From 8cd33873638c9f2d0c46cef4c0b2b8e80af07506 Mon Sep 17 00:00:00 2001 From: David Parkhurst Date: Mon, 22 May 2023 11:36:02 -0600 Subject: [PATCH] Tony's changes May 5 and 7. --- RELEASE.TXT | 149 ++++++++++++++++++++++++++++++++++++++++++++++++++++ 1 file changed, 149 insertions(+) diff --git a/RELEASE.TXT b/RELEASE.TXT index 6f40c5dd..880a075b 100644 --- a/RELEASE.TXT +++ b/RELEASE.TXT @@ -1,5 +1,154 @@ Version @PHREEQC_VER@: @PHREEQC_DATE@ + ----------------- + May 22, 2023 + ----------------- + PHREEQC: (See https://hydrochemistry.eu/ph3/release.html for html version of changes.) + Added Basic function f_visc("H+") that returns the fractional contribution of a species to + viscosity of the solution when parameters are defined for the species with -viscosity. + Actually, it gives the contribution of the species to the B and D terms in the Jones-Dole + eqution, assuming that the A term is small. The fractional contribution can be negative, for + example f_visc("K+") is usually smaller than zero. + + Bug-fix: When -Vm parameters of SOLUTION_SPECIES were read after -viscosity parameters, the + first viscosity parameter was set to 0. + + Defined -analytical_expression and -gamma for Na2SO4, K2SO4 and MgSO4 and Mg(SO4)22- species in + PHREEQC.dat, fitting the activities from pitzer.dat from 0 - 200 °C, and the solubilities of + mirabilite/thenardite (Na2SO4), arcanite (K2SO4), and epsomite, hexahydrite, kieserite (MgSO4 + and new species Mg(SO4)22-). The parameters for calculating the apparent volume (-Vm) and the + diffusion coefficients (-Dw) of the species were adapted using measured data of density and + conductance (SC). + + Removed the NaCO3- species in PHREEQC.dat since they are not necessary for the calculation of + the specific conductance (SC) and their origin is unknown. Defined parameters in the + -analytical_expression, -gamma, -dw, -Vm and -viscosity for the NaHCO3 species in PHREEQC.dat, + using the data in Appelo, 2015, Appl. Geochem. 55, 62-71. (These data were used for defining + interaction parameters in pitzer.dat.) The parameters for the apparent volume (-Vm), the + diffusion coefficient (-Dw) and the viscosity of CO32- and HCO3- were adapted using measured + data of density, conductance and viscosity of binary solutions. + + The viscosity of the solution at P, T is now calculated and printed in the output file, and can + be retrieved in Basic programs with the function viscos (in previous versions, viscos returned + the viscosity of pure water at P, T). + + The calculation uses a modified Jones-Dole equation which sums the contributions of individual + solutes: + + eta / eta0 = 1 + A sqrt(0.5 sum(zi*mi)) + sum fan (Bi*mi + Di*mi*ni), + + where eta is the viscosity of the solution (mPa s), eta0 is viscosity of pure water at the + temperature and pressure of the solution, mi is the molality of species i, made dimensionless + by dividing by 1 molal, and zi is the absolute charge number. A is derived from Debye-Hückel + theory, and fan, B, D and n are coefficients that incorporate volume, ionic strength and + temperature effects. The coefficients are: + + B = b0 + b1 exp(-b2 tC) + + where b0, b1, and b2 are coefficients, and tC is the temperature in ºC. The temperature is + limited to 200°C. + + fan = (2 - tan * Van / VCl-) + + for anions, with tan a coefficient and Van the P, T and I dependent, apparent volume of the + anion relative to the one of Cl-, which is used as reference species. For cations, fan = 1 + and tan need not be defined. + + D = d1 exp(-d2 tC) + where d1 and d2 are coefficients. + + n = ((1 + fI)^d3 + ((zi^2 + zi) / 2 * mi)^d3 / (2 + fI) + + where fI averages ionic strength effects and d3 is a parameter. + The coefficients are fitted on measured viscosities of binary solutions and entered + with item -viscosity under keyword SOLUTION_SPECIES, for example for H+: + + SOLUTION_SPECIES + H+ = H+ + -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 + + When the solute concentrations are seawater-like or higher, the viscosity is different + from pure water (see figure at). To obtain a valid model for natural waters with phreeqc.dat, + the complexes of SO42- with the major cations were redefined, as noted above. + The A parameter in the Jones-Dole equation needs temperature dependent diffusion coefficients of the species, and therefore the parameters for calculating the I and T dependency of the diffusion coefficients (-dw parameters of SOLUTION_SPECIES) were refitted for SO42- and