Input file: ..\examples\ex17 Output file: ex17.out Database file: ..\database\pitzer.dat ------------------ Reading data base. ------------------ SOLUTION_MASTER_SPECIES SOLUTION_SPECIES PHASES PITZER EXCHANGE_MASTER_SPECIES EXCHANGE_SPECIES SURFACE_MASTER_SPECIES SURFACE_SPECIES END ------------------------------------ Reading input data for simulation 1. ------------------------------------ TITLE Example 17.--Inverse modeling of Black Sea water evaporation SOLUTION 1 Black Sea water units mg/L density 1.014 pH 8.0 # estimated Ca 233 Mg 679 Na 5820 K 193 S(6) 1460 Cl 10340 Br 35 C 1 CO2(g) -3.5 SOLUTION 2 Composition during halite precipitation units mg/L density 1.271 pH 5.0 # estimated Ca 0.0 Mg 50500 Na 55200 K 15800 S(6) 76200 Cl 187900 Br 2670 C 1 CO2(g) -3.5 INVERSE_MODELING solutions 1 2 uncertainties .025 range balances Br K Mg phases H2O(g) pre Calcite pre CO2(g) pre Gypsum pre Halite pre Glauberite pre Polyhalite pre END ----- TITLE ----- Example 17.--Inverse modeling of Black Sea water evaporation ------------------------------------------- Beginning of initial solution calculations. ------------------------------------------- Initial solution 1. Black Sea water -----------------------------Solution composition------------------------------ Elements Molality Moles Br 4.401e-004 4.401e-004 C 8.453e-004 8.453e-004 Equilibrium with CO2(g) Ca 5.841e-003 5.841e-003 Cl 2.930e-001 2.930e-001 K 4.960e-003 4.960e-003 Mg 2.807e-002 2.807e-002 Na 2.544e-001 2.544e-001 S(6) 1.527e-002 1.527e-002 ----------------------------Description of solution---------------------------- pH = 8.000 pe = 4.000 Specific Conductance (uS/cm, 25 oC) = 31362 Density (g/cm3) = 1.01094 Volume (L) = 1.00889 Activity of water = 0.990 Ionic strength = 3.752e-001 Mass of water (kg) = 1.000e+000 Total alkalinity (eq/kg) = 8.684e-004 Total CO2 (mol/kg) = 8.453e-004 Temperature (deg C) = 25.00 Electrical balance (eq) = 2.250e-003 Percent error, 100*(Cat-|An|)/(Cat+|An|) = 0.35 Iterations = 9 Gamma iterations = 3 Osmotic coefficient = 0.89851 Density of water = 0.99706 Total H = 1.110132e+002 Total O = 5.556983e+001 ----------------------------Distribution of species---------------------------- MacInnes MacInnes MacInnes Log Log Log mole V Species Molality Activity Molality Activity Gamma cm3/mol OH- 1.663e-006 9.977e-007 -5.779 -6.001 -0.222 -2.99 H+ 1.290e-008 1.000e-008 -7.889 -8.000 -0.111 0.00 H2O 5.551e+001 9.903e-001 1.744 -0.004 0.000 18.07 Br 4.401e-004 Br- 4.401e-004 3.004e-004 -3.356 -3.522 -0.166 25.36 C(4) 8.453e-004 HCO3- 8.044e-004 4.944e-004 -3.095 -3.306 -0.211 25.95 CO3-2 1.612e-005 2.264e-006 -4.793 -5.645 -0.853 -1.27 MgCO3 1.441e-005 1.441e-005 -4.841 -4.841 0.000 -17.09 CO2 1.036e-005 1.096e-005 -4.985 -4.960 0.024 30.26 Ca 5.841e-003 Ca+2 5.841e-003 1.473e-003 -2.233 -2.832 -0.598 -16.97 Cl 2.930e-001 Cl- 2.930e-001 1.960e-001 -0.533 -0.708 -0.175 18.61 K 4.960e-003 K+ 4.960e-003 3.418e-003 -2.305 -2.466 -0.162 9.48 Mg 2.807e-002 Mg+2 2.805e-002 7.511e-003 -1.552 -2.124 -0.572 -20.69 MgCO3 1.441e-005 1.441e-005 -4.841 -4.841 0.000 -17.09 MgOH+ 1.244e-006 1.155e-006 -5.905 -5.938 -0.032 (0) Na 2.544e-001 Na+ 2.544e-001 1.836e-001 -0.595 -0.736 -0.142 -0.79 S(6) 1.527e-002 SO4-2 1.527e-002 2.117e-003 -1.816 -2.674 -0.858 17.27 HSO4- 2.952e-009 2.017e-009 -8.530 -8.695 -0.165 40.79 ------------------------------Saturation indices------------------------------- Phase SI log IAP log K(298 K, 1 atm) Anhydrite -1.28 -5.51 -4.22 CaSO4 Aragonite -0.26 -8.48 -8.22 CaCO3 Arcanite -5.83 -7.61 -1.78 K2SO4 Bischofite -8.02 -3.57 4.46 MgCl2:6H2O Bloedite -6.62 -8.96 -2.35 Na2Mg(SO4)2:4H2O Brucite -3.25 -14.13 -10.88 Mg(OH)2 Burkeite -14.64 -15.41 -0.77 Na6CO3(SO4)2 Calcite -0.07 -8.48 -8.41 CaCO3 Carnallite -11.07 -6.74 4.33 KMgCl3:6H2O CO2(g) -3.50 -4.96 -1.46 CO2 Pressure 0.0 atm, phi 1.000. Dolomite 0.84 -16.25 -17.08 CaMg(CO3)2 Epsomite -2.95 -4.83 -1.88 MgSO4:7H2O Gaylussite -6.19 -15.62 -9.42 CaNa2(CO3)2:5H2O Glaserite -9.68 -13.48 -3.80 NaK3(SO4)2 Glauberite -4.41 -9.65 -5.25 Na2Ca(SO4)2 Gypsum -0.93 -5.51 -4.58 CaSO4:2H2O H2O(g) -1.51 -0.00 1.50 H2O Halite -3.01 -1.44 1.57 NaCl Hexahydrite -3.19 -4.82 -1.63 MgSO4:6H2O Kainite -7.79 -7.99 -0.19 KMgClSO4:3H2O Kalicinite -6.05 -16.11 -10.06 KHCO3 Kieserite -4.68 -4.80 -0.12 MgSO4:H2O Labile_S -8.14 -13.81 -5.67 Na4Ca(SO4)3:2H2O Leonhardite -3.93 -4.82 -0.89 MgSO4:4H2O Leonite -8.44 -12.42 -3.98 K2Mg(SO4)2:4H2O Magnesite 0.06 -7.77 -7.83 MgCO3 Mirabilite -2.98 -4.19 -1.21 Na2SO4:10H2O Misenite -75.64 -86.45 -10.81 K8H6(SO4)7 Nahcolite -3.64 -14.38 -10.74 NaHCO3 Natron -6.34 -7.16 -0.82 Na2CO3:10H2O Nesquehonite -2.62 -7.78 -5.17 MgCO3:3H2O Pentahydrite -3.53 -4.82 -1.28 MgSO4:5H2O Pirssonite -6.37 -15.60 -9.23 Na2Ca(CO3)2:2H2O Polyhalite -9.68 -23.43 -13.74 K2MgCa2(SO4)4:2H2O Portlandite -9.64 -14.83 -5.19 Ca(OH)2 Schoenite -8.10 -12.43 -4.33 K2Mg(SO4)2:6H2O Sylvite -4.07 -3.17 0.90 KCl Syngenite -5.67 -13.12 -7.45 K2Ca(SO4)2:H2O Trona -10.12 -21.51 -11.38 Na3H(CO3)2:2H2O Initial solution 2. Composition during halite precipitation -----------------------------Solution composition------------------------------ Elements Molality Moles Br 3.785e-002 3.785e-002 C 7.206e-006 7.206e-006 Equilibrium with CO2(g) Cl 6.004e+000 6.004e+000 K 4.578e-001 