diff --git a/database/Amm.dat b/database/Amm.dat index 58d6c0d9..73964b43 100644 --- a/database/Amm.dat +++ b/database/Amm.dat @@ -66,7 +66,7 @@ H+ = H+ -dw 9.31e-9 838 6.96 -2.285 0.206 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 tracer diffusion. +# a = DH ion size (= 3.5 - 25), a2 = exponent (= 0 2.5), visc = viscosity exponent (= 0 2.5), a3 = switch [a3(H+) = 24.01 = new dw calculation from A.D. 2024], a_v_dif = exponent in (viscos_0_tc / viscos)^a_v_dif for tracer diffusion. # For SC, Dw(TK) *= (viscos_0_tc / viscos)^visc (visc = 0.206 for H+) # a3 > 5 or a3 = 0 or not defined ? ka = DH_B * a * (1 + (vm - v0))^a2 * mu^0.5, in Onsager-Falkenhagen eqn. (For H+, the reference ion, vm = v0 = 0, a *= (1 + mu)^a2.) @@ -76,7 +76,7 @@ H+ = H+ # If a_v_dif <> 0, Dw(TK) *= (viscos_0_tc / viscos)^a_v_dif in TRANSPORT. e- = e- H2O = H2O - -dw 2.299e-9 -249 # Holz et al., Phys. Chem. Chem. Phys., 2000, 2, 4740. + -dw 2.299e-9 -249 # Holz et al., Phys. Chem. Chem. Phys., 2000, 2, 4740. # 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 @@ -143,10 +143,10 @@ CO3-2 = CO3-2 -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 + -gamma 5.0 -0.04 + -Vm 5.36 10.69 33.566 -15.03 4.2582 25 0.341 153.8 1.089e-2 0.9224 # with Na2SO4 & better calculation of sulfates' solubilities in NaCl + -viscosity -0.5 0.521 4.2e-4 9.78e-3 1.24e-2 2.5 -4.94e-2 + -dw 1.07e-9 -77.4 10.14 0.5 0.5549 NO3- = NO3- -gamma 3 0 -Vm 6.32 6.78 0 -3.06 0.346 0 0.93 0 -0.012 1 @@ -206,14 +206,14 @@ H2Sg = H2Sg # H2S -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 + -analytic 293.29227 0.1360833 -10576.913 -123.73158 0 -6.996455e-5 -Vm -9.66 28.5 80 -22.9 1.89 0 1.09 0 0 1 -viscosity -2.26e-2 0.106 2.184e-2 -3.2e-3 0 0.4082 -1.634 # < 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 + -log_k -86.06; -delta_h 138.43 kcal + -analytic -1e3 -0.322 -5897.7 416.82 0 -1.88e-5 -Vm 5.7889 6.3536 3.2528 -3.0417 -0.3943 # supcrt -dw 2.35e-9 2 H+ + 2 e- = H2 @@ -316,11 +316,11 @@ AmmH+ = Amm + H+ -dw 2.28e-9 AmmH+ + SO4-2 = AmmHSO4- #NH4+ + SO4-2 = NH4SO4- - -gamma 2.10 -0.0419 - -log_k 1.212; -delta_h 8.61 kJ - -Vm -8.78 0 -36.09 0 -8.60 0 87.62 0 -0.3123 0.1172 - -viscosity 0 0.121 -8e-3 0.177 -8e-3 0.512 0.629 - -dw 0.9e-9 100 2.1 2 0 + -gamma 3.64 -4.75e-2 + -log_k 1.276; -delta_h -3.24 kcal + -Vm 6.64 8.5 -5.84 -3.1 2 0 19.24 0 -7.84e-2 0.289 + -viscosity 0.267 -0.207 9.75e-2 6.18e-2 1.99e-2 1.166 0.61 + -dw 1.56e-9 498 25 0.5 0.684 H3BO3 = H2BO3- + H+ -log_k -9.24 -delta_h 3.224 kcal @@ -375,10 +375,11 @@ Ca+2 + CO3-2 + H+ = CaHCO3+ -Vm 3.19 .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 + -gamma 0 4.45e-2 + -log_k 2.14; -delta_h 24.4 + -analytical_expression 1.478 8.29e-3 -538.2 + -vm 2.7 2 2 -3.7 + -dw 4.71e-9 Ca+2 + HSO4- = CaHSO4+ -log_k 1.08 Ca+2 + PO4-3 = CaPO4- @@ -415,19 +416,19 @@ Mg+2 + H+ + CO3-2 = MgHCO3+ -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 + -gamma 0 0.20 + -log_k 2.42; -delta_h 19.0 + -analytical_expression 0 9.64e-3 -136 # epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC + -Vm 