# Pitzer.DAT for calculating pressure dependence of reactions, with # molal volumina of aqueous species and of minerals, and # critical temperatures and pressures of gases used in Peng-Robinson's EOS. # Details are given at the end of this file. SOLUTION_MASTER_SPECIES H H+ -1 H 1.008 H(1) H+ -1 0.0 E e- 0 0.0 0.0 O H2O 0 O 16.00 O(-2) H2O 0 0.0 Ca Ca+2 0 Ca 40.08 Mg Mg+2 0 Mg 24.305 Na Na+ 0 Na 22.9898 K K+ 0 K 39.0983 Fe Fe+2 0 Fe 55.847 Mn Mn+2 0 Mn 54.938 Ba Ba+2 0 Ba 137.33 Sr Sr+2 0 Sr 87.62 Cl Cl- 0 Cl 35.453 C CO3-2 2 HCO3 12.0111 C(4) CO3-2 2 HCO3 12.0111 Alkalinity CO3-2 1 Ca0.5(CO3)0.5 50.05 S SO4-2 0 SO4 32.064 S(6) SO4-2 0 SO4 B B(OH)3 0 B 10.81 Li Li+ 0 Li 6.941 Br Br- 0 Br 79.904 # redox-uncoupled gases Hdg Hdg 0 Hdg 1.008 # H2 gas Oxg Oxg 0 Oxg 16.0 # Oxygen gas Mtg Mtg 0.0 Mtg 16.032 # CH4 gas Sg H2Sg 1.0 H2Sg 34.08 Ntg Ntg 0 Ntg 14.0067 # N2 gas SOLUTION_SPECIES H+ = H+ -dw 9.31e-9 e- = e- H2O = H2O Li+ = Li+ -dw 1.03e-9 -Vm 4.65 -0.069 10.2 -2.78 2.96e-3 6 -18.1 -3.44 -2.33e-2 -1.67e-2 # ref. 2 and Ellis, 1968, J. Chem. Soc. A, 1138, I.S. < 10 Na+ = Na+ -dw 1.33e-9 -Vm 2.28 -4.38 -4.1 -0.586 0.09 4 0.3 52 -3.33e-3 0.566 # ref. 1 # for calculating densities (rho) when I > 3... # -Vm 2.28 -4.38 -4.1 -0.586 0.09 4 0.3 52 -3.33e-3 0.45 K+ = K+ -dw 1.96e-9 -Vm 3.322 -1.473 6.534 -2.712 9.06e-2 3.5 0 29.70 0 1 # ref. 1 Mg+2 = Mg+2 -dw 0.705e-9 -Vm -1.410 -8.6 11.13 -2.39 1.332 5.5 1.29 -32.9 -5.86e-3 1 # ref. 1 Ca+2 = Ca+2 -dw 0.793e-9 -Vm -0.3456 -7.252 6.149 -2.479 1.239 5 1.60 -57.1 -6.12e-3 1 # ref. 1 Sr+2 = Sr+2 -dw 0.794e-9 -Vm -1.57e-2 -10.15 10.18 -2.36 0.860 5.26 0.859 -27.0 -4.1e-3 1.97 # ref. 1 Ba+2 = Ba+2 -dw 0.848e-9 -Vm 2.063 -10.06 1.9534 -2.36 0.4218 5 1.58 -12.03 -8.35e-3 1 # ref. 1 Mn+2 = Mn+2 -dw 0.688e-9 -Vm -1.10 -8.03 4.08 -2.45 1.4 6 8.07 0 -1.51e-2 0.118 # ref. 2 Fe+2 = Fe+2 -dw 0.719e-9 -Vm -0.3255 -9.687 1.536 -2.379 0.3033 6 -4.21e-2 39.7 0 1 # ref. 1 Cl- = Cl- -dw 2.03e-9 -Vm 4.465 4.801 4.325 -2.847 1.748 0 -0.331 20.16 0 1 # ref. 1 CO3-2 = CO3-2 -dw 0.955e-9 -Vm 4.91 0 0 -5.41 4.76 0 0.386 89.7 -1.57e-2 1 # ref. 1 SO4-2 = SO4-2 -dw 1.07e-9 -Vm -7.77 43.17 141.1 -42.45 3.794 0 4.97 26.5 -5.77e-2 0.45 # ref. 1 B(OH)3 = B(OH)3 -dw 1.1e-9 -Vm 7.0643 8.8547 3.5844 -3.1451 -.2000 # supcrt Br- = Br- -dw 2.01e-9 -Vm 7.05 3.95 2.03 -3.14 2.07 0 -0.983 39.9 4.05e-3 1 # ref. 2 # redox-uncoupled gases Hdg = Hdg # H2 -dw 5.13e-9 -Vm 6.52 0.78 0.12 # supcrt Oxg = Oxg # O2 -dw 2.35e-9 -Vm 5.7889 6.3536 3.2528 -3.0417 -0.3943 # supcrt Mtg = Mtg # CH4 -dw 1.85e-9 -Vm 7.7 # CH4 solubility, 25-100C, 1-700atm Ntg = Ntg # N2 -dw 1.96e-9 -Vm 7 # Pray et al., 1952, IEC 44. 1146 H2Sg = H2Sg # H2S -dw 2.1e-9 -Vm 7.81 2.96 -0.46 # supcrt # aqueous species H2O = OH- + H+ -analytic 293.29227 0.1360833 -10576.913 -123.73158 0 -6.996455e-5 -dw 5.27e-9 -Vm -9.66 28.5 80.0 -22.9 1.89 0 1.09 0 0 1 # ref. 1 CO3-2 + H+ = HCO3- log_k 10.3393 delta_h -3.561 kcal -analytic 107.8975 0.03252849 -5151.79 -38.92561 563713.9 -dw 1.18e-9 -Vm 8.54 0 -11.7 0 1.6 0 0 116 0 1 # ref. 1 CO3-2 + 2 H+ = CO2 + H2O log_k 16.6767 delta_h -5.738 kcal -analytic 464.1965 0.09344813 -26986.16 -165.75951 2248628.9 -dw 1.92e-9 -Vm 20.85 -46.93 -79.0 27.9 -0.193 # ref. 1 SO4-2 + H+ = HSO4- log_k 1.979 delta_h 4.91 kcal -analytic -5.3585 0.0183412 557.2461 -dw 1.33e-9 -Vm 8.2 9.2590 2.1108 -3.1618 1.1748 0 -0.3 15 0 1 # ref. 1 H2Sg = HSg- + H+ log_k -6.994 delta_h 5.30 kcal -analytical 11.17 -0.02386 -3279.0 -dw 2.1e-9 -Vm 5.0119 4.9799 3.4765 -2.9849 1.4410 # supcrt B(OH)3 + H2O = B(OH)4- + H+ log_k -9.239 delta_h 0 kcal 3B(OH)3 = B3O3(OH)4- + 2H2O + H+ log_k -7.528 delta_h 0 kcal 4B(OH)3 = B4O5(OH)4-2 + 3H2O + 2H+ log_k -16.134 delta_h 0 kcal Ca+2 + B(OH)3 + H2O = CaB(OH)4+ + H+ log_k -7.589 delta_h 0 kcal Mg+2 + B(OH)3 + H2O = MgB(OH)4+ + H+ log_k -7.840 delta_h 0 kcal # Ca+2 + CO3-2 = CaCO3 # log_k 3.151 # delta_h 3.547 kcal # -analytic -1228.806 -0.299440 35512.75 485.818 # -dw 4.46e-10 # complexes: calc'd with the Pikal formula # -Vm -.2430 -8.3748 9.0417 -2.4328 -.0300 # supcrt Mg+2 + H2O = MgOH+ + H+ log_k -11.809 delta_h 15.419 kcal Mg+2 + CO3-2 = MgCO3 log_k 2.928 delta_h 2.535 kcal -analytic -32.225 0.0 1093.486 12.72433 -dw 4.21e-10 -Vm -.5837 -9.2067 9.3687 -2.3984 -.0300 # supcrt PHASES Anhydrite CaSO4 = Ca+2 + SO4-2 log_k -4.362 -anal 87.836 0 -3136.79 -32.953 # 50 - 160oC, 1 - 1e3 atm, anhydrite dissolution, Blount and Dickson, 1973, Am. Mineral. 