KSulfateO4-
    log_k     0.85
    delta_h   2.25 kcal
    -analytical_expression 3.106 0 -673.6 0 0 0
    -dw       7.46e-010
HPO4-2 + K+ = KHPO4-
    log_k     0.29
Ferrous+2 + H2O = FerrousOH+ + H+
    log_k     -9.5
    delta_h   13.2 kcal
Cl- + Ferrous+2 = FerrousCl+
    log_k     0.14
Ferrous+2 + CO3-2 = FerrousCO3
    log_k     4.38
Ferrous+2 + HCO3- = FerrousHCO3+
    log_k     2
Ferrous+2 + SulfateO4-2 = FerrousSulfateO4
    log_k     2.25
    delta_h   3.23 kcal
Ferrous+2 + HSulfateO4- = FerrousHSulfateO4+
    log_k     1.08
Ferrous+2 + 2HSulfide- = Ferrous(HSulfide)2
    log_k     8.95
Ferrous+2 + 3HSulfide- = Ferrous(HSulfide)3-
    log_k     10.987
Ferrous+2 + HPO4-2 = FerrousHPO4
    log_k     3.6
Ferrous+2 + H2PO4- = FerrousH2PO4+
    log_k     2.7
F- + Ferrous+2 = FerrousF+
    log_k     1
Ferric+3 = Ferric+3
    log_k     0
    -gamma    9 0
Ferric+3 + H2O = FerricOH+2 + H+
    log_k     -2.19
    delta_h   10.4 kcal
Ferric+3 + 2H2O = Ferric(OH)2+ + 2H+
    log_k     -5.67
    delta_h   17.1 kcal
Ferric+3 + 3H2O = Ferric(OH)3 + 3H+
    log_k     -12.56
    delta_h   24.8 kcal
Ferric+3 + 4H2O = Ferric(OH)4- + 4H+
    log_k     -21.6
    delta_h   31.9 kcal
2Ferric+3 + 2H2O = Ferric2(OH)2+4 + 2H+
    log_k     -2.95
    delta_h   13.5 kcal
3Ferric+3 + 4H2O = Ferric3(OH)4+5 + 4H+
    log_k     -6.3
    delta_h   14.3 kcal
Cl- + Ferric+3 = FerricCl+2
    log_k     1.48
    delta_h   5.6 kcal
2Cl- + Ferric+3 = FerricCl2+
    log_k     2.13
3Cl- + Ferric+3 = FerricCl3
    log_k     1.13
Ferric+3 + SulfateO4-2 = FerricSulfateO4+
    log_k     4.04
    delta_h   3.91 kcal
Ferric+3 + HSulfateO4- = FerricHSulfateO4+2
    log_k     2.48
Ferric+3 + 2SulfateO4-2 = Ferric(SulfateO4)2-
    log_k     5.38
    delta_h   4.6 kcal
Ferric+3 + HPO4-2 = FerricHPO4+
    log_k     5.43
    delta_h   5.76 kcal
Ferric+3 + H2PO4- = FerricH2PO4+2
    log_k     5.43
F- + Ferric+3 = FerricF+2
    log_k     6.2
    delta_h   2.7 kcal
2F- + Ferric+3 = FerricF2+
    log_k     10.8
    delta_h   4.8 kcal
3F- + Ferric+3 = FerricF3
    log_k     14
    delta_h   5.4 kcal
H2O + Manganous+2 = ManganousOH+ + H+
    log_k     -10.59
    delta_h   14.4 kcal
Cl- + Manganous+2 = ManganousCl+
    log_k     0.61
2Cl- + Manganous+2 = ManganousCl2
    log_k     0.25
3Cl- + Manganous+2 = ManganousCl3-
    log_k     -0.31
Manganous+2 + CO3-2 = ManganousCO3
    log_k     4.9
HCO3- + Manganous+2 = ManganousHCO3+
    log_k     1.95
Manganous+2 + SulfateO4-2 = ManganousSulfateO4
    log_k     2.25
    delta_h   3.37 kcal
