# File 1 = C:\GitPrograms\phreeqc3-1\database\Amm.dat, 22/05/2024 19:38, 1948 lines, 55817 bytes, md5=78b3659799b73ddca128328b6ee7533b # Created 22 May 2024 19:55:37 # C:\3rdParty\lsp\lsp.exe -f2 -k=asis -ts Amm.dat # PHREEQC.DAT for calculating temperature and pressure dependence of reactions, and the specific conductance and viscosity of the solution. Based on: # diffusion coefficients and molal volumina of aqueous species, solubility and volume of minerals, and critical temperatures and pressures of gases in Peng-Robinson's EOS. # Details are given at the end of this file. SOLUTION_MASTER_SPECIES # #element species alk gfw_formula element_gfw # H H+ -1 H 1.008 H(0) H2 0 H H(1) H+ -1 H E e- 1 0 0 O H2O 0 O 16 O(0) O2 0 O O(-2) H2O 0 0 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 Fe Fe+2 0 Fe 55.847 Fe(+2) Fe+2 0 Fe Fe(+3) Fe+3 -2 Fe Mn Mn+2 0 Mn 54.938 Mn(+2) Mn+2 0 Mn Mn(+3) Mn+3 0 Mn 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 C(-4) CH4 0 CH4 Alkalinity CO3-2 1 Ca0.5(CO3)0.5 50.05 S SO4-2 0 SO4 32.064 S(6) SO4-2 0 SO4 S(-2) HS- 1 S N NO3- 0 N 14.0067 N(+5) NO3- 0 NO3 N(+3) NO2- 0 NO2 N(0) N2 0 N #N(-3) NH4+ 0 NH4 14.0067 Amm AmmH+ 0 AmmH 17.031 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 Cu Cu+2 0 Cu 63.546 Cu(+2) Cu+2 0 Cu Cu(+1) Cu+1 0 Cu # redox-uncoupled gases Hdg Hdg 0 Hdg 2.016 # H2 gas Oxg Oxg 0 Oxg 32 # O2 gas Mtg Mtg 0 Mtg 16.032 # CH4 gas Sg H2Sg 0 H2Sg 32.064 # H2S gas Ntg Ntg 0 Ntg 28.0134 # N2 gas SOLUTION_SPECIES H+ = H+ -gamma 9 0 -viscosity 9.35e-2 -8.31e-2 2.487e-2 4.49e-4 2.01e-2 1.57 # for viscosity parameters see ref. 4 -dw 9.31e-9 838 16.315 0 2.376 24.01 0 # Dw(25 C) dw_T a a2 visc a3 a_v_dif # Dw(TK) = 9.31e-9 * exp(838 / TK - 838 / 298.15) * viscos_0_25 / viscos_0_tc # a = DH ion size, a2 = exponent, visc = viscosity exponent, a3(H+) = 24.01 = new dw calculation from A.D. 2024, a_v_dif = exponent in (viscos_0_tc / viscos)^a_v_dif # For SC, Dw(TK) *= (viscos_0_tc / viscos)^visc (visc = 2.376 for H+) # a3 > 5 or a3 = 0 or not defined ? ka = DH_B * a * (1 + (vm - v0))^a2 * mu^0.5, in Debye-Onsager eqn. (a2 = Vm = 0 for H+, the reference for Vm) # a3 = -10 ? ka = DH_B * a * mu^a2 (Define a3 = -10, not used in this database.) (a3 = 24.01 for H+, a flag.) # -3 < a3 < 4 ? ka = DH_B * a2 * mu^0.5 / (1 + mu^a3), Appelo, 2017: Dw(I) = Dw(TK) * exp(-a * DH_A * z * sqrt_mu / (1 + ka)) (Sr+2 in this database) # If a_v_dif <> 0, Dw(TK) *= (viscos_0_tc / viscos)^a_v_dif in TRANSPORT. e- = e- H2O = H2O -dw 2.299e-9 -254 # H2O + 0.01e- = H2O-0.01; -log_k -9 # aids convergence Li+ = Li+ -gamma 6 0 # The apparent volume parameters are defined in ref. 1 & 2 -Vm -0.419 -0.069 13.16 -2.78 0.416 0 0.296 -12.4 -2.74e-3 1.26 # ref. 2 and Ellis, 1968, J. Chem. Soc. A, 1138 -viscosity 0.162 -2.45e-2 3.73e-2 9.7e-4 8.1e-4 2.087 # < 10 M LiCl -dw 1.03e-9 -14 4.03 0.8341 1.679 Na+ = Na+ -gamma 4 0.075 -gamma 4.08 0.082 # halite solubility -Vm 2.28 -4.38 -4.1 -0.586 0.09 4 0.3 52 -3.33e-3 0.566 # -Vm 2.28 -4.38 -4.1 -0.586 0.09 4 0.3 52 -3.33e-3 0.45 # for densities (rho) when I > 3. -viscosity 0.1387 -8.66e-2 1.25e-2 1.45e-2 7.5e-3 1.062 -dw 1.33e-9 75 3.627 0 0.7037 K+ = K+ -gamma 3.5 0.015 -Vm 3.322 -1.473 6.534 -2.712 9.06e-2 3.5 0 29.7 0 1 -viscosity 0.116 -0.191 1.52e-2 1.4e-2 2.59e-2 0.9028 -dw 1.96e-9 254 3.484 0 0.1964 Mg+2 = Mg+2 -gamma 5.5 0.2 -Vm -1.41 -8.6 11.13 -2.39 1.332 5.5 1.29 -32.9 -5.86e-3 1 -viscosity 0.426 0 0 1.66e-3 4.32e-3 2.461 -dw 0.705e-9 -4 5.569 0 1.047 Ca+2 = Ca+2 -gamma 5 0.165 -Vm -0.3456 -7.252 6.149 -2.479 1.239 5 1.6 -57.1 -6.12e-3 1 -viscosity 0.359 -0.158 4.2e-2 1.5e-3 8.04e-3 2.3 # ref. 4, CaCl2 < 6 M -dw 0.792e-9 34 5.411 0 1.046 Sr+2 = Sr+2 -gamma 5.26 0.121 -Vm -1.57e-2 -10.15 10.18 -2.36 0.86 5.26 0.859 -27 -4.1e-3 1.97 -viscosity 0.472 -0.252 5.51e-3 3.67e-3 0 1.876 -dw 0.794e-9 149 0.805 1.961 1e-9 0.7876 Ba+2 = Ba+2 -gamma 5 0 -gamma 4 0.153 # Barite solubility -Vm 2.063 -10.06 1.9534 -2.36 0.4218 5 1.58 -12.03 -8.35e-3 1 -viscosity 0.338 -0.227 1.39e-2 3.07e-2 0 0.768 -dw 0.848e-9 174 10.53 0 3 Fe+2 = Fe+2 -gamma 6 0 -Vm -0.3255 -9.687 1.536 -2.379 0.3033 6 -4.21e-2 39.7 0 1 -dw 0.719e-9 Mn+2 = Mn+2 -gamma 6 0 -Vm -1.1 -8.03 4.08 -2.45 1.4 6 8.07 0 -1.51e-2 0.118 -dw 0.688e-9 Al+3 = Al+3 -gamma 9 0 -Vm -2.28 -17.1 10.9 -2.07 2.87 9 0 0 5.5e-3 1 # ref. 2 and Barta and Hepler, 1986, Can. J.C. 64, 353 -dw 0.559e-9 H4SiO4 = H4SiO4 -Vm 10.5 1.7 20 -2.7 0.1291 # supcrt 2*H2O in a1 -dw 1.1e-9 Cl- = Cl- -gamma 3.5 0.015 -gamma 3.63 0.017 # cf. pitzer.dat -Vm 4.465 4.801 4.325 -2.847 1.748 0 -0.331 20.16 0 1 -viscosity 0 0 0 0 0 0 1 # the reference solute -dw 2.033e-9 216 3.16 0.2071 0.7432 CO3-2 = CO3-2 -gamma 5.4 0 -Vm 6.09 -2.78 -0.405 -5.3 5.02 0 0.169 101 -1.38e-2 0.9316 -viscosity -0.5 0.6521 5.44e-3 1.06e-3 -2.18e-2 1.208 -2.147 -dw 0.955e-9 -103 2.246 7.13e-2 0.3686 SO4-2 = SO4-2 -gamma 5 -0.04 -Vm -7.77 43.17 176 -51.45 3.794 0 42.99 -541 -0.145 0.45 # with analytical_expressions for log K of NaSO4-, KSO4- & MgSO4, 0 - 200 oC -viscosity -0.3 0.501 2.57e-3 0.195 3.14e-2 2.015 0.605 -dw 1.07e-9 -114 17 6.02e-2 4.94e-2 NO3- = NO3- -gamma 3 0 -Vm 6.32 6.78 0 -3.06 0.346 0 0.93 0 -0.012 1 -viscosity 8.37e-2 -0.458 1.54e-2 0.34 1.79e-2 5.02e-2 0.7381 -dw 1.9e-9 104 1.11 AmmH+ = AmmH+ -gamma 2.5 0 -Vm 5.35 2.345 3.72 -2.88 1.55 2.5 -4.54 217 2.344e-2 0.569 -viscosity 9.9e-2 -0.159 1.36e-2 6.51e-3 3.21e-2 0.972 -dw 1.98e-9 203 1.47 2.644 6.81e-2 H3BO3 = H3BO3 -Vm 7.0643 8.8547 3.5844 -3.1451 -0.2 # supcrt -dw 1.1e-9 PO4-3 = PO4-3 -gamma 4 0 -Vm 1.24 -9.07 9.31 -2.4 5.61 0 0 0 -1.41e-2 1 -dw 0.612e-9 F- = F- -gamma 3.5 0 -Vm 0.928 1.36 6.27 -2.84 1.84 0 0 -0.318 0 1 -viscosity 0 2.85e-2 1.35e-2 6.11e-2 4.38e-3 1.384 0.586 -dw 1.46e-9 -36 4.352 Br- = Br- -gamma 3 0 -Vm 6.72 2.85 4.21 -3.14 1.38 0 -9.56e-2 7.08 -1.56e-3 1 -viscosity -1.15e-2 -5.75e-2 5.72e-2 1.46e-2 0.116 0.9295 0.82 -dw 2.09e-9 208 3.5 0 0.5737 Zn+2 = Zn+2 -gamma 5 0 -Vm -1.96 -10.4 14.3 -2.35 1.46 5 -1.43 24 1.67e-2 1.11 -dw 0.715e-9 Cd+2 = Cd+2 -Vm 1.63 -10.7 1.01 -2.34 1.47 5 0 0 0 1 -dw 0.717e-9 Pb+2 = Pb+2 -Vm -0.0051 -7.7939 8.8134 -2.4568 1.0788 4.5 # supcrt -dw 0.945e-9 Cu+2 = Cu+2 -gamma 6 0 -Vm -1.13 -10.5 7.29 -2.35 1.61 