From d29af24a31edc009446c6e1eeded4145f73d3705 Mon Sep 17 00:00:00 2001 From: David Parkhurst Date: Sat, 16 Nov 2024 18:50:11 -0700 Subject: [PATCH] added test case for the dl_type error, generated charge imbalance --- mytest/CMakeLists.txt | 1 + mytest/dl_type_error | 49 ++++++ mytest/dl_type_error.out | 329 +++++++++++++++++++++++++++++++++++++++ mytest/dl_type_error.sel | 3 + 4 files changed, 382 insertions(+) create mode 100644 mytest/dl_type_error create mode 100644 mytest/dl_type_error.out create mode 100644 mytest/dl_type_error.sel diff --git a/mytest/CMakeLists.txt b/mytest/CMakeLists.txt index 1347abe2..c8d9f252 100644 --- a/mytest/CMakeLists.txt +++ b/mytest/CMakeLists.txt @@ -102,6 +102,7 @@ set(TESTS diff_c dissolve_only dist_x + dl_type_error donly DonnanBug dump_test diff --git a/mytest/dl_type_error b/mytest/dl_type_error new file mode 100644 index 00000000..34ffe0a1 --- /dev/null +++ b/mytest/dl_type_error @@ -0,0 +1,49 @@ +DATABASE ../database/phreeqc.dat +SELECTED_OUTPUT 101 + file dl_type_error.sel +USER_PUNCH 101 + headings Mu SC + start +10 PUNCH STR_F$(MU, 20, 12) +20 PUNCH STR_F$(SC, 20, 10) + end +RATES +Decay +-start +40 SAVE moles +-end +SOLUTION +-units mol/kgw +pH 8 +Na 1 +P 1 charge +Si 1e-10 +END +SURFACE +Hfo_w 0.1 1 600 +-donnan +END +KINETICS +Decay +-m 1 +-formula Si -1 +-steps 10 +-rk 1 +END +USER_GRAPH 1 + -headings time Si Charge + -axis_titles "Time, seconds" "Molality" "Charge balance, equivalents" + -axis_scale y_axis auto auto auto auto + -initial_solutions false + -connect_simulations true + -plot_concentration_vs x + -start +10 GRAPH_X TOTAL_TIME +20 GRAPH_Y log10(TOT("Si")) +30 GRAPH_SY CHARGE_BALANCE + -end + -active true +END +RUN_CELLS +-cell 1 +END diff --git a/mytest/dl_type_error.out b/mytest/dl_type_error.out new file mode 100644 index 00000000..6c860945 --- /dev/null +++ b/mytest/dl_type_error.out @@ -0,0 +1,329 @@ + Input file: dl_type_error + Output file: dl_type_error.out +Database file: ../database/phreeqc.dat + +------------------ +Reading data base. +------------------ + + SOLUTION_MASTER_SPECIES + SOLUTION_SPECIES + PHASES + GAS_BINARY_PARAMETERS + EXCHANGE_MASTER_SPECIES + EXCHANGE_SPECIES + SURFACE_MASTER_SPECIES + SURFACE_SPECIES + MEAN_GAMMAS + RATES + END +------------------------------------ +Reading input data for simulation 1. +------------------------------------ + + DATABASE ../database/phreeqc.dat + SELECTED_OUTPUT 101 + file dl_type_error.sel + USER_PUNCH 101 + headings Mu SC + start + 10 PUNCH STR_F$(MU, 20, 12) + 20 PUNCH STR_F$(SC, 20, 10) + end +------------------ +End of simulation. +------------------ + +------------------------------------ +Reading input data for simulation 2. +------------------------------------ + + RATES + Decay + start + 40 SAVE moles + end + SOLUTION + units mol/kgw + pH 8 + Na 1 + P 1 charge + Si 1e-10 + END +------------------------------------------- +Beginning of initial solution calculations. +------------------------------------------- + +Initial solution 1. + +-----------------------------Solution composition------------------------------ + + Elements Molality Moles + + Na 1.000e+00 1.000e+00 + P 5.072e-01 5.072e-01 Charge balance + Si 1.000e-10 1.000e-10 + +----------------------------Description of solution---------------------------- + + pH = 8.000 + pe = 4.000 + Specific Conductance (µS/cm, 25°C) = 39420 + Density (g/cm³) = 1.04881 + Volume (L) = 1.02181 + Viscosity (mPa s) = 1.03500 + Activity of water = 0.976 + Ionic strength (mol/kgw) = 1.258e+00 + Mass of water (kg) = 1.000e+00 + Total alkalinity (eq/kg) = 4.928e-01 + Temperature (°C) = 25.00 + Electrical balance (eq) = 7.518e-10 + Percent