Manganous+2 + 2NitrateO3- = Manganous(NitrateO3)2
    log_k     0.6
    delta_h   -0.396 kcal
F- + Manganous+2 = ManganousF+
    log_k     0.84
Manganic+3 = Manganic+3
    log_k     0
Al+3 + H2O = AlOH+2 + H+
    log_k     -5
    delta_h   11.49 kcal
    -analytical_expression -38.253 0 -656.27 14.327 0 0
Al+3 + 2H2O = Al(OH)2+ + 2H+
    log_k     -10.1
    delta_h   26.9 kcal
    -analytical_expression 88.5 0 -9391.6 -27.121 0 0
Al+3 + 3H2O = Al(OH)3 + 3H+
    log_k     -16.9
    delta_h   39.89 kcal
    -analytical_expression 226.374 0 -18247.8 -73.597 0 0
Al+3 + 4H2O = Al(OH)4- + 4H+
    log_k     -22.7
    delta_h   42.3 kcal
    -analytical_expression 51.578 0 -11168.9 -14.865 0 0
Al+3 + SulfateO4-2 = AlSulfateO4+
    log_k     3.5
    delta_h   2.29 kcal
Al+3 + 2SulfateO4-2 = Al(SulfateO4)2-
    log_k     5
    delta_h   3.11 kcal
Al+3 + HSulfateO4- = AlHSulfateO4+2
    log_k     0.46
Al+3 + F- = AlF+2
    log_k     7
    delta_h   1.06 kcal
Al+3 + 2F- = AlF2+
    log_k     12.7
    delta_h   1.98 kcal
Al+3 + 3F- = AlF3
    log_k     16.8
    delta_h   2.16 kcal
Al+3 + 4F- = AlF4-
    log_k     19.4
    delta_h   2.2 kcal
Al+3 + 5F- = AlF5-2
    log_k     20.6
    delta_h   1.84 kcal
Al+3 + 6F- = AlF6-3
    log_k     20.6
    delta_h   -1.67 kcal
H4SiO4 = H3SiO4- + H+
    log_k     -9.83
    delta_h   6.12 kcal
    -analytical_expression -302.3724 -0.050698 15669.69 108.18466 -1119669 0
H4SiO4 = H2SiO4-2 + 2H+
    log_k     -23
    delta_h   17.6 kcal
    -analytical_expression -294.0184 -0.07265 11204.49 108.18466 -1119669 0
6F- + 4H+ + H4SiO4 = SiF6-2 + 4H2O
    log_k     30.18
    delta_h   -16.26 kcal
Ba+2 + H2O = BaOH+ + H+
    log_k     -13.47
Ba+2 + CO3-2 = BaCO3
    log_k     2.71
    delta_h   3.55 kcal
    -analytical_expression 0.113 0.008721 0 0 0 0
Ba+2 + HCO3- = BaHCO3+
    log_k     0.982
    delta_h   5.56 kcal
    -analytical_expression -3.0938 0.013669 0 0 0 0
Ba+2 + SulfateO4-2 = BaSulfateO4
    log_k     2.7
H2O + Sr+2 = SrOH+ + H+
    log_k     -13.29
    -gamma    5 0
H+ + Sr+2 + CO3-2 = SrHCO3+
    log_k     11.509
    delta_h   2.489 kcal
    -analytical_expression 104.6391 0.04739549 -5151.79 -38.92561 563713.9 0
    -gamma    5.4 0
Sr+2 + CO3-2 = SrCO3
    log_k     2.81
    delta_h   5.22 kcal
    -analytical_expression -1.019 0.012826 0 0 0 0
Sr+2 + SulfateO4-2 = SrSulfateO4
    log_k     2.29
    delta_h   2.08 kcal
H2O + Li+ = LiOH + H+
    log_k     -13.64
Li+ + SulfateO4-2 = LiSulfateO4-
    log_k     0.64
Cuprous+ = Cuprous+