6 9.78e-2 0 3.42e-3 1 -dw 0.733e-9 # redox-uncoupled gases Hdg = Hdg # H2 -Vm 6.52 0.78 0.12 # supcrt -dw 5.13e-9 Oxg = Oxg # O2 -Vm 5.7889 6.3536 3.2528 -3.0417 -0.3943 # supcrt -dw 2.35e-9 Mtg = Mtg # CH4 -Vm 9.01 -1.11 0 -1.85 -1.5 # Hnedkovsky et al., 1996, JCT 28, 125 -dw 1.85e-9 Ntg = Ntg # N2 -Vm 7 # Pray et al., 1952, IEC 44 1146 -dw 1.96e-9 -90 # Cadogan et al. 2014, JCED 59, 519 H2Sg = H2Sg # H2S -Vm 1.39 28.3 0 -7.22 -0.59 # Hnedkovsky et al., 1996, JCT 28, 125 -dw 2.1e-9 # aqueous species H2O = OH- + H+ -analytic 293.29227 0.1360833 -10576.913 -123.73158 0 -6.996455e-5 -gamma 3.5 0 -Vm -9.66 28.5 80 -22.9 1.89 0 1.09 0 0 1 -viscosity -1.02e-1 0.189 9.4e-3 -4e-5 0 3.281 -2.053 # < 5 M Li,Na,KOH -dw 5.27e-9 478 0.8695 2 H2O = O2 + 4 H+ + 4 e- -log_k -86.08 -delta_h 134.79 kcal -Vm 5.7889 6.3536 3.2528 -3.0417 -0.3943 # supcrt -dw 2.35e-9 2 H+ + 2 e- = H2 -log_k -3.15 -delta_h -1.759 kcal -Vm 6.52 0.78 0.12 # supcrt -dw 5.13e-9 H+ + Cl- = HCl -log_k -0.5 -analytical_expression 0.334 -2.684e-3 1.015 # from Pitzer.dat, up to 15 M HCl, 0 - 50°C -gamma 0 0.4256 -viscosity 0.921 -0.765 8.32e-3 8.25e-4 2.53e-3 4.223 CO3-2 + H+ = HCO3- -log_k 10.329; -delta_h -3.561 kcal -analytic 107.8871 0.03252849 -5151.79 -38.92561 563713.9 -gamma 5.4 0 -Vm 10.26 -2.92 -12.58 -0.241 2.23 0 -5.49 320 2.83e-2 1.144 -viscosity -0.6 1.366 -1.216e-2 0e-2 3.139e-2 -1.135 1.253 -dw 1.18e-9 -190 11.386 CO3-2 + 2 H+ = CO2 + H2O -log_k 16.681 -delta_h -5.738 kcal -analytic 464.1965 0.09344813 -26986.16 -165.75951 2248628.9 -Vm 7.29 0.92 2.07 -1.23 -1.6 # McBride et al. 2015, JCED 60, 171 -gamma 0 0.066 # Rumpf et al. 1994, J. Sol. Chem. 23, 431 -dw 1.92e-9 -120 # TK dependence from Cadogan et al. 2014, , JCED 59, 519 2 CO2 = (CO2)2 # activity correction for CO2 solubility at high P, T -log_k -1.8 -analytical_expression 8.68 -0.0103 -2190 -Vm 14.58 1.84 4.14 -2.46 -3.2 -dw 1.92e-9 -120 # TK dependence from Cadogan et al. 2014, , JCED 59, 519 CO3-2 + 10 H+ + 8 e- = CH4 + 3 H2O -log_k 41.071 -delta_h -61.039 kcal -Vm 9.01 -1.11 0 -1.85 -1.5 # Hnedkovsky et al., 1996, JCT 28, 125 -dw 1.85e-9 SO4-2 + H+ = HSO4- -log_k 1.988; -delta_h 3.85 kcal -analytic -56.889 0.006473 2307.9 19.8858 -Vm 8.2 9.259 2.1108 -3.1618 1.1748 0 -0.3 15 0 1 -viscosity 0.5 -6.97e-2 6.07e-2 1e-5 -0.1333 0.4865 0.7987 -dw 1.22e-9 1000 15 2.861 HS- = S-2 + H+ -log_k -12.918 -delta_h 12.1 kcal -gamma 5 0 -dw 0.731e-9 SO4-2 + 9 H+ + 8 e- = HS- + 4 H2O -log_k 33.65 -delta_h -60.14 kcal -gamma 3.5 0 -Vm 5.0119 4.9799 3.4765 -2.9849 1.441 # supcrt -dw 1.73e-9 HS- + H+ = H2S -log_k 6.994; -delta_h -5.3 kcal -analytical -11.17 0.02386 3279 -Vm 1.39 28.3 0 -7.22 -0.59 # Hnedkovsky et al., 1996, JCT 28, 125 -dw 2.1e-9 2 H2S = (H2S)2 # activity correction for H2S solubility at high P, T -analytical_expression 10.227 -0.01384 -2200 -Vm 36.41 -71.95 0 0 2.58 -dw 2.1e-9 H2Sg = HSg- + H+ -log_k -6.994; -delta_h 5.3 kcal -analytical_expression 11.17 -0.02386 -3279 -gamma 3.5 0 -Vm 5.0119 4.9799 3.4765 -2.9849 1.441 # supcrt -dw 1.73e-9 2 H2Sg = (H2Sg)2 # activity correction for H2S solubility at high P, T -analytical_expression 10.227 -0.01384 -2200 -Vm 36.41 -71.95 0 0 2.58 -dw 2.1e-9 NO3- + 2 H+ + 2 e- = NO2- + H2O -log_k 28.57 -delta_h -43.76 kcal -gamma 3 0 -Vm 5.5864 5.859 3.4472 -3.0212 1.1847 # supcrt -dw 1.91e-9 2 NO3- + 12 H+ + 10 e- = N2 + 6 H2O -log_k 207.08 -delta_h -312.13 kcal -Vm 7 # Pray et al., 1952, IEC 44 1146 -dw 1.96e-9 -90 # Cadogan et al. 2014, JCED 59, 519 #NO3- + 10 H+ + 8 e- = AmmH+ + 3 H2O # -log_k 119.077 # -delta_h -187.055 kcal # -gamma 2.5 0 # -Vm 5.35 2.345 3.72 -2.88 1.55 2.5 -4.54 217 2.344e-2 0.569 # -viscosity 9.9e-2 -0.159 1.36e-2 6.51e-3 3.21e-2 0.972 # -dw 1.98e-9 203 1.47 2.644 6.81e-2 AmmH+ = Amm + H+ #NH4+ = NH3 + H+ -log_k -9.252 -delta_h 12.48 kcal -analytic 0.6322 -0.001225 -2835.76 -Vm 6.69 2.8 3.58 -2.88 1.43 -viscosity 0.08 0 0 7.82e-3 -0.134 -0.986 -dw 2.28e-9 AmmH+ + SO4-2 = AmmHSO4- #NH4+ + SO4-2 = NH4SO4- -gamma 6.54 -0.08 -log_k 1.106; -delta_h 4.3 kcal -Vm -3.23 0 -68.42 0 -14.27 0 68.51 0 -0.4099 0.2339 -viscosity 0.24 0 0 3.3e-3 -0.1 0.528 0.748 -dw 1.35e-9 500 12.5 3 -1 H3BO3 = H2BO3- + H+ -log_k -9.24 -delta_h 3.224 kcal H3BO3 + F- = BF(OH)3- -log_k -0.4 -delta_h 1.85 kcal H3BO3 + 2 F- + H+ = BF2(OH)2- + H2O -log_k 7.63 -delta_h 1.618 kcal H3BO3 + 2 H+ + 3 F- = BF3OH- + 2 H2O -log_k 13.67 -delta_h -1.614 kcal H3BO3 + 3 H+ + 4 F- = BF4- + 3 H2O -log_k 20.28 -delta_h -1.846 kcal PO4-3 + H+ = HPO4-2 -log_k 12.346 -delta_h -3.53 kcal -gamma 5 0 -dw 0.69e-9 -Vm 3.52 1.09 8.39 -2.82 3.34 0 0 0 0 1 PO4-3 + 2 H+ = H2PO4- -log_k 19.553 -delta_h -4.52 kcal -gamma 5.4 0 -Vm 5.58 8.06 12.2 -3.11 1.3 0 0 0 1.62e-2 1 -dw 0.846e-9 PO4-3 + 3 H+ = H3PO4 log_k 21.721 # log_k and delta_h from minteq.v4.dat, NIST46.3 delta_h -10.1 kJ -Vm 7.47 12.4 6.29 -3.29 0 H+ + F- = HF -log_k 3.18 -delta_h 3.18 kcal -analytic -2.033 0.012645 429.01 -Vm 3.4753 .7042 5.4732 -2.8081 -.0007 # supcrt H+ + 2 F- = HF2- -log_k 3.76 -delta_h 4.55 kcal -Vm 5.2263 4.9797 3.7928 -2.9849 1.2934 # supcrt Ca+2 + H2O = CaOH+ + H+ -log_k -12.78 Ca+2 + CO3-2 = CaCO3 -log_k 3.224; -delta_h 3.545 kcal -analytic -1228.732 -0.29944 35512.75 485.818 -dw 4.46e-10 # complexes: calc'd with the Pikal formula -Vm -.243 -8.3748 9.0417 -2.4328 -.03 # supcrt Ca+2 + CO3-2 + H+ = CaHCO3+ -log_k 10.91; -delta_h 4.38 kcal -analytic -6.009 3.377e-2 2044 -gamma 6 0 -Vm 30.19 .01 5.75 -2.78 .308 5.4 -dw 5.06e-10 Ca+2 + SO4-2 = CaSO4 -log_k 2.25 -delta_h 1.325 kcal -dw 4.71e-10 -Vm 2.791 -.9666 6.13 -2.739 -.001 # supcrt Ca+2 + HSO4- = CaHSO4+ -log_k 1.08 Ca+2 + PO4-3 = CaPO4- -log_k 6.459 -delta_h 3.1 kcal -gamma 5.4 0 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 -gamma 5.4 0 # Ca+2 + F- = CaF+ # -log_k 0.94 # -delta_h 4.120 kcal # -gamma 5.5 0.0 # -Vm .9846 -5.3773 7.8635 -2.5567 .6911 5.5 # supcrt Mg+2 + H2O = MgOH+ + H+ -log_k -11.44 -delta_h 15.952 kcal -gamma 6.5 0 Mg+2 + CO3-2 = MgCO3 -log_k 2.98 -delta_h 2.713 kcal -analytic 0.991 0.00667 -Vm -0.5837 -9.2067 9.3687 -2.3984 -.03 # supcrt -dw 4.21e-10 Mg+2 + H+ + CO3-2 = MgHCO3+ -log_k 11.399 -delta_h -2.771 kcal -analytic 48.6721 0.03252849 -2614.335 -18.00263 563713.9 -gamma 