4.578e-001 Mg 2.354e+000 2.354e+000 Na 2.720e+000 2.720e+000 S(6) 8.986e-001 8.986e-001 ----------------------------Description of solution---------------------------- pH = 5.000 pe = 4.000 Specific Conductance (uS/cm, 25 oC) = 598313 Density (g/cm3) = 1.26987 Volume (L) = 1.17915 Activity of water = 0.681 Ionic strength = 1.111e+001 Mass of water (kg) = 1.000e+000 Total alkalinity (eq/kg) = 7.758e-006 Total CO2 (mol/kg) = 7.206e-006 Temperature (deg C) = 25.00 Electrical balance (eq) = 4.629e-002 Percent error, 100*(Cat-|An|)/(Cat+|An|) = 0.29 Iterations = 16 Gamma iterations = 7 Osmotic coefficient = 1.71249 Density of water = 0.99706 Total H = 1.110124e+002 Total O = 5.910065e+001 ----------------------------Distribution of species---------------------------- MacInnes MacInnes MacInnes Log Log Log mole V Species Molality Activity Molality Activity Gamma cm3/mol H+ 5.602e-007 1.000e-005 -6.252 -5.000 1.252 0.00 OH- 1.205e-008 6.857e-010 -7.919 -9.164 -1.245 9.31 H2O 5.551e+001 6.806e-001 1.744 -0.167 0.000 18.07 Br 3.785e-002 Br- 3.785e-002 4.950e-002 -1.422 -1.305 0.116 27.92 C(4) 7.206e-006 HCO3- 4.558e-006 3.398e-007 -5.341 -6.469 -1.128 47.51 CO2 2.575e-006 1.096e-005 -5.589 -4.960 0.629 30.26 MgCO3 6.713e-008 6.713e-008 -7.173 -7.173 0.000 -17.09 CO3-2 5.877e-009 1.556e-012 -8.231 -11.808 -3.577 14.84 Cl 6.004e+000 Cl- 6.004e+000 4.512e+000 0.778 0.654 -0.124 20.71 K 4.578e-001 K+ 4.578e-001 4.785e-001 -0.339 -0.320 0.019 14.34 Mg 2.354e+000 Mg+2 2.354e+000 5.091e+001 0.372 1.707 1.335 -15.59 MgOH+ 6.271e-006 5.379e-006 -5.203 -5.269 -0.067 (0) MgCO3 6.713e-008 6.713e-008 -7.173 -7.173 0.000 -17.09 Na 2.720e+000 Na+ 2.720e+000 8.671e+000 0.435 0.938 0.503 2.74 S(6) 8.986e-001 SO4-2 8.986e-001 2.260e-003 -0.046 -2.646 -2.599 31.36 HSO4- 2.669e-006 2.153e-006 -5.574 -5.667 -0.093 42.44 ------------------------------Saturation indices------------------------------- Phase SI log IAP log K(298 K, 1 atm) Arcanite -1.51 -3.29 -1.78 K2SO4 Bischofite -2.44 2.01 4.46 MgCl2:6H2O Bloedite -0.03 -2.38 -2.35 Na2Mg(SO4)2:4H2O Brucite -5.74 -16.62 -10.88 Mg(OH)2 Burkeite -10.70 -11.47 -0.77 Na6CO3(SO4)2 Carnallite -1.98 2.35 4.33 KMgCl3:6H2O CO2(g) -3.50 -4.96 -1.46 CO2 Pressure 0.0 atm, phi 1.000. Epsomite -0.23 -2.11 -1.88 MgSO4:7H2O Glaserite -1.51 -5.31 -3.80 NaK3(SO4)2 H2O(g) -1.67 -0.17 1.50 H2O Halite 0.02 1.59 1.57 NaCl Hexahydrite -0.31 -1.94 -1.63 MgSO4:6H2O Kainite -0.91 -1.11 -0.19 KMgClSO4:3H2O Kalicinite -7.07 -17.13 -10.06 KHCO3 Kieserite -0.98 -1.11 -0.12 MgSO4:H2O Leonhardite -0.72 -1.61 -0.89 MgSO4:4H2O Leonite -0.91 -4.89 -3.98 K2Mg(SO4)2:4H2O Magnesite -2.27 -10.10 -7.83 MgCO3 