    log_k     0
    -gamma    2.5 0
Cupric+2 + H2O = CupricOH+ + H+
    log_k     -8
    -gamma    4 0
Cupric+2 + 2H2O = Cupric(OH)2 + 2H+
    log_k     -13.68
Cupric+2 + 3H2O = Cupric(OH)3- + 3H+
    log_k     -26.9
Cupric+2 + 4H2O = Cupric(OH)4-2 + 4H+
    log_k     -39.6
Cupric+2 + SulfateO4-2 = CupricSulfateO4
    log_k     2.31
    delta_h   1.22 kcal
H2O + Zn+2 = ZnOH+ + H+
    log_k     -8.96
    delta_h   13.4 kcal
2H2O + Zn+2 = Zn(OH)2 + 2H+
    log_k     -16.9
3H2O + Zn+2 = Zn(OH)3- + 3H+
    log_k     -28.4
4H2O + Zn+2 = Zn(OH)4-2 + 4H+
    log_k     -41.2
Cl- + Zn+2 = ZnCl+
    log_k     0.43
    delta_h   7.79 kcal
2Cl- + Zn+2 = ZnCl2
    log_k     0.45
    delta_h   8.5 kcal
3Cl- + Zn+2 = ZnCl3-
    log_k     0.5
    delta_h   9.56 kcal
4Cl- + Zn+2 = ZnCl4-2
    log_k     0.2
    delta_h   10.96 kcal
Zn+2 + CO3-2 = ZnCO3
    log_k     5.3
Zn+2 + 2CO3-2 = Zn(CO3)2-2
    log_k     9.63
HCO3- + Zn+2 = ZnHCO3+
    log_k     2.1
SulfateO4-2 + Zn+2 = ZnSulfateO4
    log_k     2.37
    delta_h   1.36 kcal
2SulfateO4-2 + Zn+2 = Zn(SulfateO4)2-2
    log_k     3.28
Cd+2 + H2O = CdOH+ + H+
    log_k     -10.08
    delta_h   13.1 kcal
Cd+2 + 2H2O = Cd(OH)2 + 2H+
    log_k     -20.35
Cd+2 + 3H2O = Cd(OH)3- + 3H+
    log_k     -33.3
Cd+2 + 4H2O = Cd(OH)4-2 + 4H+
    log_k     -47.35
Cd+2 + Cl- = CdCl+
    log_k     1.98
    delta_h   0.59 kcal
Cd+2 + 2Cl- = CdCl2
    log_k     2.6
    delta_h   1.24 kcal
Cd+2 + 3Cl- = CdCl3-
    log_k     2.4
    delta_h   3.9 kcal
Cd+2 + CO3-2 = CdCO3
    log_k     2.9
Cd+2 + 2CO3-2 = Cd(CO3)2-2
    log_k     6.4
Cd+2 + HCO3- = CdHCO3+
    log_k     1.5
Cd+2 + SulfateO4-2 = CdSulfateO4
    log_k     2.46
    delta_h   1.08 kcal
Cd+2 + 2SulfateO4-2 = Cd(SulfateO4)2-2
    log_k     3.5
H2O + Pb+2 = PbOH+ + H+
    log_k     -7.71
2H2O + Pb+2 = Pb(OH)2 + 2H+
    log_k     -17.12
3H2O + Pb+2 = Pb(OH)3- + 3H+
    log_k     -28.06
4H2O + Pb+2 = Pb(OH)4-2 + 4H+
    log_k     -39.7
H2O + 2Pb+2 = Pb2OH+3 + H+
    log_k     -6.36
Cl- + Pb+2 = PbCl+
    log_k     1.6
    delta_h   4.38 kcal
2Cl- + Pb+2 = PbCl2
    log_k     1.8
    delta_h   1.08 kcal
3Cl- + Pb+2 = PbCl3-
    log_k     1.7
    delta_h   2.17 kcal
4Cl- + Pb+2 = PbCl4-2
    log_k     1.38
    delta_h   3.53 kcal
Pb+2 + CO3-2 = PbCO3
    log_k     7.24
Pb+2 + 2CO3-2 = Pb(CO3)2-2
    log_k     10.64
HCO3- + Pb+2 = PbHCO3+
    log_k     2.9
Pb+2 + SulfateO4-2 = PbSulfateO4
    log_k     2.75
Pb+2 + 2SulfateO4-2 = Pb(SulfateO4)2-2
    log_k     3.47
NitrateO3- + Pb+2 = PbNitrateO3+
    log_k     1.17