4 0 -Vm 2.7171 -1.1469 6.2008 -2.7316 .5985 4 # supcrt -dw 4.78e-10 Mg+2 + SO4-2 = MgSO4 -gamma 0 0.2 -log_k 2.42; -delta_h 19 kJ -analytical_expression 0 9.64e-3 -136 # mean salt gamma from Pitzer.dat and epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC -Vm 8.65 -10.21 29.58 -18.6 1.061 -viscosity 0.318 -5.4e-4 -3.42e-2 0.708 3.7e-3 0.696 -dw 4.45e-10 SO4-2 + MgSO4 = Mg(SO4)2-2 -gamma 7 0.047 -log_k 0.52; -delta_h -13.6 kJ -analytical_expression 0 -1.51e-3 0 0 8.604e4 # mean salt gamma from Pitzer.dat and epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC -Vm -8.14 -62.2 -15.96 3.29 -3.01 0 150 0 0.153 3.79e-2 -viscosity -0.169 5e-4 -5.69e-2 0.11 2.03e-3 2.027 -1e-3 -dw 0.845e-9 -200 8 0 0.965 Mg+2 + PO4-3 = MgPO4- -log_k 6.589 -delta_h 3.1 kcal -gamma 5.4 0 Mg+2 + HPO4-2 = MgHPO4 -log_k 2.87 -delta_h 3.3 kcal Mg+2 + H2PO4- = MgH2PO4+ -log_k 1.513 -delta_h 3.4 kcal -gamma 5.4 0 Mg+2 + F- = MgF+ -log_k 1.82 -delta_h 3.2 kcal -gamma 4.5 0 -Vm .6494 -6.1958 8.1852 -2.5229 .9706 4.5 # supcrt Na+ + OH- = NaOH -log_k -10 # remove this complex Na+ + HCO3- = NaHCO3 -log_k -0.06; -delta_h 21 kJ -gamma 0 0.2 -Vm 7.95 0 0 0 0.609 -viscosity -4e-2 -2.717 1.67e-5 -dw 6.73e-10 Na+ + SO4-2 = NaSO4- -gamma 5.5 0 -log_k 0.6; -delta_h -14.4 kJ -analytical_expression 255.903 0.10057 0 -1.11138e2 -8.5983e5 # mirabilite/thenardite solubilities, 0 - 200 oC -Vm 1.99 -10.78 21.88 -12.7 1.601 5 32.38 501 1.565e-2 0.2325 -viscosity 0.2 -5.93e-2 -4e-4 8.46e-3 1.78e-3 2.308 -0.208 -dw 1.13e-9 -23 8.5 0.392 0.521 Na+ + HPO4-2 = NaHPO4- -log_k 0.29 -gamma 5.4 0 -Vm 5.2 8.1 13 -3 0.9 0 0 1.62e-2 1 Na+ + F- = NaF -log_k -0.24 -Vm 2.7483 -1.0708 6.1709 -2.7347 -.03 # supcrt K+ + HCO3- = KHCO3 -log_k -0.35; -delta_h 12 kJ -gamma 0 9.4e-3 -Vm 9.48 0 0 0 -0.542 -viscosity 0.7 -1.289 9e-2 K+ + SO4-2 = KSO4- -gamma 5.4 0.19 -log_k 0.6; -delta_h -10.4 kJ -analytical_expression -3.0246 9.986e-3 0 0 1.093e5 # arcanite solubility, 0 - 200 oC -Vm 13.48 -18.03 61.74 -19.6 2.046 5.4 -17.32 0 0.1522 1.919 -viscosity -1 1.06 1e-4 -0.464 3.78e-2 0.539 -0.69 -dw 0.9e-9 63 8.48 0 1.8 K+ + HPO4-2 = KHPO4- -log_k 0.29 -gamma 5.4 0 -Vm 5.4 8.1 19 -3.1 0.7 0 0 0 1.62e-2 1 Fe+2 + H2O = FeOH+ + H+ -log_k -9.5 -delta_h 13.2 kcal -gamma 5 0 Fe+2 + 3 H2O = Fe(OH)3- + 3 H+ -log_k -31 -delta_h 30.3 kcal -gamma 5 0 Fe+2 + Cl- = FeCl+ -log_k 0.14 Fe+2 + CO3-2 = FeCO3 -log_k 4.38 Fe+2 + HCO3- = FeHCO3+ -log_k 2 Fe+2 + SO4-2 = FeSO4 -log_k 2.25 -delta_h 3.23 kcal -Vm -13 0 123 Fe+2 + HSO4- = FeHSO4+ -log_k 1.08 Fe+2 + 2 HS- = Fe(HS)2 -log_k 8.95 Fe+2 + 3 HS- = Fe(HS)3- -log_k 10.987 Fe+2 + HPO4-2 = FeHPO4 -log_k 3.6 Fe+2 + H2PO4- = FeH2PO4+ -log_k 2.7 -gamma 5.4 0 Fe+2 + F- = FeF+ -log_k 1 Fe+2 = Fe+3 + e- -log_k -13.02 -delta_h 9.68 kcal -gamma 9 0 Fe+3 + H2O = FeOH+2 + H+ -log_k -2.19 -delta_h 10.4 kcal -gamma 5 0 Fe+3 + 2 H2O = Fe(OH)2+ + 2 H+ -log_k -5.67 -delta_h 17.1 kcal -gamma 5.4 0 Fe+3 + 3 H2O = Fe(OH)3 + 3 H+ -log_k -12.56 -delta_h 24.8 kcal Fe+3 + 4 H2O = Fe(OH)4- + 4 H+ -log_k -21.6 -delta_h 31.9 kcal -gamma 5.4 0 Fe+2 + 2 H2O = Fe(OH)2 + 2 H+ -log_k -20.57 -delta_h 28.565 kcal 2 Fe+3 + 2 H2O = Fe2(OH)2+4 + 2 H+ -log_k -2.95 -delta_h 13.5 kcal 3 Fe+3 + 4 H2O = Fe3(OH)4+5 + 4 H+ -log_k -6.3 -delta_h 14.3 kcal Fe+3 + Cl- = FeCl+2 -log_k 1.48 -delta_h 5.6 kcal -gamma 5 0 Fe+3 + 2 Cl- = FeCl2+ -log_k 2.13 -gamma 5 0 Fe+3 + 3 Cl- = FeCl3 -log_k 1.13 Fe+3 + SO4-2 = FeSO4+ -log_k 4.04 -delta_h 3.91 kcal -gamma 5 0 Fe+3 + HSO4- = FeHSO4+2 -log_k 2.48 Fe+3 + 2 SO4-2 = Fe(SO4)2- -log_k 5.38 -delta_h 4.6 kcal Fe+3 + HPO4-2 = FeHPO4+ -log_k 5.43 -delta_h 5.76 kcal -gamma 5 0 Fe+3 + H2PO4- = FeH2PO4+2 -log_k 5.43 -gamma 5.4 0 Fe+3 + F- = FeF+2 -log_k 6.2 -delta_h 2.7 kcal -gamma 5 0 Fe+3 + 2 F- = FeF2+ -log_k 10.8 -delta_h 4.8 kcal -gamma 5 0 Fe+3 + 3 F- = FeF3 -log_k 14 -delta_h 5.4 kcal Mn+2 + H2O = MnOH+ + H+ -log_k -10.59 -delta_h 14.4 kcal -gamma 5 0 Mn+2 + 3 H2O = Mn(OH)3- + 3 H+ -log_k -34.8 -gamma 5 0 Mn+2 + Cl- = MnCl+ -log_k 0.61 -gamma 5 0 -Vm 7.25 -1.08 -25.8 -2.73 3.99 5 0 0 0 1 Mn+2 + 2 Cl- = MnCl2 -log_k 0.25 -Vm 1e-5 0 144 Mn+2 + 3 Cl- = MnCl3- -log_k -0.31 -gamma 5 0 -Vm 11.8 0 0 0 2.4 0 0 0 3.6e-2 1 Mn+2 + CO3-2 = MnCO3 -log_k 4.9 Mn+2 + HCO3- = MnHCO3+ -log_k 1.95 -gamma 5 0 Mn+2 + SO4-2 = MnSO4 -log_k 2.25 -delta_h 3.37 kcal -Vm -1.31 -1.83 62.3 -2.7 Mn+2 + 2 NO3- = Mn(NO3)2 -log_k 0.6 -delta_h -0.396 kcal -Vm 6.16 0 29.4 0 0.9 Mn+2 + F- = MnF+ -log_k 0.84 -gamma 5 0 Mn+2 = Mn+3 + e- -log_k -25.51 -delta_h 25.8 kcal -gamma 9 0 Al+3 + H2O = AlOH+2 + H+ -log_k -5 -delta_h 11.49 kcal -analytic -38.253 0 -656.27 14.327 -gamma 5.4 0 -Vm -1.46 -11.4 10.2 -2.31 1.67 5.4 0 0 0 1 # Barta and Hepler, 1986, Can. J. Chem. 64, 353 Al+3 + 2 H2O = Al(OH)2+ + 2 H+ -log_k -10.1 -delta_h 26.9 kcal -gamma 5.4 0 -analytic 88.5 0 -9391.6 -27.121 Al+3 + 3 H2O = Al(OH)3 + 3 H+ -log_k -16.9 -delta_h 39.89 kcal -analytic 226.374 0 -18247.8 -73.597 Al+3 + 4 H2O = Al(OH)4- + 4 H+ -log_k -22.7 -delta_h 42.3 kcal -analytic 51.578 0 -11168.9 -14.865 -gamma 4.5 0 -dw 1.04e-9 # Mackin & Aller, 1983, GCA 47, 959 Al+3 + SO4-2 = AlSO4+ -log_k 3.5 -delta_h 2.29 kcal -gamma 4.5 0 Al+3 + 2 SO4-2 = Al(SO4)2- -log_k 5 -delta_h 3.11 kcal -gamma 4.5 0 Al+3 + HSO4- = AlHSO4+2 -log_k 0.46 Al+3 + F- = AlF+2 -log_k 7 -delta_h 1.06 kcal -gamma 5.4 0 Al+3 + 2 F- = AlF2+ -log_k 12.7 -delta_h 1.98 kcal -gamma 5.4 0 Al+3 + 3 F- = AlF3 -log_k 16.8 -delta_h 2.16 kcal Al+3 + 4 F- = AlF4- -log_k 19.4 -delta_h 2.2 kcal -gamma 4.5 0 # Al+3 + 5 F- = AlF5-2 # log_k 20.6 # delta_h 1.840 kcal # Al+3 + 6 F- = AlF6-3 # log_k 20.6 # delta_h -1.670 kcal H4SiO4 = H3SiO4- + H+ -log_k -9.83 -delta_h 6.12 kcal -analytic -302.3724 -0.050698 15669.69 108.18466 -1119669 -gamma 4 0 -Vm 7.94 1.0881 5.3224 -2.824 1.4767 # supcrt + H2O in a1 H4SiO4 = H2SiO4-2 + 2 H+ -log_k -23 -delta_h 17.6 kcal -analytic -294.0184 -0.07265 11204.49 108.18466 -1119669 -gamma 5.4 0 H4SiO4 + 4 H+ + 6 F- = SiF6-2 + 4 H2O -log_k 30.18 -delta_h -16.26 kcal -gamma 5 0 -Vm 8.5311 13.0492 .6211 -3.3185 2.7716 # supcrt Ba+2 + H2O = BaOH+ + H+ -log_k -13.47 -gamma 5 0 Ba+2 + CO3-2 = BaCO3 -log_k 2.71 -delta_h 3.55 kcal -analytic 0.113 0.008721 -Vm .2907 -7.0717 8.5295 -2.4867 -.03 # supcrt Ba+2 + HCO3- = BaHCO3+ -log_k 0.982 -delta_h 5.56 kcal -analytic -3.0938 0.013669 Ba+2 + SO4-2 = BaSO4 -log_k 2.7 Sr+2 + H2O = SrOH+ + H+ -log_k -13.29 -gamma 5 0 Sr+2 + CO3-2 + H+ = SrHCO3+ -log_k 11.509 -delta_h 2.489 kcal -analytic 104.6391 0.04739549 -5151.79 -38.92561 563713.9 -gamma 5.4 0 Sr+2 + CO3-2 = SrCO3 -log_k 2.81 -delta_h 5.22 kcal -analytic -1.019 0.012826 -Vm -.1787 -8.2177 8.9799 -2.4393 -.03 # supcrt Sr+2 + SO4-2 = SrSO4 -log_k 2.29 -delta_h 2.08 kcal -Vm 6.791 -.9666 6.13 -2.739 -.001 # celestite solubility Li+ + SO4-2 = LiSO4- -log_k 0.64 -gamma 5 0 Cu+2 + e- = Cu+ -log_k 2.72 -delta_h 1.65 kcal -gamma 2.5 0 Cu+ + 2 Cl- = CuCl2- -log_k 5.5 -delta_h -0.42 kcal -gamma 4 0 Cu+ + 3 Cl- = CuCl3-2 -log_k 5.7 -delta_h 0.26 kcal -gamma 5 0 Cu+2 + CO3-2 = CuCO3 -log_k 6.73 Cu+2 + 2 CO3-2 = Cu(CO3)2-2 -log_k 9.83 Cu+2 + HCO3- = CuHCO3+ -log_k 2.7 Cu+2 + Cl- = CuCl+ -log_k 0.43 -delta_h 8.65 kcal -gamma 4 0 -Vm -4.19 0 30.4 0 0 4 0 0 1.94e-2 1 Cu+2 + 2 Cl- = CuCl2 -log_k 0.16 -delta_h 10.56 kcal -Vm 26.8 0 -136 Cu+2 + 3 Cl- = CuCl3- -log_k -2.29 -delta_h 13.69 kcal -gamma 4 0 Cu+2 + 4 Cl- = CuCl4-2 -log_k -4.59 -delta_h 17.78 kcal -gamma 5 0 Cu+2 + F- = CuF+ -log_k 1.26 -delta_h 1.62 kcal Cu+2 + H2O = CuOH+ + H+ -log_k -8 -gamma 4 0 Cu+2 + 2 H2O = Cu(OH)2 + 2 H+ -log_k -13.68 Cu+2 + 3 H2O = Cu(OH)3- + 3 H+ -log_k -26.9 Cu+2 + 4 H2O = Cu(OH)4-2 + 4 H+ -log_k -39.6 2 Cu+2 + 2 H2O = Cu2(OH)2+2 + 2 H+ -log_k -10.359 -delta_h 17.539 kcal -analytical 2.497 0 -3833 Cu+2 + SO4-2 = CuSO4 -log_k 2.31 -delta_h 1.22 kcal -Vm 5.21 0 -14.6 Cu+2 + 3 HS- = Cu(HS)3- -log_k 25.9 Zn+2 + H2O = ZnOH+ + H+ -log_k -8.96 -delta_h 13.4 kcal Zn+2 + 2 H2O = Zn(OH)2 + 2 H+ -log_k -16.9 Zn+2 + 3 H2O = Zn(OH)3- + 3 H+ -log_k -28.4 Zn+2 + 4 H2O = Zn(OH)4-2 + 4 H+ -log_k -41.2 Zn+2 + Cl- = ZnCl+ -log_k 0.43 -delta_h 7.79 kcal -gamma 4 0 -Vm 14.8 -3.91 -105.7 -2.62 0.203 4 0 0 -5.05e-2 1 Zn+2 + 2 Cl- = ZnCl2 -log_k 0.45 -delta_h 8.5 kcal -Vm -10.1 4.57 241 -2.97 -1e-3 Zn+2 + 3 Cl- = ZnCl3- -log_k 0.5 -delta_h 9.56 kcal -gamma 4 0 -Vm 0.772 15.5 -0.349 -3.42 1.25 0 -7.77 0 0 1 Zn+2 + 4 Cl- = ZnCl4-2 -log_k 0.2 -delta_h 10.96 kcal -gamma 5 0 -Vm 28.42 28 -5.26 -3.94 2.67 0 0 0 4.62e-2 1 Zn+2 + H2O + Cl- = ZnOHCl + H+ -log_k -7.48 Zn+2 + 2 HS- = Zn(HS)2 -log_k 14.94 Zn+2 + 3 HS- = Zn(HS)3- -log_k 16.1 Zn+2 + CO3-2 = ZnCO3 -log_k 5.3 Zn+2 + 2 CO3-2 = Zn(CO3)2-2 -log_k 9.63 Zn+2 + HCO3- = ZnHCO3+ -log_k 2.1 Zn+2 + SO4-2 = ZnSO4 -log_k 2.37 -delta_h 1.36 kcal -Vm 2.51 0 18.8 Zn+2 + 2 SO4-2 = Zn(SO4)2-2 -log_k 3.28 -Vm 10.9 0 -98.7 0 0 0 24 0 -0.236 1 Zn+2 + Br- = ZnBr+ -log_k -0.58 Zn+2 + 2 Br- = ZnBr2 -log_k -0.98 Zn+2 + F- = ZnF+ -log_k 1.15 -delta_h 2.22 kcal Cd+2 + H2O = CdOH+ + H+ -log_k -10.08 -delta_h 13.1 kcal Cd+2 + 2 H2O = Cd(OH)2 + 2 H+ -log_k -20.35 Cd+2 + 3 H2O = Cd(OH)3- + 3 H+ -log_k -33.3 Cd+2 + 4 H2O = Cd(OH)4-2 + 4 H+ -log_k -47.35 2 Cd+2 + H2O = Cd2OH+3 + H+ -log_k -9.39 -delta_h 10.9 kcal Cd+2 + H2O + Cl- = CdOHCl + H+ -log_k -7.404 -delta_h 4.355 kcal Cd+2 + NO3- = CdNO3+ -log_k 0.4 -delta_h -5.2 kcal -Vm 5.95 0 -1.11 0 2.67 7 0 0 1.53e-2 1 Cd+2 + Cl- = CdCl+ -log_k 1.98 -delta_h 0.59 kcal -Vm 5.69 0 -30.2 0 0 6 0 0 0.112 1 Cd+2 + 2 Cl- = CdCl2 -log_k 2.6 -delta_h 1.24 kcal -Vm 5.53 Cd+2 + 3 Cl- = CdCl3- -log_k 2.4 -delta_h 3.9 kcal -Vm 4.6 0 83.9 0 0 0 0 0 0 1 Cd+2 + CO3-2 = CdCO3 -log_k 2.9 Cd+2 + 2 CO3-2 = Cd(CO3)2-2 -log_k 6.4 Cd+2 + HCO3- = CdHCO3+ -log_k 1.5 Cd+2 + SO4-2 = CdSO4 -log_k 2.46 -delta_h 1.08 kcal -Vm 10.4 0 57.9 Cd+2 + 2 SO4-2 = Cd(SO4)2-2 -log_k 3.5 -Vm -6.29 0 -93 0 9.5 7 0 0 0 1 Cd+2 + Br- = CdBr+ -log_k 2.17 -delta_h -0.81 kcal Cd+2 + 2 Br- = CdBr2 -log_k 2.9 Cd+2 + F- = CdF+ -log_k 1.1 Cd+2 + 2 F- = CdF2 -log_k 1.5 Cd+2 + HS- = CdHS+ -log_k 10.17 Cd+2 + 2 HS- = Cd(HS)2 -log_k 16.53 Cd+2 + 3 HS- = Cd(HS)3- -log_k 18.71 Cd+2 + 4 HS- = Cd(HS)4-2 -log_k 20.9 Pb+2 + H2O = PbOH+ + H+ -log_k -7.71 Pb+2 + 2 H2O = Pb(OH)2 + 2 H+ -log_k -17.12 Pb+2 + 3 H2O = Pb(OH)3- + 3 H+ -log_k -28.06 Pb+2 + 4 H2O = Pb(OH)4-2 + 4 H+ -log_k -39.7 2 Pb+2 + H2O = Pb2OH+3 + H+ -log_k -6.36 Pb+2 + Cl- = PbCl+ -log_k 1.6 -delta_h 4.38 kcal -Vm 2.8934 -.7165 6.0316 -2.7494 .1281 6 # supcrt Pb+2 + 2 Cl- = PbCl2 -log_k 1.8 -delta_h 1.08 kcal -Vm 6.5402 8.1879 2.5318 -3.1175 -.03 # supcrt Pb+2 + 3 Cl- = PbCl3- -log_k 1.7 -delta_h 2.17 kcal -Vm 11.0396 19.1743 -1.7863 -3.5717 .7356 # supcrt Pb+2 + 4 Cl- = PbCl4-2 -log_k 1.38 -delta_h 3.53 kcal -Vm 16.415 32.2997 -6.9452 -4.1143 2.3118 # supcrt Pb+2 + CO3-2 = PbCO3 -log_k 7.24 Pb+2 + 2 CO3-2 = Pb(CO3)2-2 -log_k 10.64 Pb+2 + HCO3- = PbHCO3+ -log_k 2.9 Pb+2 + SO4-2 = PbSO4 -log_k 2.75 Pb+2 + 2 SO4-2 = Pb(SO4)2-2 -log_k 3.47 Pb+2 + 2 HS- = Pb(HS)2 -log_k 15.27 Pb+2 + 3 HS- = Pb(HS)3- -log_k 16.57 3 Pb+2 + 4 H2O = Pb3(OH)4+2 + 4 H+ -log_k -23.88 -delta_h 26.5 kcal Pb+2 + NO3- = PbNO3+ -log_k 1.17 Pb+2 + Br- = PbBr+ -log_k 1.77 -delta_h 2.88 kcal Pb+2 + 2 Br- = PbBr2 -log_k 1.44 Pb+2 + F- = PbF+ -log_k 1.25 Pb+2 + 2 F- = PbF2 -log_k 2.56 Pb+2 + 3 F- = PbF3- -log_k 3.42 Pb+2 + 4 F- = PbF4-2 -log_k 3.1 PHASES Calcite CaCO3 = CO3-2 + Ca+2 -log_k -8.48 -delta_h -2.297 kcal -analytic 17.118 -0.046528 -3496 # 0 - 250°C, Ellis, 1959, Plummer and Busenberg, 1982 -Vm 36.9 cm3/mol # MW (100.09 g/mol) / rho (2.71 g/cm3) Aragonite CaCO3 = CO3-2 + Ca+2 -log_k -8.336 -delta_h -2.589 kcal -analytic -171.9773 -0.077993 2903.293 71.595 -Vm 34.04 Dolomite CaMg(CO3)2 = Ca+2 + Mg+2 + 2 CO3-2 -log_k -17.09 -delta_h -9.436 kcal -analytic 31.283 -0.0898 -6438 # 25°C: Hemingway and Robie, 1994; 50–175°C: Bénézeth et al., 2018, GCA 224, 262-275 -Vm 64.5 Siderite FeCO3 = Fe+2 + CO3-2 -log_k -10.89 -delta_h -2.48 kcal -Vm 29.2 Rhodochrosite MnCO3 = Mn+2 + CO3-2 -log_k -11.13 -delta_h -1.43 kcal -Vm 31.1 Strontianite SrCO3 = Sr+2 + CO3-2 -log_k -9.271 -delta_h -0.4 kcal -analytic 155.0305 0 -7239.594 -56.58638 -Vm 39.69 Witherite BaCO3 = Ba+2 + CO3-2 -log_k -8.562 -delta_h 0.703 kcal -analytic 607.642 0.121098 -20011.25 -236.4948 -Vm 46 Gypsum CaSO4:2H2O = Ca+2 + SO4-2 + 2 H2O -log_k -4.58 -delta_h -0.109 kcal -analytic 68.2401 0 -3221.51 -25.0627 -analytical_expression 93.7 5.99E-3 -4e3 -35.019 # better fits the appendix data of Appelo, 2015, AG 55, 62 -Vm 73.9 # 172.18 / 2.33 (Vm H2O = 13.9 cm3/mol) Anhydrite CaSO4 = Ca+2 + SO4-2 -log_k -4.36 -delta_h -1.71 kcal -analytic 84.9 0 -3135.12 -31.79 # 50 - 160oC, 1 - 1e3 atm, anhydrite dissolution, Blount and Dickson, 1973, Am. Mineral. 