diff --git a/Amm.dat b/Amm.dat index 45dab01b..62fe0c38 100644 --- a/Amm.dat +++ b/Amm.dat @@ -41,7 +41,7 @@ N(+5) NO3- 0 NO3 N(+3) NO2- 0 NO2 N(0) N2 0 N # N(-3) NH4+ NH4 14.0067 -Amm AmmH+ 0 AmmH 17.0 +Amm AmmH+ 0 AmmH 17.031 B H3BO3 0 B 10.81 P PO4-3 2.0 P 30.9738 F F- 0 F 18.9984 @@ -63,39 +63,36 @@ Ntg Ntg 0 Ntg 28.0134 # N2 gas SOLUTION_SPECIES H+ = H+ -gamma 9.0 0 - - -dw 9.31e-9 + -dw 9.31e-9 831 # Dw(TK) = 9.31e-9 * exp(831 / TK - 831 / 298.15) * TK * 0.89 / (298.15 * viscos) e- = e- H2O = H2O Ca+2 = Ca+2 -gamma 5.0 0.1650 - -dw 0.793e-9 + -dw 0.793e-9 60 -Vm -0.3456 -7.252 6.149 -2.479 1.239 5 1.60 -57.1 -6.12e-3 1 # ref. 1 Mg+2 = Mg+2 -gamma 5.5 0.20 - -dw 0.705e-9 + -dw 0.705e-9 24 -Vm -1.410 -8.6 11.13 -2.39 1.332 5.5 1.29 -32.9 -5.86e-3 1 # ref. 1 Na+ = Na+ -gamma 4.0 0.075 -gamma 4.08 0.082 # halite solubility - -dw 1.33e-9 + -dw 1.33e-9 126 -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+ -gamma 3.5 0.015 - -dw 1.96e-9 + -dw 1.96e-9 262 -Vm 3.322 -1.473 6.534 -2.712 9.06e-2 3.5 0 29.7 0 1 # ref. 1 Fe+2 = Fe+2 -gamma 6.0 0 -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 Mn+2 = Mn+2 -gamma 6.0 0 -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 Al+3 = Al+3 -gamma 9.0 0 -dw 0.559e-9 @@ -103,11 +100,11 @@ Al+3 = Al+3 Ba+2 = Ba+2 -gamma 5.0 0 -gamma 4.0 0.153 # Barite solubility - -dw 0.848e-9 + -dw 0.848e-9 46 -Vm 2.063 -10.06 1.9534 -2.36 0.4218 5 1.58 -12.03 -8.35e-3 1 # ref. 1 Sr+2 = Sr+2 -gamma 5.260 0.121 - -dw 0.794e-9 + -dw 0.794e-9 161 -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 H4SiO4 = H4SiO4 -dw 1.10e-9 @@ -115,7 +112,7 @@ H4SiO4 = H4SiO4 Cl- = Cl- -gamma 3.5 0.015 -gamma 3.63 0.017 # cf. pitzer.dat - -dw 2.03e-9 + -dw 2.03e-9 194 -Vm 4.465 4.801 4.325 -2.847 1.748 0 -0.331 20.16 0 1 # ref. 1 CO3-2 = CO3-2 -gamma 5.4 0 @@ -123,15 +120,15 @@ CO3-2 = CO3-2 -Vm 5.95 0 0 -5.67 6.85 0 1.37 106 -0.0343 1 # ref. 1 SO4-2 = SO4-2 -gamma 5.0 -0.04 - -dw 1.07e-9 + -dw 1.07e-9 108 -Vm 8.0 2.3 -46.04 6.245 3.82 0 0 0 0 1 # ref. 1 NO3- = NO3- -gamma 3.0 0 - -dw 1.9e-9 + -dw 1.9e-9 219 -Vm 6.32 6.78 0 -3.06 0.346 0 0.93 0 -0.012 1 # ref. 1 AmmH+ = AmmH+ -gamma 2.5 0 - -dw 1.98e-9 + -dw 1.98e-9 377 -Vm 4.837 2.345 5.522 -2.88 1.096 3 -1.456 75.0 7.17e-3 1 # ref. 1 H3BO3 = H3BO3 -dw 1.1e-9 @@ -146,11 +143,11 @@ F- = F- -Vm 0.928 1.36 6.27 -2.84 1.84 0 0 -0.318 0 1 # ref. 2 Li+ = Li+ -gamma 6.0 0 - -dw 1.03e-9 + -dw 1.03e-9 80 -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 Br- = Br- -gamma 3.0 0 - -dw 2.01e-9 + -dw 2.01e-9 258 -Vm 6.72 2.85 4.21 -3.14 1.38 0 -9.56e-2 7.08 -1.56e-3 1 # ref. 2 Zn+2 = Zn+2 -gamma 5.0 0 @@ -174,9 +171,8 @@ 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 + -dw 1.85e-9 + -Vm 9.01 -1.11 0 -1.85 -1.50 # ref. 1 + Hnedkovsky et al., 1996, JCT 28, 125 Ntg = Ntg # N2 -dw 1.96e-9 -Vm 7 # Pray et al., 1952, IEC 44. 