PHASES
redoxCalcite
    CaCO3 = Ca+2 + CO3-2
    log_k     -8.48
    delta_h   -2.297 kcal
    -analytical_expression -171.9065 -0.077993 2839.319 71.595 0 0
redoxAragonite
    CaCO3 = Ca+2 + CO3-2
    log_k     -8.336
    delta_h   -2.589 kcal
    -analytical_expression -171.9773 -0.077993 2903.293 71.595 0 0
redoxDolomite
    CaMg(CO3)2 = Ca+2 + Mg+2 + 2CO3-2
    log_k     -17.09
    delta_h   -9.436 kcal
redoxSiderite
    FerrousCO3 = Ferrous+2 + CO3-2
    log_k     -10.89
    delta_h   -2.48 kcal
redoxRhodochrosite
    ManganousCO3 = Manganous+2 + CO3-2
    log_k     -11.13
    delta_h   -1.43 kcal
redoxStrontianite
    SrCO3 = Sr+2 + CO3-2
    log_k     -9.271
    delta_h   -0.4 kcal
    -analytical_expression 155.0305 0 -7239.594 -56.58638 0 0
redoxWitherite
    BaCO3 = Ba+2 + CO3-2
    log_k     -8.562
    delta_h   0.703 kcal
    -analytical_expression 607.642 0.121098 -20011.25 -236.4948 0 0
redoxGypsum
    CaSulfateO4:2H2O = Ca+2 + 2H2O + SulfateO4-2
    log_k     -4.58
    delta_h   -0.109 kcal
    -analytical_expression 68.2401 0 -3221.51 -25.0627 0 0
redoxAnhydrite
    CaSulfateO4 = Ca+2 + SulfateO4-2
    log_k     -4.36
    delta_h   -1.71 kcal
    -analytical_expression 197.52 0 -8669.8 -69.835 0 0
redoxCelestite
    SrSulfateO4 = Sr+2 + SulfateO4-2
    log_k     -6.63
    delta_h   -1.037 kcal
    -analytical_expression -14805.9622 -2.4660924 756968.533 5436.3588 -40553604 0
redoxBarite
    BaSulfateO4 = Ba+2 + SulfateO4-2
    log_k     -9.97
    delta_h   6.35 kcal
    -analytical_expression 136.035 0 -7680.41 -48.595 0 0
Hydroxyapatite
    Ca5(PO4)3OH + 4H+ = 5Ca+2 + H2O + 3HPO4-2
    log_k     -3.421
    delta_h   -36.155 kcal
Fluorite
    CaF2 = Ca+2 + 2F-
    log_k     -10.6
    delta_h   4.69 kcal
    -analytical_expression 66.348 0 -4298.2 -25.271 0 0
SiO2(a)
    SiO2 + 2H2O = H4SiO4
    log_k     -2.71
    delta_h   3.34 kcal
    -analytical_expression -0.26 0 -731 0 0 0
Chalcedony
    SiO2 + 2H2O = H4SiO4
    log_k     -3.55
    delta_h   4.72 kcal
    -analytical_expression -0.09 0 -1032 0 0 0
Quartz
    SiO2 + 2H2O = H4SiO4
    log_k     -3.98
    delta_h   5.99 kcal
    -analytical_expression 0.41 0 -1309 0 0 0
Gibbsite
    Al(OH)3 + 3H+ = Al+3 + 3H2O
    log_k     8.11
    delta_h   -22.8 kcal
Al(OH)3(a)
    Al(OH)3 + 3H+ = Al+3 + 3H2O
    log_k     10.8