58, 323 -Vm 46.1 # 136.14 / 2.95 Celestite SrSO4 = Sr+2 + SO4-2 -log_k -6.63 -delta_h -4.037 kcal # -analytic -14805.9622 -2.4660924 756968.533 5436.3588 -40553604.0 -analytic -7.14 6.11e-3 75 0 0 -1.79e-5 # Howell et al., 1992, JCED 37, 464 -Vm 46.4 Barite BaSO4 = Ba+2 + SO4-2 -log_k -9.97 -delta_h 6.35 kcal -analytical_expression -282.43 -8.972e-2 5822 113.08 # Blount 1977; Templeton, 1960 -Vm 52.9 Arcanite K2SO4 = SO4-2 + 2 K+ log_k -1.776; -delta_h 5 kcal -analytical_expression 674.142 0.30423 -18037 -280.236 0 -1.44055e-4 # ref. 3 # Note, the Linke and Seidell data may give subsaturation in other xpt's, SI = -0.06 -Vm 65.5 Mirabilite Na2SO4:10H2O = SO4-2 + 2 Na+ + 10 H2O -analytical_expression -301.9326 -0.16232 0 141.078 # ref. 3 Vm 216 Thenardite Na2SO4 = 2 Na+ + SO4-2 -analytical_expression 57.185 8.6024e-2 0 -30.8341 0 -7.6905e-5 # ref. 3 -Vm 52.9 Epsomite MgSO4:7H2O = Mg+2 + SO4-2 + 7 H2O log_k -1.74; -delta_h 10.57 kJ -analytical_expression -3.59 6.21e-3 Vm 147 Hexahydrite MgSO4:6H2O = Mg+2 + SO4-2 + 6 H2O log_k -1.57; -delta_h 2.35 kJ -analytical_expression -1.978 1.38e-3 Vm 132 Kieserite MgSO4:H2O = Mg+2 + SO4-2 + H2O log_k -1.16; -delta_h 9.22 kJ -analytical_expression 29.485 -5.07e-2 0 -2.662 -7.95e5 Vm 53.8 Hydroxyapatite Ca5(PO4)3OH + 4 H+ = H2O + 3 HPO4-2 + 5 Ca+2 -log_k -3.421 -delta_h -36.155 kcal -Vm 128.9 Fluorite CaF2 = Ca+2 + 2 F- -log_k -10.6 -delta_h 4.69 kcal -analytic 66.348 0 -4298.2 -25.271 -Vm 15.7 SiO2(a) SiO2 + 2 H2O = H4SiO4 -log_k -2.71 -delta_h 3.34 kcal -analytic -0.26 0 -731 Chalcedony SiO2 + 2 H2O = H4SiO4 -log_k -3.55 -delta_h 4.72 kcal -analytic -0.09 0 -1032 -Vm 23.1 Quartz SiO2 + 2 H2O = H4SiO4 -log_k -3.98 -delta_h 5.99 kcal -analytic 0.41 0 -1309 -Vm 22.67 Gibbsite Al(OH)3 + 3 H+ = Al+3 + 3 H2O -log_k 8.11 -delta_h -22.8 kcal -Vm 32.22 Al(OH)3(a) Al(OH)3 + 3 H+ = Al+3 + 3 H2O -log_k 10.8 -delta_h -26.5 kcal Kaolinite Al2Si2O5(OH)4 + 6 H+ = H2O + 2 H4SiO4 + 2 Al+3 -log_k 7.435 -delta_h -35.3 kcal -Vm 99.35 Albite NaAlSi3O8 + 8 H2O = Na+ + Al(OH)4- + 3 H4SiO4 -log_k -18.002 -delta_h 25.896 kcal -Vm 101.31 Anorthite CaAl2Si2O8 + 8 H2O = Ca+2 + 2 Al(OH)4- + 2 H4SiO4 -log_k -19.714 -delta_h 11.58 kcal -Vm 105.05 K-feldspar KAlSi3O8 + 8 H2O = K+ + Al(OH)4- + 3 H4SiO4 -log_k -20.573 -delta_h 30.82 kcal -Vm 108.15 K-mica KAl3Si3O10(OH)2 + 10 H+ = K+ + 3 Al+3 + 3 H4SiO4 -log_k 12.703 -delta_h -59.376 kcal Chlorite(14A) Mg5Al2Si3O10(OH)8 + 16 H+ = 5 Mg+2 + 2 Al+3 + 3 H4SiO4 + 6 H2O -log_k 68.38 -delta_h -151.494 kcal Ca-Montmorillonite Ca0.165Al2.33Si3.67O10(OH)2 + 12 H2O = 0.165 Ca+2 + 2.33 Al(OH)4- + 3.67 H4SiO4 + 2 H+ -log_k -45.027 -delta_h 58.373 kcal -Vm 156.16 Talc Mg3Si4O10(OH)2 + 4 H2O + 6 H+ = 3 Mg+2 + 4 H4SiO4 -log_k 21.399 -delta_h -46.352 kcal -Vm 68.34 Illite K0.6Mg0.25Al2.3Si3.5O10(OH)2 + 11.2 H2O = 0.6 K+ + 0.25 Mg+2 + 2.3 Al(OH)4- + 3.5 H4SiO4 + 1.2 H+ -log_k -40.267 -delta_h 54.684 kcal -Vm 141.48 Chrysotile Mg3Si2O5(OH)4 + 6 H+ = H2O + 2 H4SiO4 + 3 Mg+2 -log_k 32.2 -delta_h -46.8 kcal -analytic 13.248 0 10217.1 -6.1894 -Vm 106.5808 # 277.11/2.60 Sepiolite Mg2Si3O7.5OH:3H2O + 4 H+ + 0.5 H2O = 2 Mg+2 + 3 H4SiO4 -log_k 15.76 -delta_h -10.7 kcal -Vm 143.765 Sepiolite(d) Mg2Si3O7.5OH:3H2O + 4 H+ + 0.5 H2O = 2 Mg+2 + 3 H4SiO4 -log_k 18.66 Hematite Fe2O3 + 6 H+ = 2 Fe+3 + 3 H2O -log_k -4.008 -delta_h -30.845 kcal -Vm 30.39 Goethite FeOOH + 3 H+ = Fe+3 + 2 H2O -log_k -1 -delta_h -14.48 kcal -Vm 20.84 Fe(OH)3(a) Fe(OH)3 + 3 H+ = Fe+3 + 3 H2O -log_k 4.891 Pyrite FeS2 + 2 H+ + 2 e- = Fe+2 + 2 HS- -log_k -18.479 -delta_h 11.3 kcal -Vm 23.48 FeS(ppt) FeS + H+ = Fe+2 + HS- -log_k -3.915 Mackinawite FeS + H+ = Fe+2 + HS- -log_k -4.648 -Vm 20.45 Sulfur S + 2 H+ + 2 e- = H2S -log_k 4.882 -delta_h -9.5 kcal Vivianite Fe3(PO4)2:8H2O = 3 Fe+2 + 2 PO4-3 + 8 H2O -log_k -36 Pyrolusite # H2O added for surface calc's MnO2:H2O + 4 H+ + 2 e- = Mn+2 + 3 H2O -log_k 41.38 -delta_h -65.11 kcal Hausmannite Mn3O4 + 8 H+ + 2 e- = 3 Mn+2 + 4 H2O -log_k 61.03 -delta_h -100.64 kcal Manganite MnOOH + 3 H+ + e- = Mn+2 + 2 H2O -log_k 25.34 Pyrochroite Mn(OH)2 + 2 H+ = Mn+2 + 2 H2O -log_k 15.2 Halite NaCl = Cl- + Na+ log_k 1.57 -delta_h 1.37 #-analytic -713.4616 -.1201241 37302.21 262.4583 -2106915. -Vm 27.1 Sylvite KCl = K+ + Cl- log_k 0.9 -delta_h 8.5 # -analytic 3.984 0.0 -919.55 Vm 37.5 # Gases... CO2(g) CO2 = CO2 -log_k -1.468 -delta_h -4.776 kcal -analytic 10.5624 -2.3547e-2 -3972.8 0 5.8746e5 1.9194e-5 -T_c 304.2 # critical T, K -P_c 72.86 # critical P, atm -Omega 0.225 # acentric factor H2O(g) H2O = H2O -log_k 1.506; delta_h -44.03 kJ -T_c 647.3; -P_c 217.6; -Omega 0.344 -analytic -16.5066 -2.0013E-3 2710.7 3.7646 0 2.24E-6 O2(g) O2 = O2 -log_k -2.8983 -analytic -7.5001 7.8981e-3 0 0 2.0027e5 -T_c 154.6; -P_c 49.8; -Omega 0.021 H2(g) H2 = H2 -log_k -3.105 -delta_h -4.184 kJ -analytic -9.3114 4.6473e-3 -49.335 1.4341 1.2815e5 -T_c 33.2; -P_c 12.8; -Omega -0.225 N2(g) N2 = N2 -log_k -3.1864 -analytic -58.453 1.818e-3 3199 17.909 -27460 -T_c 126.2; -P_c 33.5; -Omega 0.039 H2S(g) H2S = H+ + HS- log_k -7.93 -delta_h 9.1 -analytic -45.07 -0.02418 0 17.9205 # H2S solubilities, 0 - 300°C, 1 - 987 atm, Jiang et al., 2020, CG 555, 119816 -T_c 373.2; -P_c 88.2; -Omega 0.1 CH4(g) CH4 = CH4 -log_k -2.8 -analytic 10.44 -7.65e-3 -6669 0 1.014e6 # CH4 solubilities 25 - 100°C -T_c 190.6; -P_c 45.4; -Omega 0.008 Amm(g) Amm = Amm #NH3(g) # NH3 = NH3 -log_k 1.7966 -analytic -18.758 3.367e-4 2.5113e3 4.8619 39.192 -T_c 405.6; -P_c 111.3; -Omega 0.25 # redox-uncoupled gases Oxg(g) Oxg = Oxg -analytic -7.5001 7.8981e-3 0 0 2.0027e5 -T_c 154.6; -P_c 49.8; -Omega 0.021 Hdg(g) Hdg = Hdg -analytic -9.3114 4.6473e-3 -49.335 1.4341 1.2815e5 -T_c 33.2; -P_c 12.8; -Omega -0.225 Ntg(g) Ntg = Ntg -analytic -58.453 1.818e-3 3199 17.909 -27460 T_c 126.2; -P_c 33.5; -Omega 0.039 Mtg(g) Mtg = Mtg -log_k -2.8 -analytic 10.44 -7.65e-3 -6669 0 1.014e6 # CH4 solubilities 25 - 100°C -T_c 190.6; -P_c 45.4; -Omega 0.008 H2Sg(g) H2Sg = H+ + HSg- log_k -7.93 -delta_h 