error, 100*(Cat-|An|)/(Cat+|An|) = 0.00 + Iterations = 6 + Total H = 1.115340e+02 + Total O = 5.753495e+01 + +----------------------------Distribution of species---------------------------- + + Log Log Log mole V + Species Molality Activity Molality Activity Gamma cm³/mol + + OH- 1.757e-06 9.882e-07 -5.755 -6.005 -0.250 -1.71 + H+ 1.357e-08 1.000e-08 -7.867 -8.000 -0.133 0.00 + H2O 5.551e+01 9.764e-01 1.744 -0.010 0.000 18.07 +H(0) 1.060e-27 + H2 5.299e-28 7.079e-28 -27.276 -27.150 0.126 28.61 +Na 1.000e+00 + Na+ 8.825e-01 6.612e-01 -0.054 -0.180 -0.125 -0.17 + NaHPO4- 1.175e-01 7.566e-02 -0.930 -1.121 -0.191 122.70 +O(0) 1.187e-38 + O2 5.935e-39 7.929e-39 -38.227 -38.101 0.126 30.40 +P 5.072e-01 + HPO4-2 3.746e-01 5.868e-02 -0.426 -1.231 -0.805 10.82 + NaHPO4- 1.175e-01 7.566e-02 -0.930 -1.121 -0.191 122.70 + H2PO4- 1.468e-02 9.452e-03 -1.833 -2.024 -0.191 35.66 + PO4-3 3.190e-04 2.646e-06 -3.496 -5.577 -2.081 -15.23 + H3PO4 1.042e-08 1.392e-08 -7.982 -7.856 0.126 47.41 +Si 1.000e-10 + H4SiO4 9.675e-11 1.293e-10 -10.014 -9.889 0.126 52.08 + H3SiO4- 3.246e-12 1.906e-12 -11.489 -11.720 -0.231 29.00 + H2SiO4-2 7.554e-17 1.297e-17 -16.122 -16.887 -0.765 (0) + +------------------------------Saturation indices------------------------------- + + Phase SI** log IAP log K(298 K, 1 atm) + + Chalcedony -6.32 -9.87 -3.55 SiO2 + H2(g) -24.05 -27.15 -3.10 H2 + H2O(g) -1.51 -0.01 1.50 H2O + O2(g) -35.21 -38.10 -2.89 O2 + Quartz -5.89 -9.87 -3.98 SiO2 + SiO2(a) -7.16 -9.87 -2.71 SiO2 + +**For a gas, SI = log10(fugacity). Fugacity = pressure * phi / 1 atm. + For ideal gases, phi = 1. + +------------------ +End of simulation. +------------------ + +------------------------------------ +Reading input data for simulation 3. +------------------------------------ + + SURFACE + Hfo_w 0.1 1 600 + donnan + END +------------------ +End of simulation. +------------------ + +------------------------------------ +Reading input data for simulation 4. +------------------------------------ + + KINETICS + Decay + m 1 + formula Si -1 + steps 10 + rk 1 + END +------------------ +End of simulation. +------------------ + +------------------------------------ +Reading input data for simulation 5. +------------------------------------ + + USER_GRAPH 1 + -headings time Si Charge + -axis_titles "Time, seconds" "Molality" "Charge balance, equivalents" + -axis_scale y_axis auto auto auto auto + -initial_solutions false + -connect_simulations true + -plot_concentration_vs x + -start + 10 GRAPH_X TOTAL_TIME + 20 GRAPH_Y log10(TOT("Si")) + 30 GRAPH_SY CHARGE_BALANCE + -end + -active true + END +------------------ +End of simulation. +------------------ + +------------------------------------ +Reading input data for simulation 6. +------------------------------------ + + RUN_CELLS + -cell 1 + END +-------------------------- +Beginning of run as cells. +-------------------------- + +----------------------------------------- +Beginning of batch-reaction calculations. +----------------------------------------- + +Reaction step 1. + +Using solution 1. +Using surface 1. +Using kinetics 1. + +Kinetics 1. + + Time step: 10 seconds + + Rate name Delta Moles Total Moles Reactant Coefficient + + Decay -0.000e+00 1.000e+00 Si -1 + +------------------------------Surface composition------------------------------ + +Diffuse Double Layer Surface-Complexation Model + +Hfo + -3.759e-10 Surface + diffuse layer charge, eq + -6.626e-03 Surface charge, eq + -1.066e+00 sigma, C/m² + -1.423e-01 psi, V + 5.538e+00 -F*psi/RT + 2.542e+02 exp(-F*psi/RT) + 1.000e+00 specific area, m²/g + 6.000e+02 m² for 6.000e+02 g + + Water in diffuse layer: 6.000e-03 kg, 100.0% of total