11.92 -27.758 29.752 -10.302 -0.1 + -viscosity -0.799 1 2.2e-4 8.53e-2 -4.6e-3 1.35 -0.796 -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 + -log_k 0.52; -delta_h -13.6 + -analytical_expression 0 -1.51e-3 0 0 8.604e4 # epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC + -Vm 4.248 9.83 -7 -2.672 2 3.5 5 100 0.3359 9.518e-2 + -viscosity 0.324 6.84e-2 -2.09e-2 0.104 6.19e-3 1.983 1e-3 + -dw 1.11e-9 -500 3.5 0.5 0.731 Mg+2 + PO4-3 = MgPO4- -log_k 6.589 -delta_h 3.1 kcal @@ -453,12 +454,19 @@ Na+ + HCO3- = NaHCO3 -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 + -gamma 3.5 0.1072 + -log_k 0.94; -delta_h 8.23 + -analytical_expression -0.304 4.51e-3 -28.9 # mirabilite/thenardite solubilities, 0 - 200 oC + -Vm 8.523 -4.685 -8.61 0.106 2.7 25 3.634 13.4 3.738e-2 0.5476 + -viscosity -1 0.33 0.128 1.143 7.7e-4 1.9e-2 -0.387 + -dw 4e-10 -200 3.5 0.5 0.5 +2 Na+ + SO4-2 = Na2SO4 + -gamma 0 8.85e-2 + -log_k -2.37; -delta_h 82 + -analytical_expression 15.432 -5.75e-3 -4796 # sulfates solubilities in NaCl + -Vm 9.405 -15.5 25 8.4 0.25 + -viscosity -0.5 0.485 -1e-3 0.147 0 0.947 -0.175 + -dw 0.8e-9 Na+ + HPO4-2 = NaHPO4- -log_k 0.29 -gamma 5.4 0 @@ -473,11 +481,11 @@ K+ + HCO3- = KHCO3 -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 + -log_k 1.18; -delta_h 3 -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 + -Vm 3.443 5.04 13 -3.324 2.447 0 20 0 7.77e-3 0.3497 + -viscosity 0.107 0.19 2.23e-2 -0.148 -4.91e-2 0.537 0.195 + -dw 1.22e-9 100 25 0.5 2.5 K+ + HPO4-2 = KHPO4- -log_k 0.29 -gamma 5.4 0 @@ -497,9 +505,8 @@ Fe+2 + CO3-2 = FeCO3 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 + -log_k 2.25; -delta_h 3.23 kcal + -Vm 5.8 6.5 3.7 -3 -0.09 Fe+2 + HSO4- = FeHSO4+ -log_k 1.08 Fe+2 + 2 HS- = Fe(HS)2 @@ -601,9 +608,9 @@ 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 + -gamma 0 -0.098 + -log_k 1.408; -delta_h 21.55 + -Vm 1.88 6.5 10 -3 0.1 Mn+2 + 2 NO3- = Mn(NO3)2 -log_k 0.6 -delta_h -0.396 kcal @@ -696,7 +703,8 @@ Ba+2 + HCO3- = BaHCO3+ -delta_h 5.56 kcal -analytic -3.0938 0.013669 Ba+2 + SO4-2 = BaSO4 - -log_k 2.7 + -log_k 3.457; -delta_h 26.15 + -vm -6.25 24.66 -4.38 10.97 0.5 Sr+2 + H2O = SrOH+ + H+ -log_k -13.29 -gamma 5 0 @@ -815,12 +823,13 @@ Zn+2 + 2 CO3-2 = Zn(CO3)2-2 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 + -gamma 0 0.1 + -log_k 2.26; -delta_h 16.15 + -Vm 0.409 6.5 2 -3 0 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 + -gamma 0.59 0.1 + -log_k 1.15; -delta_h 17.52 + -Vm 9.21 10.6 9 -3.2 3.8 25 0 100 -1e-3 0.256 Zn+2 + Br- = ZnBr+ -log_k -0.58 Zn+2 + 2 Br- = ZnBr2 @@ -866,12 +875,13 @@ Cd+2 + 2 CO3-2 = Cd(CO3)2-2 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 + -gamma 0 0.1 + -log_k 1.016; -delta_h 6.84 + -Vm 2.11 6.5 10 -3 0.1 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 + -gamma 5.201 -0.1 + -log_k 2.688; -delta_h 0.19 + -Vm 9.14 10.6 -3.06 -3.2 3.8 7.44 1.27 0.32 -1e-3 2.5 Cd+2 + Br- = CdBr+ -log_k 2.17 -delta_h -0.81 kcal @@ -991,29 +1001,24 @@ Witherite -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) + -log_k -4.55; -delta_h -6.70 + -analytical_expression 72.244 -1.474e-2 -4040 -23.7823 # fits the appendix data of Appelo, 2015, AG 55, 62 + -Vm 73.9 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 + log_k -4.25; -delta_h -22.4 + -analytical_expression 5.725 -2.478e-2 -790.4 # 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 + -log_k -9.89; -delta_h 11.82 + -analytical_expression -34.438 -3.316e-2 -1500 15.9485 # Blount 1977; Templeton, 1960 -Vm 52.9 Arcanite K2SO4 = SO4-2 + 2 K+ @@ -1023,12 +1028,14 @@ Arcanite -Vm 65.5 Mirabilite Na2SO4:10H2O = SO4-2 + 2 Na+ + 10 H2O - -analytical_expression -301.9326 -0.16232 0 141.078 # ref. 3 + -log_k -0.706; -delta_h 124 + -analytical_expression -53.037 0.1242 4562 # 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 + -log_k 0.65; -delta_h -23.1 + -analytical_expression 159.849 1.699e-2 -5000 -59.6073 # ref. 3 + Vm 52.9 Epsomite MgSO4:7H2O = Mg+2 + SO4-2 + 7 H2O log_k -1.74; -delta_h 10.57 kJ @@ -1901,7 +1908,6 @@ Pyrolusite 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. @@ -1943,14 +1949,14 @@ END # 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. +# a0 = -gamma x for cations, = 0 for anions (or fitted). # For details, consult ref. 1 and subroutine calc_vm(tc, pa) in prep.cpp. # ============================================================================================= # The viscosity is calculated with a (modified) Jones-Dole equation: # viscos / viscos_0 = 1 + A * Sum(0.5 z_i m_i) + fan * Sum(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 +# -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 and neutral species diff --git a/database/phreeqc.dat b/database/phreeqc.dat index 51d44013..9aec9ecf 100644 --- a/database/phreeqc.dat +++ b/database/phreeqc.dat @@ -70,7 +70,7 @@ H+ = H+ -dw 9.31e-9 838 6.96 -2.285 0.206 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 tracer diffusion. +# a = DH ion size (= 3.5 - 25), a2 = exponent (= 0 2.5), visc = viscosity exponent (= 0 2.5), a3 = switch [a3(H+) = 24.01 = new dw calculation from A.D. 2024], a_v_dif = exponent in (viscos_0_tc / viscos)^a_v_dif for tracer diffusion. # For SC, Dw(TK) *= (viscos_0_tc / viscos)^visc (visc = 0.206 for H+) # a3 > 5 or a3 = 0 or not defined ? ka = DH_B * a * (1 + (vm - v0))^a2 * mu^0.5, in Onsager-Falkenhagen eqn. (For H+, the reference ion, vm = v0 = 0, a *= (1 + mu)^a2.) @@ -80,7 +80,7 @@ H+ = H+ # If a_v_dif <> 0, Dw(TK) *= (viscos_0_tc / viscos)^a_v_dif in TRANSPORT. e- = e- H2O = H2O - -dw 2.299e-9 -249 # Holz et al., Phys. Chem. Chem. Phys., 2000, 2, 4740. + -dw 2.299e-9 -249 # Holz et al., Phys. Chem. Chem. Phys., 2000, 2, 4740. # 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 @@ -147,16 +147,16 @@ CO3-2 = CO3-2 -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 + -gamma 5.0 -0.04 + -Vm 5.36 10.69 33.566 -15.03 4.2582 25 0.341 153.8 1.089e-2 0.9224 # with Na2SO4 & better calculation of sulfates' solubilities in NaCl + -viscosity -0.5 0.521 4.2e-4 9.78e-3 1.24e-2 2.5 -4.94e-2 + -dw 1.07e-9 -77.4 10.14 0.5 0.5549 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+ +#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 6.94e-2 -0.141 2.04e-2 9.4e-3 3.73e-2 0.898 @@ -210,14 +210,14 @@ H2Sg = H2Sg # H2S -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 + -analytic 293.29227 0.1360833 -10576.913 -123.73158 0 -6.996455e-5 -Vm -9.66 28.5 80 -22.9 1.89 0 1.09 0 0 1 -viscosity -2.26e-2 0.106 2.184e-2 -3.2e-3 0 0.4082 -1.634 # < 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 + -log_k -86.06; -delta_h 138.43 kcal + -analytic -1e3 -0.322 -5897.7 416.82 0 -1.88e-5 -Vm 5.7889 6.3536 3.2528 -3.0417 -0.3943 # supcrt -dw 2.35e-9 2 H+ + 2 e- = H2 @@ -304,8 +304,8 @@ NO3- + 2 H+ + 2 e- = NO2- + H2O -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- = NH4+ + 3 H2O - -log_k 119.077 - -delta_h -187.055 kcal + -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 6.94e-2 -0.141 2.04e-2 9.4e-3 3.73e-2 0.898 @@ -320,11 +320,11 @@ NH4+ = NH3 + H+ -dw 2.28e-9 #AmmH+ + SO4-2 = AmmHSO4- NH4+ + SO4-2 = NH4SO4- - -gamma 2.10 -0.0419 - -log_k 1.212; -delta_h 8.61 kJ - -Vm -8.78 0 -36.09 0 -8.60 0 87.62 0 -0.3123 0.1172 - -viscosity 0 0.121 -8e-3 0.177 -8e-3 0.512 0.629 - -dw 0.9e-9 100 2.1 2 0 + -gamma 3.64 -4.75e-2 + -log_k 1.276; -delta_h -3.24 kcal + -Vm 6.64 8.5 -5.84 -3.1 2 0 19.24 0 -7.84e-2 0.289 + -viscosity 0.267 -0.207 9.75e-2 6.18e-2 1.99e-2 1.166 0.61 + -dw 1.56e-9 498 25 0.5 0.684 H3BO3 = H2BO3- + H+ -log_k -9.24 -delta_h 3.224 kcal @@ -379,10 +379,11 @@ Ca+2 + CO3-2 + H+ = CaHCO3+ -Vm 3.19 .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 + -gamma 0 4.45e-2 + -log_k 2.14; -delta_h 24.4 + -analytical_expression 1.478 8.29e-3 -538.2 + -vm 2.7 2 2 -3.7 + -dw 4.71e-9 Ca+2 + HSO4- = CaHSO4+ -log_k 1.08 Ca+2 + PO4-3 = CaPO4- @@ -419,19 +420,19 @@ Mg+2 + H+ + CO3-2 = MgHCO3+ -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 + -gamma 0 0.20 + -log_k 2.42; -delta_h 19.0 + -analytical_expression 0 9.64e-3 -136 # epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC + -Vm 11.92 -27.758 29.752 -10.302 -0.1 + -viscosity -0.799 1 2.2e-4 8.53e-2 -4.6e-3 1.35 -0.796 -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 + -log_k 0.52; -delta_h -13.6 + -analytical_expression 0 -1.51e-3 0 0 8.604e4 # epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC + -Vm 4.248 9.83 -7 -2.672 2 3.5 5 100 0.3359 9.518e-2 + -viscosity 0.324 6.84e-2 -2.09e-2 0.104 6.19e-3 1.983 1e-3 + -dw 1.11e-9 -500 3.5 0.5 0.731 Mg+2 + PO4-3 = MgPO4- -log_k 6.589 -delta_h 3.1 kcal @@ -457,12 +458,19 @@ Na+ + HCO3- = NaHCO3 -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 + -gamma 3.5 0.1072 + -log_k 0.94; -delta_h 8.23 + -analytical_expression -0.304 4.51e-3 -28.9 # mirabilite/thenardite solubilities, 0 - 200 oC + -Vm 8.523 -4.685 -8.61 0.106 2.7 25 3.634 13.4 3.738e-2 0.5476 + -viscosity -1 0.33 0.128 1.143 7.7e-4 1.9e-2 -0.387 + -dw 4e-10 -200 3.5 0.5 0.5 +2 Na+ + SO4-2 = Na2SO4 + -gamma 0 8.85e-2 + -log_k -2.37; -delta_h 82 + -analytical_expression 15.432 -5.75e-3 -4796 # sulfates solubilities in NaCl + -Vm 9.405 -15.5 25 8.4 0.25 + -viscosity -0.5 0.485 -1e-3 0.147 0 0.947 -0.175 + -dw 0.8e-9 Na+ + HPO4-2 = NaHPO4- -log_k 0.29 -gamma 5.4 0 @@ -477,11 +485,11 @@ K+ + HCO3- = KHCO3 -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 + -log_k 1.18; -delta_h 3 -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 + -Vm 3.443 5.04 13 -3.324 2.447 0 20 0 7.77e-3 0.3497 + -viscosity 0.107 0.19 2.23e-2 -0.148 -4.91e-2 0.537 0.195 + -dw 1.22e-9 100 25 0.5 2.5 K+ + HPO4-2 = KHPO4- -log_k 0.29 -gamma 5.4 0 @@ -501,9 +509,8 @@ Fe+2 + CO3-2 = FeCO3 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 + -log_k 2.25; -delta_h 3.23 kcal + -Vm 5.8 6.5 3.7 -3 -0.09 Fe+2 + HSO4- = FeHSO4+ -log_k 1.08 Fe+2 + 2 HS- = Fe(HS)2 @@ -605,9 +612,9 @@ 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 + -gamma 0 -0.098 + -log_k 1.408; -delta_h 21.55 + -Vm 1.88 6.5 10 -3 0.1 Mn+2 + 2 NO3- = Mn(NO3)2 -log_k 0.6 -delta_h -0.396 kcal @@ -700,7 +707,8 @@ Ba+2 + HCO3- = BaHCO3+ -delta_h 5.56 kcal -analytic -3.0938 0.013669 Ba+2 + SO4-2 = BaSO4 - -log_k 2.7 + -log_k 3.457; -delta_h 26.15 + -vm -6.25 24.66 -4.38 10.97 0.5 Sr+2 + H2O = SrOH+ + H+ -log_k -13.29 -gamma 5 0 @@ -819,12 +827,13 @@ Zn+2 + 2 CO3-2 = Zn(CO3)2-2 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 + -gamma 0 0.1 + -log_k 2.26; -delta_h 16.15 + -Vm 0.409 6.5 2 -3 0 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 + -gamma 0.59 0.1 + -log_k 1.15; -delta_h 17.52 + -Vm 9.21 10.6 9 -3.2 3.8 25 0 100 -1e-3 0.256 Zn+2 + Br- = ZnBr+ -log_k -0.58 Zn+2 + 2 Br- = ZnBr2 @@ -870,12 +879,13 @@ Cd+2 + 2 CO3-2 = Cd(CO3)2-2 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 + -gamma 0 0.1 + -log_k 1.016; -delta_h 6.84 + -Vm 2.11 6.5 10 -3 0.1 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 + -gamma 5.201 -0.1 + -log_k 2.688; -delta_h 0.19 + -Vm 9.14 10.6 -3.06 -3.2 3.8 7.44 1.27 0.32 -1e-3 2.5 Cd+2 + Br- = CdBr+ -log_k 2.17 -delta_h -0.81 kcal @@ -995,29 +1005,24 @@ Witherite -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) + -log_k -4.55; -delta_h -6.70 + -analytical_expression 72.244 -1.474e-2 -4040 -23.7823 # fits the appendix data of Appelo, 2015, AG 55, 62 + -Vm 73.9 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 + log_k -4.25; -delta_h -22.4 + -analytical_expression 5.725 -2.478e-2 -790.4 # 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 + -log_k -9.89; -delta_h 11.82 + -analytical_expression -34.438 -3.316e-2 -1500 15.9485 # Blount 1977; Templeton, 1960 -Vm 52.9 Arcanite K2SO4 = SO4-2 + 2 K+ @@ -1027,12 +1032,14 @@ Arcanite -Vm 65.5 Mirabilite Na2SO4:10H2O = SO4-2 + 2 Na+ + 10 H2O - -analytical_expression -301.9326 -0.16232 0 141.078 # ref. 3 + -log_k -0.706; -delta_h 124 + -analytical_expression -53.037 0.1242 4562 # 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 + -log_k 0.65; -delta_h -23.1 + -analytical_expression 159.849 1.699e-2 -5000 -59.6073 # ref. 3 + Vm 52.9 Epsomite MgSO4:7H2O = Mg+2 + SO4-2 + 7 H2O log_k -1.74; -delta_h 10.57 kJ @@ -1905,7 +1912,6 @@ Pyrolusite 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. @@ -1947,14 +1953,14 @@ END # 