9.1 -analytic -45.07 -0.02418 0 17.9205 # H2S solubilities, 0 - 300°C, 1 - 987 atm, Jiang et al., 2020, CG 555, 119816 -T_c 373.2; -P_c 88.2; -Omega 0.1 Melanterite FeSO4:7H2O = 7 H2O + Fe+2 + SO4-2 -log_k -2.209 -delta_h 4.91 kcal -analytic 1.447 -0.004153 0 0 -214949 Alunite KAl3(SO4)2(OH)6 + 6 H+ = K+ + 3 Al+3 + 2 SO4-2 + 6 H2O -log_k -1.4 -delta_h -50.25 kcal Jarosite-K KFe3(SO4)2(OH)6 + 6 H+ = 3 Fe+3 + 6 H2O + K+ + 2 SO4-2 -log_k -9.21 -delta_h -31.28 kcal Zn(OH)2(e) Zn(OH)2 + 2 H+ = Zn+2 + 2 H2O -log_k 11.5 Smithsonite ZnCO3 = Zn+2 + CO3-2 -log_k -10 -delta_h -4.36 kcal Sphalerite ZnS + H+ = Zn+2 + HS- -log_k -11.618 -delta_h 8.25 kcal Willemite 289 Zn2SiO4 + 4 H+ = 2 Zn+2 + H4SiO4 -log_k 15.33 -delta_h -33.37 kcal Cd(OH)2 Cd(OH)2 + 2 H+ = Cd+2 + 2 H2O -log_k 13.65 Otavite 315 CdCO3 = Cd+2 + CO3-2 -log_k -12.1 -delta_h -0.019 kcal CdSiO3 328 CdSiO3 + H2O + 2 H+ = Cd+2 + H4SiO4 -log_k 9.06 -delta_h -16.63 kcal CdSO4 329 CdSO4 = Cd+2 + SO4-2 -log_k -0.1 -delta_h -14.74 kcal Cerussite 365 PbCO3 = Pb+2 + CO3-2 -log_k -13.13 -delta_h 4.86 kcal Anglesite 384 PbSO4 = Pb+2 + SO4-2 -log_k -7.79 -delta_h 2.15 kcal Pb(OH)2 389 Pb(OH)2 + 2 H+ = Pb+2 + 2 H2O -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 4.08 0.082 K+ + X- = KX -log_k 0.7 -gamma 3.5 0.015 -delta_h -4.3 # Jardine & Sparks, 1984 Li+ + X- = LiX -log_k -0.08 -gamma 6 0 -delta_h 1.4 # Merriam & Thomas, 1956 # !!!!! # H+ + X- = HX # -log_k 1.0 # -gamma 9.0 0 AmmH+ + X- = AmmHX # NH4+ + X- = NH4X -log_k 0.6 -gamma 2.5 0 -delta_h -2.4 # Laudelout et al., 1968 Ca+2 + 2 X- = CaX2 -log_k 0.8 -gamma 5 0.165 -delta_h 7.2 # Van Bladel & Gheyl, 1980 Mg+2 + 2 X- = MgX2 -log_k 0.6 -gamma 5.5 0.2 -delta_h 7.4 # Laudelout et al., 1968 Sr+2 + 2 X- = SrX2 -log_k 0.91 -gamma 5.26 0.121 -delta_h 5.5 # Laudelout et al., 1968 Ba+2 + 2 X- = BaX2 -log_k 0.91 -gamma 4 0.153 -delta_h 4.5 # Laudelout et al., 1968 Mn+2 + 2 X- = MnX2 -log_k 0.52 -gamma 6 0 Fe+2 + 2 X- = FeX2 -log_k 0.44 -gamma 6 0 Cu+2 + 2 X- = CuX2 -log_k 0.6 -gamma 6 0 Zn+2 + 2 X- = ZnX2 -log_k 0.8 -gamma 5 0 Cd+2 + 2 X- = CdX2 -log_k 0.8 -gamma 0 0 Pb+2 + 2 X- = PbX2 -log_k 1.05 -gamma 0 0 Al+3 + 3 X- = AlX3 -log_k 0.41 -gamma 9 0 AlOH+2 + 2 X- = AlOHX2 -log_k 0.89 -gamma 0 0 SURFACE_MASTER_SPECIES Hfo_s Hfo_sOH Hfo_w Hfo_wOH SURFACE_SPECIES # All surface data from # Dzombak and Morel, 1990 # # # Acid-base data from table 5.7 # # strong binding site--Hfo_s, Hfo_sOH = Hfo_sOH -log_k 0 Hfo_sOH + H+ = Hfo_sOH2+ -log_k 7.29 # = pKa1,int Hfo_sOH = Hfo_sO- + H+ -log_k -8.93 # = -pKa2,int # weak binding site--Hfo_w Hfo_wOH = Hfo_wOH -log_k 0 Hfo_wOH + H+ = Hfo_wOH2+ -log_k 7.29 # = pKa1,int Hfo_wOH = Hfo_wO- + H+ -log_k -8.93 # = -pKa2,int ############################################### # CATIONS # ############################################### # # Cations from table 10.1 or 10.5 # # Calcium Hfo_sOH + Ca+2 = Hfo_sOHCa+2 -log_k 4.97 Hfo_wOH + Ca+2 = Hfo_wOCa+ + H+ -log_k -5.85 # Strontium Hfo_sOH + Sr+2 = Hfo_sOHSr+2 -log_k 5.01 Hfo_wOH + Sr+2 = Hfo_wOSr+ + H+ -log_k -6.58 Hfo_wOH + Sr+2 + H2O = Hfo_wOSrOH + 2 H+ -log_k -17.6 # Barium Hfo_sOH + Ba+2 = Hfo_sOHBa+2 -log_k 5.46 Hfo_wOH + Ba+2 = Hfo_wOBa+ + H+ -log_k -7.2 # table 10.5 # # Cations from table 10.2 # # Cadmium Hfo_sOH + Cd+2 = Hfo_sOCd+ + H+ -log_k 0.47 Hfo_wOH + Cd+2 = Hfo_wOCd+ + H+ -log_k -2.91 # Zinc Hfo_sOH + Zn+2 = Hfo_sOZn+ + H+ -log_k 0.99 Hfo_wOH + Zn+2 = Hfo_wOZn+ + H+ -log_k -1.99 # Copper Hfo_sOH + Cu+2 = Hfo_sOCu+ + H+ -log_k 2.89 Hfo_wOH + Cu+2 = Hfo_wOCu+ + H+ -log_k 0.6 # table 10.5 # Lead Hfo_sOH + Pb+2 = Hfo_sOPb+ + H+ -log_k 4.65 Hfo_wOH + Pb+2 = Hfo_wOPb+ + H+ -log_k 0.3 # table 10.5 # # Derived constants table 10.5 # # Magnesium Hfo_wOH + Mg+2 = Hfo_wOMg+ + H+ -log_k -4.6 # Manganese Hfo_sOH + Mn+2 = Hfo_sOMn+ + H+ -log_k -0.4 # table 10.5 Hfo_wOH + Mn+2 = Hfo_wOMn+ + H+ -log_k -3.5 # table 10.5 # Iron, strong site: Appelo, Van der Weiden, Tournassat & Charlet, EST 36, 3096 Hfo_sOH + Fe+2 = Hfo_sOFe+ + H+ -log_k -0.95 # Iron, weak site: Liger et al., GCA 63, 2939, re-optimized for D&M Hfo_wOH + Fe+2 = Hfo_wOFe+ + H+ -log_k -2.98 Hfo_wOH + Fe+2 + H2O = Hfo_wOFeOH + 2 H+ -log_k -11.55 ############################################### # ANIONS # ############################################### # # Anions from table 10.6 # # Phosphate Hfo_wOH + PO4-3 + 3 H+ = Hfo_wH2PO4 + H2O -log_k 31.29 Hfo_wOH + PO4-3 + 2 H+ = Hfo_wHPO4- + H2O -log_k 25.39 Hfo_wOH + PO4-3 + H+ = Hfo_wPO4-2 + H2O -log_k 17.72 # # Anions from table 10.7 # # Borate Hfo_wOH + H3BO3 = Hfo_wH2BO3 + H2O -log_k 0.62 # # Anions from table 10.8 # # Sulfate Hfo_wOH + SO4-2 + H+ = Hfo_wSO4- + H2O -log_k 7.78 Hfo_wOH + SO4-2 = Hfo_wOHSO4-2 -log_k 0.79 # # Derived constants table 10.10 # Hfo_wOH + F- + H+ = Hfo_wF + H2O -log_k 8.7 Hfo_wOH + F- = Hfo_wOHF- -log_k 1.6 # # Carbonate: Van Geen et al., 1994 reoptimized for D&M model # Hfo_wOH + CO3-2 + H+ = Hfo_wCO3- + H2O -log_k 12.56 Hfo_wOH + CO3-2 + 2 H+ = Hfo_wHCO3 + H2O -log_k 20.62 # # Silicate: Swedlund, P.J. and Webster, J.G., 1999. Water Research 33, 3413-3422. # Hfo_wOH + H4SiO4 = Hfo_wH3SiO4 + H2O ; log_K 4.28 Hfo_wOH + H4SiO4 = Hfo_wH2SiO4- + H+ + H2O; log_K -3.22 Hfo_wOH + H4SiO4 = Hfo_wHSiO4-2 + 2 H+ + H2O; log_K -11.69 MEAN_GAMMAS CaCl2 Ca+2 1 Cl- 2 CaSO4 Ca+2 1 SO4-2 1 CaCO3 Ca+2 1 CO3-2 1 Ca(OH)2 Ca+2 1 OH- 2 MgCl2 Mg+2 1 Cl- 2 MgSO4 Mg+2 1 SO4-2 1 MgCO3 Mg+2 1 CO3-2 1 Mg(OH)2 Mg+2 1 OH- 2 NaCl Na+ 1 Cl- 1 Na2SO4 Na+ 2 SO4-2 1 NaHCO3 Na+ 1 HCO3- 1 Na2CO3 Na+ 2 CO3-2 1 NaOH Na+ 1 OH- 1 KCl K+ 1 Cl- 1 K2SO4 K+ 2 SO4-2 1 HCO3 K+ 1 HCO3- 1 K2CO3 K+ 2 CO3-2 1 KOH K+ 1 OH- 1 HCl H+ 1 Cl- 1 H2SO4 H+ 2 SO4-2 1 HBr H+ 1 Br- 1 RATES ########### #Quartz ########### # ####### # Example of quartz kinetic rates block: # KINETICS # Quartz # -m0 158.8 # 90 % Qu # -parms 0.146 1.5 # -step 3.1536e8 in 10 # -tol 1e-12 Quartz -start 1 REM Specific rate k from Rimstidt and Barnes, 1980, GCA 44,1683 2 REM k = 10^-13.7 mol/m2/s (25 C), Ea = 90 kJ/mol 3 REM sp. rate * parm(2) due to salts (Dove and Rimstidt, MSA Rev. 29, 259) 4 REM PARM(1) = Specific area of Quartz, m^2/mol Quartz 5 REM PARM(2) = salt correction: (1 + 1.5 * c_Na (mM)), < 35 10 dif_temp = 1/TK - 1/298 20 pk_w = 13.7 + 4700.4 * dif_temp 40 moles = PARM(1) * M0 * PARM(2) * (M/M0)^0.67 * 10^-pk_w * (1 - SR("Quartz")) # Integrate... 