DDL-water. + viscosity: 0.00000 mPa s for DDL water. + + Total moles in diffuse layer (excluding water), Donnan calculation. + Donnan Layer potential, psi_DL = -1.270e-02 V. + Boltzmann factor, exp(-psi_DL * F / RT) = 1.639e+00 (= c_DL / c_free if z is +1). + + Element Moles + H 1.7761e-03 + Na 9.0866e-03 + O 4.8512e-03 + P 1.2127e-03 + Si 6.1252e-16 + +Hfo_w + 1.000e-01 moles + Mole Log + Species Moles Fraction Molality Molality + + Hfo_wOH 4.713e-02 0.471 4.719e-02 -1.326 + Hfo_wOH2+ 2.773e-02 0.277 2.777e-02 -1.556 + Hfo_wHPO4- 1.345e-02 0.135 1.347e-02 -1.871 + Hfo_wPO4-2 9.533e-03 0.095 9.546e-03 -2.020 + Hfo_wO- 1.835e-03 0.018 1.838e-03 -2.736 + Hfo_wH2PO4 3.225e-04 0.003 3.229e-04 -3.491 + Hfo_wH2SiO4- 4.832e-11 0.000 4.839e-11 -10.315 + Hfo_wH3SiO4 4.611e-11 0.000 4.617e-11 -10.336 + Hfo_wHSiO4-2 5.426e-12 0.000 5.434e-12 -11.265 + +-----------------------------Solution composition------------------------------ + + Elements Molality Moles + + Na 9.923e-01 9.909e-01 + P 4.833e-01 4.827e-01 + Si 1.437e-13 1.435e-13 + +----------------------------Description of solution---------------------------- + + pH = 9.925 Charge balance + pe = -10.914 Adjusted to redox equilibrium + Specific Conductance (µS/cm, 25°C) = 39932 + Density (g/cm³) = 1.04684 + Volume (L) = 1.02002 + Viscosity (mPa s) = 1.03726 + Activity of water = 0.976 + Ionic strength (mol/kgw) = 1.309e+00 + Mass of water (kg) = 9.986e-01 + Total alkalinity (eq/kg) = 5.090e-01 + Temperature (°C) = 25.00 + Electrical balance (eq) = -2.351e-09 + Percent error, 100*(Cat-|An|)/(Cat+|An|) = -0.00 + Iterations = 0 (30 overall) + Total H = 1.114155e+02 + Total O = 5.736017e+01 + +----------------------------Distribution of species---------------------------- + + Log Log Log mole V + Species Molality Activity Molality Activity Gamma cm³/mol + + OH- 1.486e-04 8.320e-05 -3.828 -4.080 -0.252 -1.63 + H+ 1.613e-10 1.187e-10 -9.792 -9.925 -0.133 0.00 + H2O 5.551e+01 9.759e-01 1.744 -0.011 0.000 18.07 +H(0) 9.954e-02 + H2 4.977e-02 6.727e-02 -1.303 -1.172 0.131 28.61 +Na 9.923e-01 + Na+ 8.833e-01 6.654e-01 -0.054 -0.177 -0.123 -0.15 + NaHPO4- 1.090e-01 6.994e-02 -0.963 -1.155 -0.193 126.28 +O(0) 0.000e+00 + O2 0.000e+00 0.000e+00 -90.188 -90.057 0.131 30.40 +P 4.833e-01 + HPO4-2 3.486e-01 5.390e-02 -0.458 -1.268 -0.811 10.91 + NaHPO4- 1.090e-01 6.994e-02 -0.963 -1.155 -0.193 126.28 + PO4-3 2.564e-02 2.047e-04 -1.591 -3.689 -2.098 -15.09 + H2PO4- 1.606e-04 1.031e-04 -3.794 -3.987 -0.193 35.74 + H3PO4 1.333e-12 1.802e-12 -11.875 -11.744 0.131 47.41 +Si 1.437e-13 + H3SiO4- 1.064e-13 6.224e-14 -12.973 -13.206 -0.233 29.02 + H4SiO4 3.707e-14 5.011e-14 -13.431 -13.300 0.131 52.08 + H2SiO4-2 2.102e-16 3.566e-17 -15.677 -16.448 -0.770 (0) + +------------------------------Saturation indices------------------------------- + + Phase SI** log IAP log K(298 K, 1 atm) + + Chalcedony -9.73 -13.28 -3.55 SiO2 + H2(g) 1.93 -1.17 -3.10 H2 + H2O(g) -1.51 -0.01 1.50 H2O + O2(g) -87.16 -90.06 -2.89 O2 + Quartz -9.30 -13.28 -3.98 SiO2 + SiO2(a) -10.57 -13.28 -2.71 SiO2 + +**For a gas, SI = log10(fugacity). Fugacity = pressure * phi / 1 atm. + For ideal gases, phi = 1. + +------------------ +End of simulation. +------------------ + +------------------------------------ +Reading input data for simulation 7. +------------------------------------ + +------------------------------- +End of Run after 2.467 Seconds. +------------------------------- + diff --git a/mytest/dl_type_error.sel b/mytest/dl_type_error.sel new file mode 100644 index 00000000..f67280b7 --- /dev/null +++ b/mytest/dl_type_error.sel @@ -0,0 +1,3 @@ + Mu SC + 1.258047983469 39420.3633966330 + 1.308789599523 39932.2352633495