Mirabilite -1.23 -2.44 -1.21 Na2SO4:10H2O Misenite -40.28 -51.08 -10.81 K8H6(SO4)7 Nahcolite -5.13 -15.87 -10.74 NaHCO3 Natron -10.78 -11.60 -0.82 Na2CO3:10H2O Nesquehonite -5.44 -10.60 -5.17 MgCO3:3H2O Pentahydrite -0.49 -1.77 -1.28 MgSO4:5H2O Schoenite -0.90 -5.23 -4.33 K2Mg(SO4)2:6H2O Sylvite -0.57 0.33 0.90 KCl Trona -14.75 -26.14 -11.38 Na3H(CO3)2:2H2O --------------------------------------------- Beginning of inverse modeling 1 calculations. --------------------------------------------- Using Cl1 standard precision optimization routine. Solution 1: Black Sea water Input Delta Input+Delta pH 8.000e+000 + 0.000e+000 = 8.000e+000 Alkalinity 8.684e-004 + 0.000e+000 = 8.684e-004 Br 4.401e-004 + 0.000e+000 = 4.401e-004 C(4) 8.453e-004 + 0.000e+000 = 8.453e-004 Ca 5.841e-003 + 0.000e+000 = 5.841e-003 Cl 2.930e-001 + 8.006e-004 = 2.938e-001 K 4.960e-003 + 1.034e-004 = 5.063e-003 Mg 2.807e-002 + -7.018e-004 = 2.737e-002 Na 2.544e-001 + 0.000e+000 = 2.544e-001 S(6) 1.527e-002 + 7.486e-005 = 1.535e-002 Solution 2: Composition during halite precipitation Input Delta Input+Delta pH 5.000e+000 + 0.000e+000 = 5.000e+000 Alkalinity 7.758e-006 + -1.940e-007 = 7.564e-006 Br 3.785e-002 + 9.440e-004 = 3.880e-002 C(4) 7.206e-006 + 1.802e-007 = 7.387e-006 Ca 0.000e+000 + 0.000e+000 = 0.000e+000 Cl 6.004e+000 + 1.501e-001 = 6.154e+000 K 4.578e-001 + -1.144e-002 = 4.464e-001 Mg 2.354e+000 + 5.884e-002 = 2.413e+000 Na 2.720e+000 + -4.642e-002 = 2.674e+000 S(6) 8.986e-001 + -2.247e-002 = 8.761e-001 Solution fractions: Minimum Maximum Solution 1 8.815e+001 8.780e+001 8.815e+001 Solution 2 1.000e+000 1.000e+000 1.000e+000 Phase mole transfers: Minimum Maximum H2O(g) -4.837e+003 -4.817e+003 -4.817e+003 H2O Calcite -3.827e-002 -3.923e-002 -3.716e-002 CaCO3 CO2(g) -3.624e-002 -3.906e-002 -3.328e-002 CO2 Gypsum -4.767e-001 -4.905e-001 -4.609e-001 CaSO4:2H2O Halite -1.975e+001 -2.033e+001 -1.901e+001 NaCl Redox mole transfers: Sum of residuals (epsilons in documentation): 1.923e+002 Sum of delta/uncertainty limit: 9.820e+000 Maximum fractional error in element concentration: 2.500e-002 Model contains minimum number of phases. =============================================================================== Summary of inverse modeling: Number of models found: 1 Number of minimal models found: 1 Number of infeasible sets of phases saved: 11 Number of calls to cl1: 29 ------------------ End of simulation. ------------------ ------------------------------------ Reading input data for simulation 2. ------------------------------------ ------------------------------- End of Run after 0.593 Seconds. -------------------------------