50 SAVE moles * TIME -end ########### #K-feldspar ########### # # Sverdrup and Warfvinge, 1995, Estimating field weathering rates # using laboratory kinetics: Reviews in mineralogy and geochemistry, # vol. 31, p. 485-541. # # As described in: # Appelo and Postma, 2005, Geochemistry, groundwater # and pollution, 2nd Edition: A.A. Balkema Publishers, # p. 162-163 and 395-399. # # Assume soil is 10% K-feldspar by mass in 1 mm spheres (radius 0.05 mm) # Assume density of rock and Kspar is 2600 kg/m^3 = 2.6 kg/L # GFW Kspar 0.278 kg/mol # # Moles of Kspar per liter pore space calculation: # Mass of rock per liter pore space = 0.7*2.6/0.3 = 6.07 kg rock/L pore space # Mass of Kspar per liter pore space 6.07x0.1 = 0.607 kg Kspar/L pore space # Moles of Kspar per liter pore space 0.607/0.278 = 2.18 mol Kspar/L pore space # # Specific area calculation: # Volume of sphere 4/3 x pi x r^3 = 5.24e-13 m^3 Kspar/sphere # Mass of sphere 2600 x 5.24e-13 = 1.36e-9 kg Kspar/sphere # Moles of Kspar in sphere 1.36e-9/0.278 = 4.90e-9 mol Kspar/sphere # Surface area of one sphere 4 x pi x r^2 = 3.14e-8 m^2/sphere # Specific area of K-feldspar in sphere 3.14e-8/4.90e-9 = 6.41 m^2/mol Kspar # # # Example of KINETICS data block for K-feldspar rate: # KINETICS 1 # K-feldspar # -m0 2.18 # 10% Kspar, 0.1 mm cubes # -m 2.18 # Moles per L pore space # -parms 6.41 0.1 # m^2/mol Kspar, fraction adjusts lab rate to field rate # -time 1.5 year in 40 K-feldspar -start 1 REM Sverdrup and Warfvinge, 1995, mol m^-2 s^-1 2 REM PARM(1) = Specific area of Kspar m^2/mol Kspar 3 REM PARM(2) = Adjusts lab rate to field rate 4 REM temp corr: from A&P, p. 162: E (kJ/mol) / R / 2.303 = H in H*(1/T-1/281) 5 REM K-Feldspar parameters 10 DATA 11.7, 0.5, 4e-6, 0.4, 500e-6, 0.15, 14.5, 0.14, 0.15, 13.1, 0.3 20 RESTORE 10 30 READ pK_H, n_H, lim_Al, x_Al, lim_BC, x_BC, pK_H2O, z_Al, z_BC, pK_OH, o_OH 40 DATA 3500, 2000, 2500, 2000 50 RESTORE 40 60 READ e_H, e_H2O, e_OH, e_CO2 70 pk_CO2 = 13 80 n_CO2 = 0.6 100 REM Generic rate follows 110 dif_temp = 1/TK - 1/281 120 BC = ACT("Na+") + ACT("K+") + ACT("Mg+2") + ACT("Ca+2") 130 REM rate by H+ 140 pk_H = pk_H + e_H * dif_temp 150 rate_H = 10^-pk_H * ACT("H+")^n_H / ((1 + ACT("Al+3") / lim_Al)^x_Al * (1 + BC / lim_BC)^x_BC) 160 REM rate by hydrolysis 170 pk_H2O = pk_H2O + e_H2O * dif_temp 180 rate_H2O = 10^-pk_H2O / ((1 + ACT("Al+3") / lim_Al)^z_Al * (1 + BC / lim_BC)^z_BC) 190 REM rate by OH- 200 pk_OH = pk_OH + e_OH * dif_temp 210 rate_OH = 10^-pk_OH * ACT("OH-")^o_OH 220 REM rate by CO2 230 pk_CO2 = pk_CO2 + e_CO2 * dif_temp 240 rate_CO2 = 10^-pk_CO2 * (SR("CO2(g)"))^n_CO2 250 rate = rate_H + rate_H2O + rate_OH + rate_CO2 260 area = PARM(1) * M0 *(M/M0)^0.67 270 rate = PARM(2) * area * rate * (1-SR("K-feldspar")) 280 moles = rate * TIME 290 SAVE moles -end ########### #Albite ########### # # Sverdrup and Warfvinge, 1995, Estimating field weathering rates # using laboratory kinetics: Reviews in mineralogy and geochemistry, # vol. 31, p. 485-541. # # As described in: # Appelo and Postma, 2005, Geochemistry, groundwater # and pollution, 2nd Edition: A.A. Balkema Publishers, # p. 162-163 and 395-399. # # Example of KINETICS data block for Albite rate: # KINETICS 1 # Albite # -m0 0.46 # 2% Albite, 0.1 mm cubes # -m 0.46 # Moles per L pore space # -parms 6.04 0.1 # m^2/mol Albite, fraction adjusts lab rate to field rate # -time 1.5 year in 40 # # Assume soil is 2% Albite by mass in 1 mm spheres (radius 0.05 mm) # Assume density of rock and Albite is 2600 kg/m^3 = 2.6 kg/L # GFW Albite 0.262 kg/mol # # Moles of Albite per liter pore space calculation: # Mass of rock per liter pore space = 0.7*2.6/0.3 = 6.07 kg rock/L pore space # Mass of Albite per liter pore space 6.07x0.02 = 0.121 kg Albite/L pore space # Moles of Albite per liter pore space 0.607/0.262 = 0.46 mol Albite/L pore space # # Specific area calculation: # Volume of sphere 4/3 x pi x r^3 = 5.24e-13 m^3 Albite/sphere # Mass of sphere 2600 x 5.24e-13 = 1.36e-9 kg Albite/sphere # Moles of Albite in sphere 1.36e-9/0.262 = 5.20e-9 mol Albite/sphere # Surface area of one sphere 4 x pi x r^2 = 3.14e-8 m^2/sphere # Specific area of Albite in sphere 3.14e-8/5.20e-9 = 6.04 m^2/mol Albite Albite -start 1 REM Sverdrup and Warfvinge, 1995, mol m^-2 s^-1 2 REM PARM(1) = Specific area of Albite m^2/mol Albite 3 REM PARM(2) = Adjusts lab rate to field rate 4 REM temp corr: from A&P, p. 162 E (kJ/mol) / R / 2.303 = H in H*(1/T-1/281) 5 REM Albite parameters 10 DATA 11.5, 0.5, 4e-6, 0.4, 500e-6, 0.2, 13.7, 0.14, 0.15, 11.8, 0.3 20 RESTORE 10 30 READ pK_H, n_H, lim_Al, x_Al, lim_BC, x_BC, pK_H2O, z_Al, z_BC, pK_OH, o_OH 40 DATA 3500, 2000, 2500, 2000 50 RESTORE 40 60 READ e_H, e_H2O, e_OH, e_CO2 70 pk_CO2 = 13 80 n_CO2 = 0.6 100 REM Generic rate follows 110 dif_temp = 1/TK - 1/281 120 BC = ACT("Na+") + ACT("K+") + ACT("Mg+2") + ACT("Ca+2") 130 REM rate by H+ 140 pk_H = pk_H + e_H * dif_temp 150 rate_H = 10^-pk_H * ACT("H+")^n_H / ((1 + ACT("Al+3") / lim_Al)^x_Al * (1 + BC / lim_BC)^x_BC) 160 REM rate by hydrolysis 170 pk_H2O = pk_H2O + e_H2O * dif_temp 180 rate_H2O = 10^-pk_H2O / ((1 + ACT("Al+3") / lim_Al)^z_Al * (1 + BC / lim_BC)^z_BC) 190 REM rate by OH- 200 pk_OH = pk_OH + e_OH * dif_temp 210 rate_OH = 10^-pk_OH * ACT("OH-")^o_OH 220 REM rate by CO2 230 pk_CO2 = pk_CO2 + e_CO2 * dif_temp 240 rate_CO2 = 10^-pk_CO2 * (SR("CO2(g)"))^n_CO2 250 rate = rate_H + rate_H2O + rate_OH + rate_CO2 260 area = PARM(1) * M0 *(M/M0)^0.67 270 rate = PARM(2) * area * rate * (1-SR("Albite")) 280 moles = rate * TIME 290 SAVE moles -end ######## #Calcite ######## # Example of KINETICS data block for calcite rate, # in mmol/cm2/s, Plummer et al., 1978, AJS 278, 179; Appelo et al., AG 13, 257 # KINETICS 1 # Calcite # -tol 1e-8 # -m0 3.e-3 # -m 3.e-3 # -parms 1.67e5 0.6 # cm^2/mol calcite, exp factor # -time 1 day Calcite -start 1 REM PARM(1) = specific surface area of calcite, cm^2/mol calcite 2 REM PARM(2) = exponent for M/M0 10 si_cc = SI("Calcite") 20 IF (M <= 0 and si_cc < 0) THEN GOTO 200 30 k1 = 10^(0.198 - 444 / TK ) 40 k2 = 10^(2.84 - 2177 /TK ) 50 IF TC <= 25 THEN k3 = 10^(-5.86 - 317 / TK) 60 IF TC > 25 THEN k3 = 10^(-1.1 - 1737 / TK ) 80 IF M0 > 0 THEN area = PARM(1)*M0*(M/M0)^PARM(2) ELSE area = PARM(1)*M 110 rate = area * (k1 * ACT("H+") + k2 * ACT("CO2") + k3 * ACT("H2O")) 120 rate = rate * (1 - 10^(2/3*si_cc)) 130 moles = rate * 0.001 * TIME # convert from mmol to mol 200 SAVE moles -end ####### #Pyrite ####### # # Williamson, M.A. and Rimstidt, J.D., 1994, # Geochimica et Cosmochimica Acta, v. 58, p. 5443-5454, # rate equation is mol m^-2 s^-1. # # Example of KINETICS data block for pyrite rate: # KINETICS 1 # Pyrite # -tol 1e-8 # -m0 5.e-4 # -m 5.e-4 # -parms 0.3 0.67 .5 -0.11 # -time 1 day in 10 Pyrite -start 1 REM Williamson and Rimstidt, 1994 2 REM PARM(1) = log10(specific area), log10(m^2 per mole pyrite) 3 REM PARM(2) = exp for (M/M0) 4 REM PARM(3) = exp for O2 5 REM PARM(4) = exp for H+ 10 REM Dissolution in presence of DO 20 if (M <= 0) THEN GOTO 200 30 if (SI("Pyrite") >= 0) THEN GOTO 200 40 log_rate = -8.19 + PARM(3)*LM("O2") + PARM(4)*LM("H+") 50 log_area = PARM(1) + LOG10(M0) + PARM(2)*LOG10(M/M0) 60 moles = 10^(log_area + log_rate) * TIME 200 SAVE moles -end ########## #Organic_C ########## # # Example of KINETICS data block for SOC (sediment organic carbon): # KINETICS 1 # Organic_C # -formula C # -tol 1e-8 # -m 5e-3 # SOC in mol # -time 30 year in 15 Organic_C -start 1 REM Additive Monod kinetics for SOC (sediment organic carbon) 2 REM Electron acceptors: O2, NO3, and SO4 10 if (M <= 0) THEN GOTO 200 20 mO2 = MOL("O2") 30 mNO3 = TOT("N(5)") 40 mSO4 = TOT("S(6)") 50 k_O2 = 1.57e-9 # 1/sec 60 k_NO3 = 1.67e-11 # 1/sec 70 k_SO4 = 1.e-13 # 1/sec 80 rate = k_O2 * mO2/(2.94e-4 + mO2) 90 rate = rate + k_NO3 * mNO3/(1.55e-4 + mNO3) 100 rate = rate + k_SO4 * mSO4/(1.e-4 + mSO4) 110 moles = rate * M * (M/M0) * TIME 200 SAVE moles -end ########### #Pyrolusite ########### # # Postma, D. and Appelo, C.A.J., 2000, GCA, vol. 64, pp. 1237-1247. # Rate equation given as mol L^-1 s^-1 # # Example of KINETICS data block for Pyrolusite # KINETICS 1-12 # Pyrolusite # -tol 1.e-7 # -m0 0.1 # -m 0.1 # -time 0.5 day in 10 Pyrolusite -start 10 if (M <= 0) THEN GOTO 200 20 sr_pl = SR("Pyrolusite") 30 if (sr_pl > 1) THEN GOTO 100 40 REM sr_pl <= 1, undersaturated 50 Fe_t = TOT("Fe(2)") 60 if Fe_t < 1e-8 then goto 200 70 moles = 6.98e-5 * Fe_t * (M/M0)^0.67 * TIME * (1 - sr_pl) 80 GOTO 200 100 REM sr_pl > 1, supersaturated 110 moles = 2e-3 * 6.98e-5 * (1 - sr_pl) * TIME 200 SAVE moles * SOLN_VOL -end END # ============================================================================================= #(a) means amorphous. (d) means disordered, or less crystalline. #(14A) refers to 14 angstrom spacing of clay planes. FeS(ppt), #precipitated, indicates an initial precipitate that is less crystalline. #Zn(OH)2(e) indicates a specific crystal form, epsilon. # ============================================================================================= # For the reaction aA + bB = cC + dD, # with delta_v = c*Vm(C) + d*Vm(D) - a*Vm(A) - b*Vm(B), # PHREEQC adds the pressure term to log_k: -= delta_v * (P - 1) / (2.3RT). # Vm(A) is volume of A, cm3/mol, P is pressure, atm, R is the gas constant, T is Kelvin. # Gas-pressures and fugacity coefficients are calculated with Peng-Robinson's EOS. # Binary interaction coefficients from Soreide and Whitson, 1992, FPE 77, 217 are # hard-coded in calc_PR(): # kij CH4 CO2 H2S N2 # H2O 0.49 0.19 0.19 0.49 # ============================================================================================= # The molar volumes of solids are entered with # -Vm vm cm3/mol # vm is the molar volume, cm3/mol (default), but dm3/mol and m3/mol are permitted. # Data for minerals' vm (= MW (g/mol) / rho (g/cm3)) are defined using rho from # Deer, Howie and Zussman, The rock-forming minerals, Longman. # -------------------- # Temperature- and pressure-dependent volumina of aqueous species are calculated with a Redlich- # type equation (cf. Redlich and Meyer, Chem. Rev. 64, 221), from parameters entered with # -Vm a1 a2 a3 a4 W a0 i1 i2 i3 i4 # The volume (cm3/mol) is # Vm(T, pb, I) = 41.84 * (a1 * 0.1 + a2 * 100 / (2600 + pb) + a3 / (T - 228) + # a4 * 1e4 / (2600 + pb) / (T - 228) - W * QBrn) # + z^2 / 2 * Av * f(I^0.5) # + (i1 + i2 / (T - 228) + i3 * (T - 228)) * I^i4 # Volumina at I = 0 are obtained using supcrt92 formulas (Johnson et al., 1992, CG 18, 899). # 41.84 transforms cal/bar/mol into cm3/mol. # pb is pressure in bar. # W * QBrn is the energy of solvation, calculated from W and the pressure dependence of the Born equation, # W is fitted on measured solution densities. # z is charge of the solute species. # Av is the Debye-Hückel limiting slope (DH_AV in PHREEQC basic). # a0 is the ion-size parameter in the extended Debye-Hückel equation: # f(I^0.5) = I^0.5 / (1 + a0 * DH_B * I^0.5), # a0 = -gamma x for cations, = 0 for anions. # For details, consult ref. 1. # ============================================================================================= # The viscosity is calculated with a (modified) Jones-Dole equation: # viscos / viscos_0 = 1 + A Sum(0.5 z_i m_i) + fan (B_i m_i + D_i m_i n_i) # Parameters are for calculating the B and D terms: # -viscosity 9.35e-2 -8.31e-2 2.487e-2 4.49e-4 2.01e-2 1.570 0 # # b0 b1 b2 d1 d2 d3 tan # z_i is absolute charge number, m_i is molality of i # B_i = b0 + b1 exp(-b2 * tc) # fan = (2 - tan V_i / V_Cl-), corrects for the volume of anions # D_i = d1 + exp(-d2 tc) # n_i = ((1 + fI)^d3 + ((z_i^2 + z_i) / 2 · m_i)d^3 / (2 + fI), fI is an ionic strength term. # For details, consult ref. 4. # # ref. 1: Appelo, Parkhurst and Post, 2014. Geochim. Cosmochim. Acta 125, 49–67. # ref. 2: Procedures from ref. 1 using data compiled by Laliberté, 2009, J. Chem. Eng. Data 54, 1725. # ref. 3: Appelo, 2017, Cem. Concr. Res. 101, 102-113. # ref. 4: Appelo and Parkhurst in prep., for details see subroutine viscosity in transport.cpp # # ============================================================================================= # It remains the responsibility of the user to check the calculated results, for example with # measured solubilities as a function of (P, T).