58, 323. -Vm 46.1 # 136.14 / 2.95 Aragonite CaCO3 = CO3-2 + Ca+2 log_k -8.336 delta_h -2.589 kcal -analytic -171.8607 -.077993 2903.293 71.595 -Vm 34.04 Arcanite K2SO4 = SO4-- + 2 K+ log_k -1.776; -delta_h 5 kcal # Freyer and Voigt, 2004, GCA 68, 307 # -analytic 2.823 0.0 -1371.2 -Vm 65.5 Barite BaSO4 = Ba+2 + SO4-2 log_k -9.97 delta_h 6.35 kcal -analytic 136.035 0.0 -7680.41 -48.595 -Vm 51.9 Bischofite MgCl2:6H2O = Mg++ + 2 Cl- + 6 H2O log_k 4.455 -analytic 3.524 0.0 277.6 Vm 127.1 Bloedite Na2Mg(SO4)2:4H2O = Mg++ + 2 Na+ + 2 SO4-- + 4 H2O log_k -2.347 -delta_H 0 # Not possible to calculate enthalpy of reaction Bloedite Vm 147 Brucite Mg(OH)2 = Mg++ + 2 OH- log_k -10.88 -delta_H 4.85 kcal/mol # -analytic -1.0280e+002 -1.9759e-002 9.0180e+003 3.8282e+001 1.4075e+002 # -Range: 0-300 Vm 24.6 Burkeite Na6CO3(SO4)2 = CO3-2 + 2 SO4-- + 6 Na+ log_k -0.772 Vm 152 Calcite CaCO3 = CO3-2 + Ca+2 log_k -8.406 delta_h -2.297 kcal -analytic -171.8329 -0.077993 2839.319 71.595 -Vm 36.9 Carnallite KMgCl3:6H2O = K+ + Mg++ + 3Cl- + 6H2O log_k 4.330 Vm 173.7 Celestite SrSO4 = Sr+2 + SO4-2 log_k -6.630 -analytic -7.14 6.11E-03 75 0 0 -1.79E-05 # Howell et al., 1992, JCED 37, 464. -Vm 46.4 Dolomite CaMg(CO3)2 = Ca+2 + Mg+2 + 2 CO3-2 log_k -17.083 delta_h -9.436 kcal -Vm 64.5 Epsomite MgSO4:7H2O = Mg+2 + SO4-2 + 7 H2O log_k -1.881 -analytical 1.718 0.0 -1073. Vm 147 Gaylussite CaNa2(CO3)2:5H2O = Ca+2 + 2 CO3-2 + 2 Na+ + 5 H2O log_k -9.421 Glaserite NaK3(SO4)2 = Na+ + 3K+ + 2SO4-2 log_k -3.803 Glauberite Na2Ca(SO4)2 = Ca+2 + 2 Na+ + 2 SO4-2 log_k -5.245 Vm 99 Gypsum CaSO4:2H2O = Ca+2 + SO4-2 + 2 H2O log_k -4.581 delta_h -0.109 kcal -analytic 90.318 0.0 -4213. -32.641 -Vm 73.9 Halite NaCl = Cl- + Na+ log_k 1.570 -analytic -713.4616 -.1201241 37302.21 262.4583 -2106915. -Vm 27.1 Hexahydrite MgSO4:6H2O = Mg+2 + SO4-2 + 6 H2O log_k -1.635 -analytic -62.666 0.0 1828. 