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. +# a0 = -gamma x for cations, = 0 for anions (or fitted). # For details, consult ref. 1 and subroutine calc_vm(tc, pa) in prep.cpp. # ============================================================================================= # The viscosity is calculated with a (modified) Jones-Dole equation: # viscos / viscos_0 = 1 + A * Sum(0.5 z_i m_i) + fan * Sum(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 +# -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 and neutral species diff --git a/database/phreeqc_rates.dat b/database/phreeqc_rates.dat index 47cd6072..620eba40 100644 --- a/database/phreeqc_rates.dat +++ b/database/phreeqc_rates.dat @@ -4,7 +4,7 @@ SOLUTION_MASTER_SPECIES # -#element species alk gfw_formula element_gfw +#element species alk gfw_formula element_gfw # H H+ -1 H 1.008 H(0) H2 0 H @@ -40,7 +40,7 @@ N(+5) NO3- 0 N N(+3) NO2- 0 N N(0) N2 0 N N(-3) NH4+ 0 N 14.0067 -#Amm AmmH+ 0 AmmH 17.031 +#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 @@ -66,7 +66,7 @@ H+ = H+ -dw 9.31e-9 838 6.96 -2.285 0.206 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 tracer diffusion. +# a = DH ion size (= 3.5 - 25), a2 = exponent (= 0 2.5), visc = viscosity exponent (= 0 2.5), a3 = switch [a3(H+) = 24.01 = new dw calculation from A.D. 2024], a_v_dif = exponent in (viscos_0_tc / viscos)^a_v_dif for tracer diffusion. # For SC, Dw(TK) *= (viscos_0_tc / viscos)^visc (visc = 0.206 for H+) # a3 > 5 or a3 = 0 or not defined ? ka = DH_B * a * (1 + (vm - v0))^a2 * mu^0.5, in Onsager-Falkenhagen eqn. (For H+, the reference ion, vm = v0 = 0, a *= (1 + mu)^a2.) @@ -76,7 +76,7 @@ H+ = H+ # If a_v_dif <> 0, Dw(TK) *= (viscos_0_tc / viscos)^a_v_dif in TRANSPORT. e- = e- H2O = H2O - -dw 2.299e-9 -249 # Holz et al., Phys. Chem. Chem. Phys., 2000, 2, 4740. + -dw 2.299e-9 -249 # Holz et al., Phys. Chem. Chem. Phys., 2000, 2, 4740. # 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 @@ -143,20 +143,20 @@ CO3-2 = CO3-2 -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 + -gamma 5.0 -0.04 + -Vm 5.36 10.69 33.566 -15.03 4.2582 25 0.341 153.8 1.089e-2 0.9224 # with Na2SO4 & better calculation of sulfates' solubilities in NaCl + -viscosity -0.5 0.521 4.2e-4 9.78e-3 1.24e-2 2.5 -4.94e-2 + -dw 1.07e-9 -77.4 10.14 0.5 0.5549 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 6.94e-2 -0.141 2.04e-2 9.4e-3 3.73e-2 0.898 - # -dw 1.98e-9 203 1.47 2.644 6.81e-2 +#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 6.94e-2 -0.141 2.04e-2 9.4e-3 3.73e-2 0.898 +# -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 @@ -206,14 +206,14 @@ H2Sg = H2Sg # H2S -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 + -analytic 293.29227 0.1360833 -10576.913 -123.73158 0 -6.996455e-5 -Vm -9.66 28.5 80 -22.9 1.89 0 1.09 0 0 1 -viscosity -2.26e-2 0.106 2.184e-2 -3.2e-3 0 0.4082 -1.634 # < 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 + -log_k -86.06; -delta_h 138.43 kcal + -analytic -1e3 -0.322 -5897.7 416.82 0 -1.88e-5 -Vm 5.7889 6.3536 3.2528 -3.0417 -0.3943 # supcrt -dw 