diff --git a/Phreeqc.h b/Phreeqc.h index 21ef40b5..1902f538 100644 --- a/Phreeqc.h +++ b/Phreeqc.h @@ -1066,6 +1066,7 @@ public: LDBLE calc_vm_Cl(void); int multi_D(LDBLE DDt, int mobile_cell, int stagnant); LDBLE find_J(int icell, int jcell, LDBLE mixf, LDBLE DDt, int stagnant); + void calc_b_ij(int icell, int jcell, int k, LDBLE b_i, LDBLE b_j, LDBLE g_i, LDBLE g_j, LDBLE free_i, LDBLE free_j, int stagnant); void diffuse_implicit(LDBLE DDt, int stagnant); int fill_spec(int cell_no, int ref_cell); LDBLE moles_from_redox_states(cxxSolution *sptr, const char *name); diff --git a/transport.cpp b/transport.cpp index 918a86a3..e7001b20 100644 --- a/transport.cpp +++ b/transport.cpp @@ -3664,6 +3664,46 @@ fill_m_s(struct J_ij *l_J_ij, int l_J_ij_count_spec, int icell, int stagnant) } return (OK); } +/* ---------------------------------------------------------------------- */ +void Phreeqc:: +calc_b_ij(int icell, int jcell, int k, LDBLE b_i, LDBLE b_j, LDBLE g_i, LDBLE g_j, LDBLE free_i, LDBLE free_j, int stagnant) +/* ---------------------------------------------------------------------- */ +{ + ct[icell].v_m[k].b_ij = b_i * (free_i + g_i) * b_j * (free_j + g_j) / (b_i * (free_i + g_i) + b_j * (free_j + g_j)); + // At filterends, concentrations of ions change step-wise to the DL. + // We take the harmonic mean for f_free, the average for the DL. + if (ct[icell].v_m[k].z) + { + if (!g_i && g_j) + { + ct[icell].v_m[k].b_ij = free_j * b_i * b_j / (b_i + b_j) + + b_i * (1 - free_j) / 4 + b_j * g_j / 4; + } + else if (g_i && !g_j) + ct[icell].v_m[k].b_ij = free_i * b_i * b_j / (b_i + b_j) + + b_j * (1 - free_i) / 4 + b_i * g_i / 4; + } + // for boundary cells... + if (stagnant > 1) + { /* for a diffusion experiment with well-mixed reservoir in cell 3 and the last stagnant cell, + and with the mixf * 2 for the boundary cells in the input... */ + if (icell == 3 && !g_i && g_j) + ct[icell].v_m[k].b_ij = b_j * (free_j + g_j) / 2; + else if (jcell == all_cells - 1 && !g_j && g_i) + ct[icell].v_m[k].b_ij = b_i * (free_i + g_i) / 2; + } + else + { + if (icell == 0 || (icell == count_cells + 1 && jcell == count_cells + count_cells + 1)) + ct[icell].v_m[k].b_ij = b_j * (free_j + g_j); + else if (icell == count_cells && jcell == count_cells + 1) + ct[icell].v_m[k].b_ij = b_i * (free_i + g_i); + } + if (ct[icell].v_m[k].z) + ct[icell].Dz2c += ct[icell].v_m[k].b_ij * ct[icell].v_m[k].zc * ct[icell].v_m[k].z; + return; +} + /* ---------------------------------------------------------------------- */ LDBLE Phreeqc:: find_J(int icell, int jcell, LDBLE mixf, LDBLE DDt, int stagnant) @@ -4142,7 +4182,7 @@ find_J(int icell, int jcell, LDBLE mixf, LDBLE DDt, int stagnant) g_j += it_sc->Get_z_gMCD_map()[ct[icell].v_m[k].z]; else { - dum1 = it_sc->Get_mass_water() / mass_water_bulk_x; + dum1 = it_sc->Get_mass_water() / t_aq2; dum2 = it_sc->Get_z_gMCD_map()[1] / dum1; g_j += pow(dum2, ct[icell].v_m[k].z) * dum1; } @@ -4152,32 +4192,18 @@ find_J(int icell, int jcell, LDBLE mixf, LDBLE DDt, int stagnant) } } - b_i = A1 * sol_D[icell].spec[i].Dwt * (f_free_i + g_i / ct[icell].visc1); - b_j = A2 * (f_free_j + g_j / ct[icell].visc2); - if (icell == count_cells && !stagnant) - ct[icell].v_m[k].b_ij = b_i; - else if (icell == all_cells - 1 && stagnant) - ct[icell].v_m[k].b_ij = b_i / 2; /* with the mixf *= 2 for this 'reservoir' cell in the input */ + b_i = A1 * sol_D[icell].spec[i].Dwt; + b_j = A2; + if (sol_D[icell].tk_x == sol_D[jcell].tk_x) + b_j *= sol_D[icell].spec[i].Dwt; else { - if (sol_D[icell].tk_x == sol_D[jcell].tk_x) - b_j *= sol_D[icell].spec[i].Dwt; - else - { - dum2 = sol_D[icell].spec[i].Dwt / sol_D[icell].viscos_f; - dum2 *= exp(sol_D[icell].spec[i].dw_t / sol_D[jcell].tk_x - sol_D[icell].spec[i].dw_t / sol_D[icell].tk_x); - dum2 *= sol_D[jcell].viscos_f; - b_j *= dum2; - } - ct[icell].v_m[k].b_ij = b_i * b_j / (b_i + b_j); - if (icell == 0 && !stagnant) - ct[icell].v_m[k].b_ij = b_j; - else if (icell == 3 && stagnant && !g_i && g_j) - ct[icell].v_m[k].b_ij = b_j / 2; /* with the mixf *= 2 for stagnant cell 3 in the input */ + dum2 = sol_D[icell].spec[i].Dwt / sol_D[icell].viscos_f; + dum2 *= exp(sol_D[icell].spec[i].dw_t / sol_D[jcell].tk_x - sol_D[icell].spec[i].dw_t / sol_D[icell].tk_x); + dum2 *= sol_D[jcell].viscos_f; + b_j *= dum2; } - - if (ct[icell].v_m[k].z) - ct[icell].Dz2c += ct[icell].v_m[k].b_ij * ct[icell].v_m[k].zc * ct[icell].v_m[k].z; + calc_b_ij(icell, jcell, k, b_i, b_j, g_i, g_j, f_free_i, f_free_j, stagnant); k++; } @@ -4249,7 +4275,7 @@ find_J(int icell, int jcell, LDBLE mixf, LDBLE DDt, int stagnant) g_i += it_sc->Get_z_gMCD_map()[ct[icell].v_m[k].z]; else { - dum1 = it_sc->Get_mass_water() / mass_water_bulk_x; + dum1 = it_sc->Get_mass_water() / t_aq1; dum2 = it_sc->Get_z_gMCD_map()[1] / dum1; g_i += pow(dum2, ct[icell].v_m[k].z) * dum1; } @@ -4266,31 +4292,18 @@ find_J(int icell, int jcell, LDBLE mixf, LDBLE DDt, int stagnant) g_j *= sol_D[jcell].spec[j].erm_ddl; } } - b_i = A1 * (f_free_i + g_i / ct[icell].visc1); - b_j = A2 * sol_D[jcell].spec[j].Dwt * (f_free_j + g_j / ct[icell].visc2); - if (icell == 0 && !stagnant) - ct[icell].v_m[k].b_ij = b_j; - else if (icell == 3 && stagnant && g_j && !g_i) - ct[icell].v_m[k].b_ij = b_j / 2; /* with the mixf *= 2 for 'reservoir' cell 3 in the input */ + b_i = A1; + b_j = A2 * sol_D[jcell].spec[j].Dwt; + if (sol_D[icell].tk_x == sol_D[jcell].tk_x) + b_i *= sol_D[jcell].spec[j].Dwt; else { - if (sol_D[icell].tk_x == sol_D[jcell].tk_x) - b_i *= sol_D[jcell].spec[j].Dwt; - else - { - dum2 = sol_D[jcell].spec[j].Dwt / sol_D[jcell].viscos_f; - dum2 *= exp(sol_D[jcell].spec[j].dw_t / sol_D[icell].tk_x - sol_D[jcell].spec[j].dw_t / sol_D[jcell].tk_x); - dum2 *= sol_D[icell].viscos_f; - b_i *= dum2; - } - ct[icell].v_m[k].b_ij = b_i * b_j / (b_i + b_j); - if (icell == count_cells && !stagnant) - ct[icell].v_m[k].b_ij = b_i; - else if (jcell == all_cells - 1 && stagnant && !g_j && g_i) - ct[icell].v_m[k].b_ij = b_i / 2; /* with the mixf * 2 for this 'reservoir' cell in the input */ + dum2 = sol_D[jcell].spec[j].Dwt / sol_D[jcell].viscos_f; + dum2 *= exp(sol_D[jcell].spec[j].dw_t / sol_D[icell].tk_x - sol_D[jcell].spec[j].dw_t / sol_D[jcell].tk_x); + dum2 *= sol_D[icell].viscos_f; + b_i *= dum2; } - if (ct[icell].v_m[k].z) - ct[icell].Dz2c += ct[icell].v_m[k].b_ij * ct[icell].v_m[k].zc * ct[icell].v_m[k].z; + calc_b_ij(icell, jcell, k, b_i, b_j, g_i, g_j, f_free_i, f_free_j, stagnant); k++; } @@ -4373,28 +4386,9 @@ find_J(int icell, int jcell, LDBLE mixf, LDBLE DDt, int stagnant) g_j *= sol_D[jcell].spec[j].erm_ddl; } } - b_i = A1 * sol_D[icell].spec[i].Dwt * (f_free_i + g_i / ct[icell].visc1); - b_j = A2 * sol_D[jcell].spec[j].Dwt * (f_free_j + g_j / ct[icell].visc2); - ct[icell].v_m[k].b_ij = b_i * b_j / (b_i + b_j); - // but for boundary cells... - if (stagnant > 1) - { /* for a diffusion experiment with well-mixed reservoir in cell 3 and the last stagnant cell, - and with the mixf * 2 for the boundary cells in the input... */ - if (icell == 3 && !g_i && g_j) - ct[icell].v_m[k].b_ij = b_j / 2; - else if (jcell == all_cells - 1 && !g_j && g_i) - ct[icell].v_m[k].b_ij = b_i / 2; - } - else - { - if (icell == 0 || (icell == count_cells + 1 && jcell == count_cells + count_cells + 1)) - ct[icell].v_m[k].b_ij = b_j; - else if (icell == count_cells && jcell == count_cells + 1) - ct[icell].v_m[k].b_ij = b_i; - } - - if (ct[icell].v_m[k].z) - ct[icell].Dz2c += ct[icell].v_m[k].b_ij * ct[icell].v_m[k].zc * ct[icell].v_m[k].z; + b_i = A1 * sol_D[icell].spec[i].Dwt; + b_j = A2 * sol_D[jcell].spec[j].Dwt; + calc_b_ij(icell, jcell, k, b_i, b_j, g_i, g_j, f_free_i, f_free_j, stagnant); //ddlm = sol_D[jcell].spec[j].lm - sol_D[icell].spec[i].lm; // appt: this could give an incorrect large factor for implicit //if (fabs(ddlm) > 1e-10)