22.187 Vm 132 Kainite KMgClSO4:3H2O = Cl- + K+ + Mg+2 + SO4-2 + 3 H2O log_k -0.193 Kalicinite KHCO3 = K+ + H+ + CO3-2 log_k -10.058 Kieserite MgSO4:H2O = Mg+2 + SO4-2 + H2O log_k -0.123 Vm 53.8 Labile_S Na4Ca(SO4)3:2H2O = 4Na+ + Ca+2 + 3SO4-2 + 2H2O log_k -5.672 Leonhardite MgSO4:4H2O = Mg+2 + SO4-2 + 4H2O log_k -0.887 Leonite K2Mg(SO4)2:4H2O = Mg+2 + 2 K+ + 2 SO4-2 + 4 H2O log_k -3.979 Magnesite MgCO3 = CO3-2 + Mg+2 log_k -7.834 delta_h -6.169 Vm 28.3 Mirabilite Na2SO4:10H2O = SO4-2 + 2 Na+ + 10 H2O log_k -1.214 -analytic -3862.234 -1.19856 93713.54 1577.756 0. Vm 216 Misenite K8H6(SO4)7 = 6 H+ + 7 SO4-2 + 8 K+ log_k -10.806 Nahcolite NaHCO3 = CO3-2 + H+ + Na+ log_k -10.742 Natron Na2CO3:10H2O = CO3-2 + 2 Na+ + 10.0000 H2O log_k -0.825 Nesquehonite MgCO3:3H2O = CO3-2 + Mg+2 + 3 H2O log_k -5.167 Pentahydrite MgSO4:5H2O = Mg+2 + SO4-2 + 5 H2O log_k -1.285 Pirssonite Na2Ca(CO3)2:2H2O = 2Na+ + Ca+2 + 2CO3-2 + 2 H2O log_k -9.234 Polyhalite K2MgCa2(SO4)4:2H2O = 2K+ + Mg+2 + 2 Ca+2 + 4SO4-2 + 2 H2O log_k -13.744 Vm 218 Portlandite Ca(OH)2 = Ca+2 + 2 OH- log_k -5.190 Schoenite K2Mg(SO4)2:6H2O = 2K+ + Mg+2 + 2 SO4-2 + 6H2O log_k -4.328 Sylvite KCl = K+ + Cl- log_k 0.900 -analytic 3.984 0.0 -919.55 Vm 37.5 Syngenite K2Ca(SO4)2:H2O = 2K+ + Ca+2 + 2SO4-2 + H2O log_k -7.448 Thenardite Na2SO4 = 2 Na+ + SO4-2 -log_k -0.35 Vm 52.9 Trona Na3H(CO3)2:2H2O = 3 Na+ + H+ + 2CO3-2 + 2H2O log_k -11.384 Vm 106 Borax Na2(B4O5(OH)4):8H2O + 2 H+ = 4 B(OH)3 + 2 Na+ + 5 H2O log_k 12.464 Vm 223 Boric_acid,s B(OH)3 = B(OH)3 log_k -0.030 KB5O8:4H2O KB5O8:4H2O + 3H2O + H+ = 5B(OH)3 + K+ log_k 4.671 K2B4O7:4H2O K2B4O7:4H2O + H2O + 2H+ = 4B(OH)3 + 2K+ log_k 13.906 NaBO2:4H2O NaBO2:4H2O + H+ = B(OH)3 + Na+ + 3H2O log_k 9.568 NaB5O8:5H2O NaB5O8:5H2O + 2H2O + H+ = 5B(OH)3 + Na+ log_k 5.895 Teepleite Na2B(OH)4Cl + H+ = B(OH)3 + 2Na+ + Cl- + H2O log_k 10.840 CO2(g) CO2 = CO2 log_k -1.468 delta_h -4.776 kcal -analytic 109.534 1.9913e-2 -6986.04 -40.83 669370 -T_c 304.2 # critical T, K -P_c 72.80 # 