2.35e-9 2 H+ + 2 e- = H2 @@ -300,8 +300,8 @@ NO3- + 2 H+ + 2 e- = NO2- + H2O -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- = NH4+ + 3 H2O - -log_k 119.077 - -delta_h -187.055 kcal + -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 6.94e-2 -0.141 2.04e-2 9.4e-3 3.73e-2 0.898 @@ -316,11 +316,11 @@ NH4+ = NH3 + H+ -dw 2.28e-9 #AmmH+ + SO4-2 = AmmHSO4- NH4+ + SO4-2 = NH4SO4- - -gamma 2.10 -0.0419 - -log_k 1.212; -delta_h 8.61 kJ - -Vm -8.78 0 -36.09 0 -8.60 0 87.62 0 -0.3123 0.1172 - -viscosity 0 0.121 -8e-3 0.177 -8e-3 0.512 0.629 - -dw 0.9e-9 100 2.1 2 0 + -gamma 3.64 -4.75e-2 + -log_k 1.276; -delta_h -3.24 kcal + -Vm 6.64 8.5 -5.84 -3.1 2 0 19.24 0 -7.84e-2 0.289 + -viscosity 0.267 -0.207 9.75e-2 6.18e-2 1.99e-2 1.166 0.61 + -dw 1.56e-9 498 25 0.5 0.684 H3BO3 = H2BO3- + H+ -log_k -9.24 -delta_h 3.224 kcal @@ -375,10 +375,11 @@ Ca+2 + CO3-2 + H+ = CaHCO3+ -Vm 3.19 .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 + -gamma 0 4.45e-2 + -log_k 2.14; -delta_h 24.4 + -analytical_expression 1.478 8.29e-3 -538.2 + -vm 2.7 2 2 -3.7 + -dw 4.71e-9 Ca+2 + HSO4- = CaHSO4+ -log_k 1.08 Ca+2 + PO4-3 = CaPO4- @@ -415,19 +416,19 @@ Mg+2 + H+ + CO3-2 = MgHCO3+ -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 + -gamma 0 0.20 + -log_k 2.42; -delta_h 19.0 + -analytical_expression 0 9.64e-3 -136 # epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC + -Vm 11.92 -27.758 29.752 -10.302 -0.1 + -viscosity -0.799 1 2.2e-4 8.53e-2 -4.6e-3 1.35 -0.796 -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 + -log_k 0.52; -delta_h -13.6 + -analytical_expression 0 -1.51e-3 0 0 8.604e4 # epsomite/hexahydrite/kieserite solubilities, 0 - 200 oC + -Vm 4.248 9.83 -7 -2.672 2 3.5 5 100 0.3359 9.518e-2 + -viscosity 0.324 6.84e-2 -2.09e-2 0.104 6.19e-3 1.983 1e-3 + -dw 1.11e-9 -500 3.5 0.5 0.731 Mg+2 + PO4-3 = MgPO4- -log_k 6.589 -delta_h 3.1 kcal @@ -453,12 +454,19 @@ Na+ + HCO3- = NaHCO3 -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 + -gamma 3.5 0.1072 + -log_k 0.94; -delta_h 8.23 + -analytical_expression -0.304 4.51e-3 -28.9 # mirabilite/thenardite solubilities, 0 - 200 oC + -Vm 8.523 -4.685 -8.61 0.106 2.7 25 3.634 13.4 3.738e-2 0.5476 + -viscosity -1 0.33 0.128 1.143 7.7e-4 1.9e-2 -0.387 + -dw 4e-10 -200 3.5 0.5 0.5 +2 Na+ + SO4-2 = Na2SO4 + -gamma 0 8.85e-2 + -log_k -2.37; -delta_h 82 + -analytical_expression 15.432 -5.75e-3 -4796 # sulfates solubilities in NaCl + -Vm 9.405 -15.5 25 8.4 0.25 + -viscosity -0.5 0.485 -1e-3 0.147 0 0.947 -0.175 + -dw 0.8e-9 Na+ + HPO4-2 = NaHPO4- -log_k 0.29 -gamma 5.4 0 @@ -473,11 +481,11 @@ K+ + HCO3- = KHCO3 -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 + -log_k 1.18; -delta_h 3 -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 + -Vm 3.443 5.04 13 -3.324 2.447 0 20 0 7.77e-3 0.3497 + -viscosity 0.107 0.19 2.23e-2 -0.148 -4.91e-2 0.537 0.195 + -dw 1.22e-9 100 25 0.5 2.5 K+ + HPO4-2 = KHPO4- -log_k 0.29 -gamma 5.4 0 @@ -497,9 +505,8 @@ Fe+2 + CO3-2 = FeCO3 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 + -log_k 2.25; -delta_h 3.23 kcal + -Vm 