    delta_h   -26.5 kcal
Kaolinite
    Al2Si2O5(OH)4 + 6H+ = 2Al+3 + H2O + 2H4SiO4
    log_k     7.435
    delta_h   -35.3 kcal
Albite
    NaAlSi3O8 + 8H2O = Al(OH)4- + 3H4SiO4 + Na+
    log_k     -18.002
    delta_h   25.896 kcal
Anorthite
    CaAl2Si2O8 + 8H2O = 2Al(OH)4- + Ca+2 + 2H4SiO4
    log_k     -19.714
    delta_h   11.58 kcal
K-feldspar
    KAlSi3O8 + 8H2O = Al(OH)4- + 3H4SiO4 + K+
    log_k     -20.573
    delta_h   30.82 kcal
K-mica
    KAl3Si3O10(OH)2 + 10H+ = 3Al+3 + 3H4SiO4 + K+
    log_k     12.703
    delta_h   -59.376 kcal
Chlorite(14A)
    Mg5Al2Si3O10(OH)8 + 16H+ = 2Al+3 + 6H2O + 3H4SiO4 + 5Mg+2
    log_k     68.38
    delta_h   -151.494 kcal
Ca-Montmorillonite
    Ca0.165Al2.33Si3.67O10(OH)2 + 12H2O = 2.33Al(OH)4- + 0.165Ca+2 + 2H+ + 3.67H4SiO4
    log_k     -45.027
    delta_h   58.373 kcal
Talc
    Mg3Si4O10(OH)2 + 6H+ + 4H2O = 4H4SiO4 + 3Mg+2
    log_k     21.399
    delta_h   -46.352 kcal
Illite
    K0.6Mg0.25Al2.3Si3.5O10(OH)2 + 11.2H2O = 2.3Al(OH)4- + 1.2H+ + 3.5H4SiO4 + 0.6K+ + 0.25Mg+2
    log_k     -40.267
    delta_h   54.684 kcal
Chrysotile
    Mg3Si2O5(OH)4 + 6H+ = H2O + 2H4SiO4 + 3Mg+2
    log_k     32.2
    delta_h   -46.8 kcal
    -analytical_expression 13.248 0 10217.1 -6.1894 0 0
Sepiolite
    Mg2Si3O7.5OH:3H2O + 4H+ + 0.5H2O = 3H4SiO4 + 2Mg+2
    log_k     15.76
    delta_h   -10.7 kcal
Sepiolite(d)
    Mg2Si3O7.5OH:3H2O + 4H+ + 0.5H2O = 3H4SiO4 + 2Mg+2
    log_k     18.66
redoxHematite
    Ferric2O3 + 6H+ = 2Ferric+3 + 3H2O
    log_k     -4.008
    delta_h   -30.845 kcal
redoxGoethite
    FerricOOH + 3H+ = Ferric+3 + 2H2O
    log_k     -1
    delta_h   -14.48 kcal
redoxFe(OH)3(a)
    Ferric(OH)3 + 3H+ = Ferric+3 + 3H2O
    log_k     4.891
redoxPyrite
    FerrousSulfide2 + 2H+ + 2e- = Ferrous+2 + 2HSulfide-
    log_k     -18.479
    delta_h   11.3 kcal
redoxFeS(ppt)
    FerrousSulfide + H+ = Ferrous+2 + HSulfide-
    log_k     -3.915
redoxMackinawite
    FerrousSulfide + H+ = Ferrous+2 + HSulfide-
    log_k     -4.648
redoxSulfur
    Sulfide + 2H+ + 2e- = H2Sulfide
    log_k     4.882
    delta_h   -9.5 kcal
redoxVivianite
    Ferrous3(PO4)2:8H2O = 3Ferrous+2 + 8H2O + 2PO4-3
    log_k     -36
redoxHausmannite
    ManganousManganic2O4 + 8H+ = 4H2O + 2Manganic+3 + Manganous+2
    log_k     10.01
redoxManganite
    ManganicOOH + 3H+ = 2H2O + Manganic+3