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 # critical T, K -P_c 217.60 # critical P, atm -Omega 0.344 # acentric factor -analytic -16.5066 -2.0013E-3 2710.7 3.7646 0 2.24E-6 # redox-uncoupled gases Oxg(g) Oxg = Oxg -analytic -7.5001 7.8981e-003 0.0 0.0 2.0027e+005 T_c 154.6 ; -P_c 49.80 ; -Omega 0.021 Hdg(g) Hdg = Hdg -analytic -9.3114e+000 4.6473e-003 -4.9335e+001 1.4341e+000 1.2815e+005 -T_c 33.2 ; -P_c 12.80 ; -Omega 0.225 Ntg(g) Ntg = Ntg -analytic -58.453 1.81800E-03 3199 17.909 -27460 T_c 126.2 ; -P_c 33.50 ; -Omega 0.039 Mtg(g) Mtg = Mtg -analytic -2.4027e+001 4.7146e-003 3.7227e+002 6.4264e+000 2.3362e+005 T_c 190.6 ; -P_c 45.40 ; -Omega 0.008 H2Sg(g) H2Sg = H+ + HSg- -analytic -9.7354e+001 -3.1576e-002 1.8285e+003 3.7440e+001 2.8560e+001 T_c 373.2 ; -P_c 88.20 ; -Omega 0.1 PITZER -B0 B(OH)4- K+ 0.035 B(OH)4- Na+ -0.0427 B3O3(OH)4- K+ -0.13 B3O3(OH)4- Na+ -0.056 B4O5(OH)4-2 K+ -0.022 B4O5(OH)4-2 Na+ -0.11 Ba+2 Br- 0.31455 0 0 -0.33825E-3 Ba+2 Cl- 0.2628 0 0 0.6405E-3 Ba+2 OH- 0.17175 Br- H+ 0.1960 0 0 -2.049E-4 Br- K+ 0.0569 0 0 7.39E-4 Br- Li+ 0.1748 0 0 -1.819E-4 Br- Mg+2 0.4327 0 0 -5.625E-5 Br- Na+ 0.0973 0 0 7.692E-4 Br- Sr+2 0.331125 0 0 -0.32775E-3 Ca+2 Br- 0.3816 0 0 -5.2275E-4 Ca+2 Cl- 0.3159 0 0 -1.725E-4 Ca+2 HCO3- 0.4 Ca+2 HSO4- 0.2145 Ca+2 OH- -0.1747 Ca+2 SO4-2 0.2 CaB(OH)4+ Cl- 0.12 Cl- Fe+2 0.335925 Cl- H+ 0.1775 0 0 -3.081E-4 Cl- K+ 0.04835 0 0 5.794E-4 Cl- Li+ 0.1494 0 0 -1.685E-4 Cl- Mg+2 0.35235 0 0 -1.943E-4 Cl- MgB(OH)4+ 0.16 Cl- MgOH+ -0.1 Cl- Mn+2 0.327225 Cl- Na+ 0.0765 -777.03 -4.4706 0.008946 -3.3158E-6 Cl- Sr+2 0.2858 0 0 0.717E-3 CO3-2 K+ 0.1488 0 0 1.788E-3 CO3-2 Na+ 0.0399 0 0 1.79E-3 Fe+2 HSO4- 0.4273 Fe+2 SO4-2 0.2568 H+ HSO4- 0.2065 H+ SO4-2 0.0298 HCO3- K+ 0.0296 0 0 0.996E-3 HCO3- Mg+2 0.329 HCO3- Na+ 0.0277 0 0 1.00E-3 HCO3- Sr+2 0.12 HSO4- K+ -0.0003 HSO4- Mg+2 0.4746 HSO4- Na+ 0.0454 K+ OH- 0.1298 K+ SO4-2 0.04995 0 0 1.44E-3 Li+ OH- 0.015 Li+ SO4-2 0.136275 0 0 0.5055E-3 Mg+2 SO4-2 0.221 0 0 -0.69E-3 Mn+2 SO4-2 0.2065 Na+ OH- 0.0864 0 0 7.00E-4 Na+ SO4-2 0.01958 0 0 2.367E-3 SO4-2 Sr+2 0.200 