1146 @@ -187,7 +183,7 @@ H2Sg = H2Sg # H2S H2O = OH- + H+ -analytic 293.29227 0.1360833 -10576.913 -123.73158 0 -6.996455e-5 -gamma 3.5 0 - -dw 5.27e-9 + -dw 5.27e-9 470 -Vm -9.66 28.5 80.0 -22.9 1.89 0 1.09 0 0 1 # ref. 1 2 H2O = O2 + 4 H+ + 4 e- -log_k -86.08 @@ -219,7 +215,7 @@ CO3-2 + 2 H+ = CO2 + H2O CO3-2 + 10 H+ + 8 e- = CH4 + 3 H2O -log_k 41.071 -delta_h -61.039 kcal - -dw 1.85e-9 + -dw 1.85e-9 -Vm 9.01 -1.11 0 -1.85 -1.50 # ref. 1 + Hnedkovsky et al., 1996, JCT 28, 125 SO4-2 + H+ = HSO4- -log_k 1.988 @@ -938,7 +934,7 @@ Gypsum -log_k -4.58 -delta_h -0.109 kcal -analytic 68.2401 0.0 -3221.51 -25.0627 - + -analytical_expression 93.7 5.99E-03 -4e3 -35.019 # Appelo, submitted -Vm 73.9 # 172.18 / 2.33 (Vm H2O = 13.9 cm3/mol) Anhydrite CaSO4 = Ca+2 + SO4-2 @@ -1118,50 +1114,33 @@ O2(g) O2 = O2 -log_k -2.8983 -analytic -7.5001 7.8981e-3 0.0 0.0 2.0027e5 - - -T_c 154.6 - -P_c 49.80 - -Omega 0.021 + -T_c 154.6; -P_c 49.80; -Omega 0.021 H2(g) H2 = H2 -log_k -3.1050 -delta_h -4.184 kJ -analytic -9.3114 4.6473e-3 -49.335 1.4341 1.2815e5 - - -T_c 33.2 - -P_c 12.80 - -Omega -0.225 + -T_c 33.2; -P_c 12.80; -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 33.50 - -Omega 0.039 + -T_c 126.2; -P_c 33.50; -Omega 0.039 H2S(g) H2S = H+ + HS- -log_k -7.9759 -analytic -97.354 -3.1576e-2 1.8285e3 37.44 28.56 - - -T_c 373.2 - -P_c 88.20 - -Omega 0.1 + -T_c 373.2; -P_c 88.20; -Omega 0.1 CH4(g) CH4 = CH4 - -log_k -2.8502 + -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 45.40 - -Omega 0.008 + -T_c 190.6 ; -P_c 45.40 ; -Omega 0.008 Amm(g) Amm = Amm -log_k 1.7966 -analytic -18.758 3.3670e-4 2.5113e3 4.8619 39.192 - - -T_c 405.6 - -P_c 111.3 - -Omega 0.25 + -T_c 405.6; -P_c 111.3; -Omega 0.25 # redox-uncoupled gases Oxg(g) Oxg = Oxg @@ -1803,19 +1782,18 @@ END # -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) +# a4 * 1e4 / (2600 + pb) / (T - 228) - W * 1e5 * 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 * QBrn is the energy of solvation, QBrn is 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. +# 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), +# 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. #