    log_k     -0.17
redoxPyrochroite
    Manganous(OH)2 + 2H+ = 2H2O + Manganous+2
    log_k     15.2
Halite
    NaCl = Cl- + Na+
    log_k     1.582
    delta_h   0.918 kcal
redoxCO2(g)
    CO2 = CO2
    log_k     -1.468
    delta_h   -4.776 kcal
    -analytical_expression 108.3865 0.01985076 -6919.53 -40.45154 669365 0
redoxO2(g)
    Ozero2 = Ozero2
    log_k     -2.8983
    -analytical_expression -7.5001 0.0078981 0 0 200270 0
H2(g)
    H2 = H2
    log_k     -3.15
    delta_h   -1.759 kcal
redoxH2(g)
    Hzero2 = Hzero2
    log_k     -3.15
    delta_h   -1.759 kcal
H2O(g)
    H2O = H2O
    log_k     1.51
    delta_h   -44.03 kJ
redoxN2(g)
    Nzero2 = Nzero2
    log_k     -3.26
    delta_h   -1.358 kcal
redoxH2S(g)
    H2Sulfide = H2Sulfide
    log_k     -0.997
    delta_h   -4.57 kcal
redoxCH4(g)
    MethaneH4 = MethaneH4
    log_k     -2.86
    delta_h   -3.373 kcal
redoxNH3(g)
    AmmH3 = AmmH3
    log_k     1.77
    delta_h   -8.17 kcal
redoxMelanterite
    FerrousSulfateO4:7H2O = Ferrous+2 + 7H2O + SulfateO4-2
    log_k     -2.209
    delta_h   4.91 kcal
    -analytical_expression 1.447 -0.004153 0 0 -214949 0
redoxAlunite
    KAl3(SulfateO4)2(OH)6 + 6H+ = 3Al+3 + 6H2O + K+ + 2SulfateO4-2
    log_k     -1.4
    delta_h   -50.25 kcal
redoxJarosite-K
    KFerric3(SulfateO4)2(OH)6 + 6H+ = 3Ferric+3 + 6H2O + K+ + 2SulfateO4-2
    log_k     -9.21
    delta_h   -31.28 kcal
Zn(OH)2(e)
    Zn(OH)2 + 2H+ = 2H2O + Zn+2
    log_k     11.5
redoxSmithsonite
    ZnCO3 = Zn+2 + CO3-2
    log_k     -10
    delta_h   -4.36 kcal
redoxSphalerite
    ZnSulfide + H+ = HSulfide- + Zn+2
    log_k     -11.618
    delta_h   8.25 kcal
Willemite
    Zn2SiO4 + 4H+ = H4SiO4 + 2Zn+2
    log_k     15.33
    delta_h   -33.37 kcal
Cd(OH)2
    Cd(OH)2 + 2H+ = Cd+2 + 2H2O
    log_k     13.65
redoxOtavite
    CdCO3 = Cd+2 + CO3-2
    log_k     -12.1
    delta_h   -0.019 kcal
CdSiO3
    CdSiO3 + 2H+ + H2O = Cd+2 + H4SiO4
    log_k     9.06
    delta_h   -16.63 kcal
redoxCdSO4
    CdSulfateO4 = Cd+2 + SulfateO4-2
    log_k     -0.1
    delta_h   -14.74 kcal
redoxCerrusite
    PbCO3 = Pb+2 + CO3-2
    log_k     -13.13
    delta_h   4.86 kcal
redoxAnglesite
    PbSulfateO4 = Pb+2 + SulfateO4-2
    log_k     -7.79
    delta_h   2.15 kcal
Pb(OH)2
    Pb(OH)2 + 2H+ = 2H2O + Pb+2
    log_k     8.15
    delta_h   -13.99 kcal