0 0 -2.9E-3 -B1 B(OH)4- K+ 0.14 B(OH)4- Na+ 0.089 B3O3(OH)4- Na+ -0.910 B4O5(OH)4-2 Na+ -0.40 Ba+2 Br- 1.56975 0 0 6.78E-3 Ba+2 Cl- 1.49625 0 0 3.2325E-3 Ba+2 OH- 1.2 Br- H+ 0.3564 0 0 4.467E-4 Br- K+ 0.2212 0 0 17.40E-4 Br- Li+ 0.2547 0 0 6.636E-4 Br- Mg+2 1.753 0 0 3.8625E-3 Br- Na+ 0.2791 0 0 10.79E-4 Br- Sr+2 1.7115 0 0 6.5325E-3 Ca+2 Br- 1.613 0 0 6.0375E-3 Ca+2 Cl- 1.614 0 0 3.9E-3 Ca+2 HCO3- 2.977 Ca+2 HSO4- 2.53 Ca+2 OH- -0.2303 Ca+2 SO4-2 3.1973 0 0 5.46E-2 Cl- Fe+2 1.53225 Cl- H+ 0.2945 0 0 1.419E-4 Cl- K+ 0.2122 0 0 10.71E-4 Cl- Li+ 0.3074 0 0 5.366E-4 Cl- Mg+2 1.6815 0 0 3.6525E-3 Cl- MgOH+ 1.658 Cl- Mn+2 1.55025 Cl- Na+ 0.2664 0 0 6.1608E-5 1.0715E-6 Cl- Sr+2 1.667 0 0 2.8425E-3 CO3-2 K+ 1.43 0 0 2.051E-3 CO3-2 Na+ 1.389 0 0 2.05E-3 Fe+2 HSO4- 3.48 Fe+2 SO4-2 3.063 H+ HSO4- 0.5556 HCO3- K+ -0.013 0 0 1.104E-3 HCO3- Mg+2 0.6072 HCO3- Na+ 0.0411 0 0 1.10E-3 HSO4- K+ 0.1735 HSO4- Mg+2 1.729 HSO4- Na+ 0.398 K+ OH- 0.32 K+ SO4-2 0.7793 0 0 6.6975E-3 Li+ OH- 0.14 Li+ SO4-2 1.2705 0 0 1.41E-3 Mg+2 SO4-2 3.343 0 0 1.53E-2 Mn+2 SO4-2 2.9511 Na+ OH- 0.253 0 0 1.34E-4 Na+ SO4-2 1.113 0 0 5.6325E-3 SO4-2 Sr+2 3.1973 0 0 27.0E-3 -B2 Ca+2 OH- -5.72 Ca+2 SO4-2 -54.24 0 0 -0.516 Fe+2 SO4-2 -42.0 Mg+2 SO4-2 -37.23 0 0 -0.253 Mn+2 SO4-2 -40.0 SO4-2 Sr+2 -54.24 0 0 -0.42 -C0 B(OH)4- Na+ 0.0114 Ba+2 Br- -0.0159576 Ba+2 Cl- -0.0193782 0 0 -1.53796E-4 Br- Ca+2 -0.00257 Br- H+ 0.00827 0 0 -5.685E-5 Br- K+ -0.00180 0 0 -7.004E-5 Br- Li+ 0.0053 0 0 -2.813E-5 Br- Mg+2 0.00312 Br- Na+ 0.00116 0 0 -9.30E-5 Br- Sr+2 0.00122506 Ca+2 Cl- -0.00034 Cl- Fe+2 -0.00860725 Cl- H+ 0.0008 0 0 6.213E-5 Cl- K+ -0.00084 0 0 -5.095E-5 Cl- Li+ 0.00359 0 0 -4.520E-5 Cl- Mg+2 0.00519 0 0 -1.64933E-4 Cl- Mn+2 -0.0204972 Cl- Na+ 0.00127 33.317 0.09421 -4.655E-5 Cl- Sr+2 -0.00130 CO3-2 K+ -0.0015 CO3-2 Na+ 0.0044 Fe+2 SO4-2 0.0209 H+ SO4-2 0.0438 HCO3- K+ -0.008 K+ OH- 0.0041 Li+ SO4-2 -0.00399338 0 0 -2.33345E-4 Mg+2 SO4-2 0.025 0 0 0.523E-3 Mn+2 SO4-2 0.01636 Na+ OH- 0.0044 0 0 -18.94E-5 Na+ SO4-2 0.00497 0 0 -4.87904E-4 -THETA B(OH)4- Cl- -0.065 B(OH)4- SO4-2 -0.012 