5.8 6.5 3.7 -3 -0.09 Fe+2 + HSO4- = FeHSO4+ -log_k 1.08 Fe+2 + 2 HS- = Fe(HS)2 @@ -601,9 +608,9 @@ 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 + -gamma 0 -0.098 + -log_k 1.408; -delta_h 21.55 + -Vm 1.88 6.5 10 -3 0.1 Mn+2 + 2 NO3- = Mn(NO3)2 -log_k 0.6 -delta_h -0.396 kcal @@ -696,7 +703,8 @@ Ba+2 + HCO3- = BaHCO3+ -delta_h 5.56 kcal -analytic -3.0938 0.013669 Ba+2 + SO4-2 = BaSO4 - -log_k 2.7 + -log_k 3.457; -delta_h 26.15 + -vm -6.25 24.66 -4.38 10.97 0.5 Sr+2 + H2O = SrOH+ + H+ -log_k -13.29 -gamma 5 0 @@ -815,12 +823,13 @@ Zn+2 + 2 CO3-2 = Zn(CO3)2-2 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 + -gamma 0 0.1 + -log_k 2.26; -delta_h 16.15 + -Vm 0.409 6.5 2 -3 0 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 + -gamma 0.59 0.1 + -log_k 1.15; -delta_h 17.52 + -Vm 9.21 10.6 9 -3.2 3.8 25 0 100 -1e-3 0.256 Zn+2 + Br- = ZnBr+ -log_k -0.58 Zn+2 + 2 Br- = ZnBr2 @@ -866,12 +875,13 @@ Cd+2 + 2 CO3-2 = Cd(CO3)2-2 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 + -gamma 0 0.1 + -log_k 1.016; -delta_h 6.84 + -Vm 2.11 6.5 10 -3 0.1 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 + -gamma 5.201 -0.1 + -log_k 2.688; -delta_h 0.19 + -Vm 9.14 10.6 -3.06 -3.2 3.8 7.44 1.27 0.32 -1e-3 2.5 Cd+2 + Br- = CdBr+ -log_k 2.17 -delta_h -0.81 kcal @@ -991,29 +1001,24 @@ Witherite -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) + -log_k -4.55; -delta_h -6.70 + -analytical_expression 72.244 -1.474e-2 -4040 -23.7823 # fits the appendix data of Appelo, 2015, AG 55, 62 + -Vm 73.9 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 + log_k -4.25; -delta_h -22.4 + -analytical_expression 5.725 -2.478e-2 -790.4 # 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 + -log_k -9.89; -delta_h 11.82 + -analytical_expression -34.438 -3.316e-2 -1500 15.9485 # Blount 1977; Templeton, 1960 -Vm 52.9 Arcanite K2SO4 = SO4-2 + 2 K+ @@ -1023,12 +1028,14 @@ Arcanite -Vm 65.5 Mirabilite Na2SO4:10H2O = SO4-2 + 2 Na+ + 10 H2O - -analytical_expression -301.9326 -0.16232 0 141.078 # ref. 3 + -log_k -0.706; -delta_h 124 + -analytical_expression -53.037 0.1242 4562 # 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 + -log_k 0.65; -delta_h -23.1 + -analytical_expression 159.849 1.699e-2 -5000 -59.6073 # ref. 3 + Vm 52.9 Epsomite MgSO4:7H2O = Mg+2 + SO4-2 + 7 H2O log_k -1.74; -delta_h 10.57 kJ @@ -1240,7 +1247,7 @@ CH4(g) #Amm(g) # Amm = Amm NH3(g) - NH3 = NH3 + 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 @@ -3133,14 +3140,14 @@ Wollastonite -6.97 700 56 0.4 0 0 # 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. +# a0 = -gamma x for cations, = 0 for anions (or fitted). # For details, consult ref. 1 and subroutine calc_vm(tc, pa) in prep.cpp. # ============================================================================================= # The viscosity is calculated with a (modified) Jones-Dole equation: # viscos / viscos_0 = 1 + A * Sum(0.5 z_i m_i) + fan * Sum(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 +# -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 and neutral species