CO32- species. + Example files are in c:\phreeqc\viscosity. + + Implicit calculations with option -fix_current will now account for changing concentrations in + the boundary solutions of the column. + + Activated the print of statements defined in USER_PRINT when the initial EXCHANGE, SURFACE and + GAS_PHASE are calculated. + + Changed the dw_t parameter for CO3-2 to 30 (was 0) and for HCO3- to -150 (was 0) to better fit + McCleskey's data + + Bug fix: removed the factor (TK / 298.15) from the calculation of the temperature dependence of + the diffusion coefficient. For an example, see the calculation of Dw(TK) of H+ in the next + paragraph. + + Bug fixes in printing/punching of diffusion coefficients with diff_c and setdiff_c: the numbers + are now corrected for I and T effects when the appropriate factors are defined in keyword + SOLUTION_SPECIES, item -dw. For example: + + H+ = H+ + -gamma 9.0 0 + -dw 9.31e-9 1000 0.46 1e-10 # The dw parameters are defined in Appelo, 2017, CCR 101, 102-113. + + It will set Dw(TK) = 9.31e-9 * exp(1000 / TK - 1000 / 298.15) * viscos_0_25 / viscos_0_tc + and Dw(I) = Dw(TK) * exp(-0.46 * DH_A * |zi| * I 0.5 / (1 + DH_B * I 0.5 * 1e-10 / (1 + I 0.75))), + + where viscos_0_25 is the viscosity of pure water at 25 °C, viscos_0_tc is the viscosity of pure + water at the temperature of the solution. DH_A and DH_B are Debye-Hückel parameters, + retrievable with PHREEQC Basic. + + + The temperature correction is always applied in multicomponent, diffusive transport and for + calculating the viscosity. + + The ionic strength correction is for electromigration calculations (Appelo, 2017, CCR 101, 102). The correction is applied when the option is set true in TRANSPORT, item -multi_D: + -multi_d true 1e-9 0.3 0.05 1.0 true # multicomponent diffusion + + # true/false, default tracer diffusion coefficient (Dw = 1e-9 m2/s) in water at 25 °C (used in + case -dw is not defined for a species), porosity (por = 0.3), limiting porosity (0.05) below + which diffusion stops, exponent n (1.0) used in calculating the porewater diffusion coefficient + Dp = Dw * por^n, true/false: correct Dw for ionic strength (false by default). + + ----------------- + May 19, 2023 + ----------------- + PhreeqcRM: + Renamed GetDensity and related functions to GetDensityCalculated. + Renamed SetDensity and related functions to SetDensityUser. + + Density is used to convert user-model concentrations to module solution definitions only if the + units of the user-model concentrations are specified to be parts per million. The density specified by + SetDensityUser is used by SetConcentrations to convert from per kg of solution to + per L of solution. For GetConcentrations, two options are available to convert from module solutions + to user-model concentrations, depending on the value used for the method SetUseSolutionDensityVolume: + (1) the module-calculated density is used to convert from the calculated volume of solution + to the mass (kg) of solution, or (2) the user-specified value of density is used to make the conversion. + Again, density is only used if the user-model concentration units are ppm. + + The change in method names is intended to emphasize the difference between the user-specified densities + and the module-calculated densities. + + Renamed GetSaturation and related functions to GetSaturationCalculated. + Renamed SetSaturation and related functions to SetSaturationUser. + + The values specified by SetSaturation are used to convert user-model concentrations to module solution definitions. + For SetConcentrations, the volume of solution is calculated to be the user-specified saturation * porosity * + representative volume. For GetConcentrations, two options are available to determine the solution volume, depending + on the value specified for SetUseSolutionDensityVolume: (1) the solution volume is calculated by the reaction module + and used to convert to user-model concentrations, or (2) the solution volume is again calculated by + user-specified saturation * porosity * representative volume, and those values are used to convert to user-model + concentrations. In either case, the values returned by GetSaturationCalculated are the calculated solution volume divided + by (porosity * representative volume). + + The change in method names is intended to emphasize the difference between the user-specified saturations and + and the module-calculated saturations. + + ----------------- April 16, 2023 -----------------