B3O3(OH)4- Cl- 0.12 B3O3(OH)4- HCO3- -0.10 B3O3(OH)4- SO4-2 0.10 B4O5(OH)4-2 Cl- 0.074 B4O5(OH)4-2 HCO3- -0.087 B4O5(OH)4-2 SO4-2 0.12 Br- OH- -0.065 Ca+2 H+ 0.092 Ca+2 K+ 0.032 Ca+2 Mg+2 0.007 Ca+2 Na+ 0.07 Cl- CO3-2 -0.02 Cl- HCO3- 0.03 Cl- HSO4- -0.006 Cl- OH- -0.05 Cl- SO4-2 0.02 CO3-2 OH- 0.1 CO3-2 SO4-2 0.02 H+ K+ 0.005 H+ Mg+2 0.1 H+ Na+ 0.036 HCO3- CO3-2 -0.04 HCO3- SO4-2 0.01 K+ Na+ -0.012 Mg+2 Na+ 0.07 Na+ Sr+2 0.051 OH- SO4-2 -0.013 -LAMDA B(OH)3 Cl- 0.091 B(OH)3 K+ -0.14 B(OH)3 Na+ -0.097 B(OH)3 SO4-2 0.018 B3O3(OH)4- B(OH)3 -0.20 Ca+2 CO2 0.183 Cl- CO2 -0.005 CO2 HSO4- -0.003 CO2 K+ 0.051 CO2 Mg+2 0.183 CO2 Na+ 0.085 CO2 SO4-2 0.097 -ZETA B(OH)3 Cl- H+ -0.0102 B(OH)3 Na+ SO4-2 0.046 CO2 Na+ SO4-2 -0.015 -PSI B(OH)4- Cl- Na+ -0.0073 B3O3(OH)4- Cl- Na+ -0.024 B4O5(OH)4-2 Cl- Na+ 0.026 Br- K+ Na+ -0.0022 Br- K+ OH- -0.014 Br- Na+ H+ -0.012 Br- Na+ OH- -0.018 Ca+2 Cl- H+ -0.015 Ca+2 Cl- K+ -0.025 Ca+2 Cl- Mg+2 -0.012 Ca+2 Cl- Na+ -0.007 Ca+2 Cl- OH- -0.025 Ca+2 Cl- SO4-2 -0.018 Ca+2 Mg+2 SO4-2 0.024 Ca+2 Na+ SO4-2 -0.055 Cl- Br- K+ 0.000 Cl- CO3-2 K+ 0.004 Cl- CO3-2 Na+ 0.0085 Cl- H+ K+ -0.011 Cl- H+ Mg+2 -0.011 Cl- H+ Na+ -0.004 Cl- HCO3- Mg+2 -0.096 Cl- HCO3- Na+ -0.015 Cl- HSO4- H+ 0.013 Cl- HSO4- Na+ -0.006 Cl- K+ Mg+2 -0.022 Cl- K+ Na+ -0.0018 Cl- K+ OH- -0.006 Cl- Mg+2 MgOH+ 0.028 Cl- Mg+2 Na+ -0.012 Cl- Mg+2 SO4-2 -0.004 Cl- Na+ OH- -0.006 Cl- Na+ SO4-2 0.0014 Cl- Na+ Sr+2 -0.0021 CO3-2 HCO3- K+ 0.012 CO3-2 HCO3- Na+ 0.002 CO3-2 K+ Na+ 0.003 CO3-2 K+ OH- -0.01 CO3-2 K+ SO4-2 -0.009 CO3-2 Na+ OH- -0.017 CO3-2 Na+ SO4-2 -0.005 H+ HSO4- K+ -0.0265 H+ HSO4- Mg+2 -0.0178 H+ HSO4- Na+ -0.0129 H+ K+ Br- -0.021 H+ K+ SO4-2 0.197 HCO3- K+ Na+ -0.003 HCO3- Mg+2 SO4-2 -0.161 HCO3- Na+ SO4-2 -0.005 HSO4- K+ SO4-2 -0.0677 HSO4- Mg+2 SO4-2 -0.0425 HSO4- Na+ SO4-2 -0.0094 K+ Mg+2 SO4-2 -0.048 K+ Na+ SO4-2 -0.010 K+ OH- SO4-2 -0.050 Mg+2 Na+ SO4-2 -0.015 Na+ OH- SO4-2 -0.009 EXCHANGE_MASTER_SPECIES X X- EXCHANGE_SPECIES X- = X- log_k 0.0 Na+ + X- = NaX log_k 0.0 K+ + X- = KX log_k 0.7 delta_h -4.3 # Jardine & Sparks, 1984 Li+ + X- = LiX log_k -0.08 delta_h 1.4 # Merriam & Thomas, 1956 Ca+2 + 2X- = CaX2 log_k 0.8 delta_h 7.2 # Van Bladel & Gheyl, 1980 Mg+2 + 2X- = MgX2 log_k 0.6 delta_h 7.4 # Laudelout et al., 1968 Sr+2 + 2X- = SrX2 log_k 0.91 delta_h 5.5 # Laudelout et al., 1968 Ba+2 + 2X- = BaX2 log_k 0.91 delta_h 4.5 # Laudelout et al., 1968 Mn+2 + 2X- = MnX2 log_k 0.52 Fe+2 + 2X- = FeX2 log_k 0.44 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 0.0 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 0.0 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 + 2H+ log_k -17.60 # 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 # # 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 # Hfo_sOH + Fe+2 = Hfo_sOFe+ + H+ # log_k 0.7 # LFER using table 10.5 # Hfo_wOH + Fe+2 = Hfo_wOFe+ + H+ # log_k -2.5 # LFER using table 10.5 # Iron, strong site: Appelo, Van der Weiden, Tournassat & Charlet, subm. 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 + 2H+ log_k -11.55 ############################################### # ANIONS # ############################################### # # Anions from table 10.6 # # # Anions from table 10.7 # # Borate Hfo_wOH + B(OH)3 = 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 # # Carbonate: Van Geen et al., 1994 reoptimized for HFO # 0.15 g HFO/L has 0.344 mM sites == 2 g of Van Geen's Goethite/L # # Hfo_wOH + CO3-2 + H+ = Hfo_wCO3- + H2O # log_k 12.56 # # Hfo_wOH + CO3-2 + 2H+= Hfo_wHCO3 + H2O # log_k 20.62 END MEAN GAM CaCl2 CaSO4 CaCO3 Ca(OH)2 MgCl2 MgSO4 MgCO3 Mg(OH)2 NaCl Na2SO4 NaHCO3 Na2CO3 NaOH KCl K2SO4 KHCO3 K2CO3 KOH HCl H2SO4 HBr END # 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. # z is charge of the solute species. # Av is the Debye-Hückel limiting slope. # 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. # # 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. # # # ============================================================================================= # It remains the responsibility of the user to check the calculated results, for example with # measured solubilities as a function of (P, T).