EXCHANGE_MASTER_SPECIES
    X             X-           
EXCHANGE_SPECIES
X- = X-
    log_k     0
Na+ + X- = NaX
    log_k     0
    -gamma    4 0.075
K+ + X- = KX
    log_k     0.7
    delta_h   -4.3 kJ
    -gamma    3.5 0.015
Li+ + X- = LiX
    log_k     -0.08
    delta_h   1.4 kJ
    -gamma    6 0
AmmH4+ + X- = AmmH4X
    log_k     0.6
    delta_h   -2.4 kJ
    -gamma    2.5 0
Ca+2 + 2X- = CaX2
    log_k     0.8
    delta_h   7.2 kJ
    -gamma    5 0.165
Mg+2 + 2X- = MgX2
    log_k     0.6
    delta_h   7.4 kJ
    -gamma    5.5 0.2
Sr+2 + 2X- = SrX2
    log_k     0.91
    delta_h   5.5 kJ
    -gamma    5.26 0.121
Ba+2 + 2X- = BaX2
    log_k     0.91
    delta_h   4.5 kJ
    -gamma    5 0
Manganous+2 + 2X- = ManganousX2
    log_k     0.52
    -gamma    6 0
Ferrous+2 + 2X- = FerrousX2
    log_k     0.44
    -gamma    6 0
Cupric+2 + 2X- = CupricX2
    log_k     0.6
    -gamma    6 0
2X- + Zn+2 = ZnX2
    log_k     0.8
    -gamma    5 0
Cd+2 + 2X- = CdX2
    log_k     0.8
    -davies 
Pb+2 + 2X- = PbX2
    log_k     1.05
    -davies 
Al+3 + 3X- = AlX3
    log_k     0.41
    -gamma    9 0
AlOH+2 + 2X- = AlOHX2
    log_k     0.89
    -davies 
SURFACE_MASTER_SPECIES
    Hfo_s         Hfo_sOH     
    Hfo_w         Hfo_wOH     
SURFACE_SPECIES
Hfo_sOH = Hfo_sOH
    log_k     0
H+ + Hfo_sOH = Hfo_sOH2+
    log_k     7.29
Hfo_sOH = Hfo_sO- + H+
    log_k     -8.93
Hfo_wOH = Hfo_wOH
    log_k     0
H+ + Hfo_wOH = Hfo_wOH2+
    log_k     7.29
Hfo_wOH = Hfo_wO- + H+
    log_k     -8.93
Ca+2 + Hfo_sOH = Hfo_sOHCa+2
    log_k     4.97
Ca+2 + Hfo_wOH = Hfo_wOCa+ + H+
    log_k     -5.85
Hfo_sOH + Sr+2 = Hfo_sOHSr+2
    log_k     5.01
Hfo_wOH + Sr+2 = Hfo_wOSr+ + H+
    log_k     -6.58
H2O + Hfo_wOH + Sr+2 = Hfo_wOSrOH + 2H+
    log_k     -17.6
Ba+2 + Hfo_sOH = Hfo_sOHBa+2
    log_k     5.46
Ba+2 + Hfo_wOH = Hfo_wOBa+ + H+
    log_k     -7.2
Cd+2 + Hfo_sOH = Hfo_sOCd+ + H+
    log_k     0.47
Cd+2 + Hfo_wOH = Hfo_wOCd+ + H+
    log_k     -2.91
Hfo_sOH + Zn+2 = Hfo_sOZn+ + H+
    log_k     0.99
Hfo_wOH + Zn+2 = Hfo_wOZn+ + H+
    log_k     -1.99
Cupric+2 + Hfo_sOH = Hfo_sOCupric+ + H+
    log_k     2.89
Cupric+2 + Hfo_wOH = Hfo_wOCupric+ + H+
    log_k     0.6
Hfo_sOH + Pb+2 = Hfo_sOPb+ + H+
    log_k     4.65
Hfo_wOH + Pb+2 = Hfo_wOPb+ + H+
    log_k     0.3
Hfo_wOH + Mg+2 = Hfo_wOMg+ + H+
    log_k     -4.6
Hfo_sOH + Manganous+2 = Hfo_sOManganous+ + H+
    log_k     -0.4
Hfo_wOH + Manganous+2 = Hfo_wOManganous+ + H+
    log_k     -3.5
Ferrous+2 + Hfo_sOH = Hfo_sOFerrous+ + H+
    log_k     -0.95
Ferrous+2 + Hfo_wOH = Hfo_wOFerrous+ + H+
    log_k     -2.98
Ferrous+2 + H2O + Hfo_wOH = Hfo_wOFerrousOH + 2H+
    log_k     -11.55
3H+ + Hfo_wOH + PO4-3 = Hfo_wH2PO4 + H2O
    log_k     31.29
2H+ + Hfo_wOH + PO4-3 = Hfo_wHPO4- + H2O
    log_k     25.39
H+ + Hfo_wOH + PO4-3 = Hfo_wPO4-2 + H2O
    log_k     17.72
H3BO3 + Hfo_wOH = Hfo_wH2BO3 + H2O
    log_k     0.62
H+ + Hfo_wOH + SulfateO4-2 = Hfo_wSulfateO4- + H2O
    log_k     7.78
Hfo_wOH + SulfateO4-2 = Hfo_wOHSulfateO4-2
    log_k     0.79
F- + H+ + Hfo_wOH = Hfo_wF + H2O
    log_k     8.7
F- + Hfo_wOH = Hfo_wOHF-
    log_k     1.6

END


[ahmadreza_shojaee]

Hi David

Thanks for sharing this valuable data.

We had a conversation about adding kinetics of aqueous species reaction. That approach was based on setting rate model for Hdg conversion to H2.

Here you show a database for solving the problem like example 9.
I think the reactions that we are going to add their kinetics to the model play the importing role to modify the database; isn't it?

If my goal is to add kinetics of the following reactions:

Code: [Select]

#Reactions
HCO3- + 4H2 + H+ = CH4 + 3H2O         #MET
2HCO3- + 4H2 + H+ = C2H3O2- + 4H2O  #ACE
SO4-2 + 4H2 + H+ = HS- + 4H2O          #SRB
Should we use the whole modified solution master species/solution species data, or I should just modify elements that are presented in the above three reactions?

Thanks in advance

Ahmad

[dlparkhurst]

At least to start with, I would use the script I put in the other post that converts Hdg to H2 kinetically to produce HS- and CH4 in thermodynamic order, with an additional kinetic reaction to consume Hdg, H, O, and C to produce Acetate.

If you want complete kinetics, I think you will need separate elements for methane, sulfate, sulfide, and acetate.

[ahmadreza_shojaee]

Should I define a new element for carbonate too?

[dlparkhurst]

If you use this uncoupled redox database, CH4 is not defined as part of the C aqueous species, so C is decoupled from Methane.

If you insert pieces of the redox database into another database or an input file, you should insure that the species CH4 is either not defined, or that it is disabled by using a very small log K.

[ahmadreza_shojaee]

I am a bit confused about this reaction in original PHREEQC data base. This reaction represents the Methanogenesis reaction is the original PHREEQC database.

Code: [Select]

CO3-2 + 10 H+ + 8 e- = CH4 + 3 H2O
-log_k 41.071
-delta_h -61.039 kcal
-dw   1.85e-9
-Vm   9.01  -1.11  0  -1.85  -1.50 # ref. 1 + Hnedkovsky et al., 1996, JCT 28, 125

I know that Acetogenesis in not defined in the original database and we can define its kinetics by adding a new element and solution species of Acetate.
For Sulfate reduction, by defining new element for sulfate and sulfide and omitting the below reaction in the new database, we can add the kinetics of this reaction to our model.

Code: [Select]

SO4-2 + 9 H+ + 8 e- = HS- + 4 H2O
-log_k 33.65
-delta_h -60.140 kcal
-gamma 3.5 0
-dw 1.73e-9
-Vm  5.0119  4.9799  3.4765  -2.9849  1.4410 # supcrt

However, for Methanogenesis reaction, if Hydrogen and Carbonate are being introduced to each other, that reaction happens instantly. So, I think maybe we should define a new element for carbonate.

[dlparkhurst]

If the species CH4(aq) is not defined, which means the reaction

Code: [Select]

CO3-2 + 10 H+ + 8 e- = CH4 + 3 H2O
is not included in the database or input file (or the log K for this reaction is very small), then there will be no automatic creation of CH4. You can use "C" to represent C(4) and Methane to represent methane. The creation of Methane from C(4) will require a kinetic reaction.