ThommyW

Hello Tom, I already tried to adapt data bases. <<The only way to benchmark one application against another is to be sure that you are using the same thermodynamic dataset. If indeed the two <<applications do not share a common thermodynamic database, you'll unfortunately need to do the work of formatting one database so that it can be used <<within the other application. unfortunately even only deleting all data of organic compounds only resulted in a data base which does not work any more, for an unknown reason. Is there no tool to do this in a more convenient way ? I even not sure to know all the rules that must be followed for the data base to stay readable .... I got an error that last line read is 20345 data base is incomplete or corrupt. I counted all species but the number is right so what is the problem ??? Can you help me in any other way ?? Thomas How can I get a message from the board telling me if there is a posting ? That's what I would like to have, but I didn't found this option.

Hello, I made a calculation with Vanadium and some Na2CO3 at pH 10 and 7.9 (Na+ was reduced to 1 mol instead of 2). I get vanadate species in the first case and V2O4 in the second. and the following messages: Solving for initial system. Loaded: 193 aqueous species, 15 minerals, 13 gases, 0 surface species, 5 elements, 2 oxides. <<<<Converged in 53 iterations, max. residual = 4.27e-012, Xi = 0.0000 <<<<Charge balance: Na+ molality adjusted from 1 to 1.177 Removing e- from basis vector Swapping (VO)2(OH)2++ in for e- <<<<<4 supersaturated phases, most = V4O7 <<<<Swapping V4O7 in for H+ <<<<Converged in 67 iterations, max. residual = 9.43e-012, Xi = 0.0000 <<<<<1 supersaturated phase, V2O4 <<<<<Swapping V2O4 in for VO(OH)3(aq) <<<<<Converged in 51 iterations, max. residual = 1.03e-011, Xi = 0.0000 <<<< V4O7 is undersaturated <<< Swapping HVO4-- in for V4O7 <<<<Converged in 54 iterations, max. residual = 6.94e-012, Xi = 0.0000 <<<<No reaction path specified. So the calculation works. I get V2O4 as with ChemApp. Aqueous species molality mg/kg sol'n act. coef. log act. --------------------------------------------------------------------------- Na+ 0.8378 1.752e+004 0.6619 -0.2561 HCO3- 0.6397 3.550e+004 0.6619 -0.3732 NaHCO3(aq) 0.3348 2.558e+004 1.0000 -0.4752 HVO4-- 0.07557 7969. 0.1478 -1.9521 H2VO4- 0.02415 2569. 0.6619 -1.7963 CO2(aq) 0.01179 471.9 1.0000 -1.9285 CO3-- 0.009370 511.4 0.1684 -2.8020 NaCO3- 0.004320 326.1 0.6619 -2.5437 (VO)2(OH)2++ 9.714e-005 14.83 0.1684 -4.7864 V(OH)2+ 3.153e-005 2.436 0.6619 -4.6805 VOOH+ 3.061e-005 2.337 0.6619 -4.6933 VO+ 1.572e-005 0.9570 0.6619 -4.9828 VO4--- 3.948e-006 0.4127 0.0121 -7.3194 H3VO4(aq) 1.327e-006 0.1423 1.0000 -5.8773 VO(OH)3(aq) 1.268e-006 0.1361 1.0000 -5.8968 OH- 1.260e-006 0.01949 0.6375 -6.0951 VO++ 6.540e-007 0.03982 0.1684 -6.9582 NaOH(aq) 2.749e-007 0.01000 1.0000 -6.5608 H+ 1.549e-008 1.420e-005 0.8128 -7.9000 (only species > 1e-8 molal listed) Mineral saturation states log Q/K log Q/K ---------------------------------------------------------------- V4O7 17.1666s/sat Ice -0.1387 V3O5 13.6880s/sat Nahcolite -0.5175 V2O4 9.1117s/sat Natron -2.5956 Karelianite 8.3351s/sat Na2CO3:7H2O -2.9313 (only minerals with log Q/K > -3 listed) As the other one does not work with V what would you propose to do ? Eliminating all species from our data base (all = 2064) until they are equal to the species of CHEMAPP (about 600 ) ? (Which would be a horrible work) Beginning to add species to V until it doesn't work any more ???? (which means that there is an element which is not compatible with V in the set of all which are compatible with each other (where the calculation works) But how find the reason of incompatibility ? <<<<<By the way the message: no reaction path specified: Does this mean, I can specify it ??? Thanks Thomas Willms

Hello, We are doing calculations on the speciation of spent fuel in waste disposals. We considered 21 compounds. When I added As, V, Mo, Zr to the mixture of elements, a calculation was not possible. After some experiments I found out that this is due to Vanadium. So the calculation works for the aqueous solution of Na+, K+, Mg++,Ca++,Cl-,SO4--,HCO3-,H+, O2(aq)<-> e-, FeO, B(OH)3 Ti(OH)4(aq), Sn(OH)4, NH3(aq), CuO,HCrO2(aq),Ni++,HPO4-,HAsO2, AlO(OH), MnO,SiO2,U(OH)4,ZrO2,HMoO4-. Eliminating Vanadium from "reactants" and "basis" in react the calculation works. With Vanadium included no calculation is possible. We did some calculations with chemApp. With the only species VO2+, VO++, V+++, V++ and V2O4. This calculation works, giving the solid phase V2O4. Using GWB and suppressing all species except these ones, this doesn't work and gives the result below this text. I wonder how it is possible that there is a swapping between two compounds with no metal in common. e.g. Swapping HFeO2- in for Dolomite (I often observed this) ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ Solving for initial system. ...suppressed loading of: H2VO4- ...suppressed loading of: H3VO4(aq) ...suppressed loading of: HVO4-- ...suppressed loading of: V(OH)2+ ...suppressed loading of: V2(OH)2++++ ...suppressed loading of: VO(OH)3(aq) ...suppressed loading of: VO+ ...suppressed loading of: VO2(HPO4)2--- ...suppressed loading of: VO2H2PO4(aq) ...suppressed loading of: VO2HPO4- ...suppressed loading of: VO2SO4- ...suppressed loading of: VO4--- ...suppressed loading of: VOH+ ...suppressed loading of: VOH++ ...suppressed loading of: VOOH+ ...suppressed loading of: VOSO4(aq) ...suppressed loading of: VSO4+ ...suppressed loading of: Spent_Fuel ...suppressed loading of: (VO)3(PO4)2 ...suppressed loading of: Ca2V2O7 ...suppressed loading of: Ca3V2O8 ...suppressed loading of: CaV2O6 ...suppressed loading of: FeV2O4 ...suppressed loading of: Karelianite ...suppressed loading of: Mg2V2O7 ...suppressed loading of: MgV2O6 ...suppressed loading of: MnV2O6 ...suppressed loading of: Shcherbinaite ...suppressed loading of: V3O5 ...suppressed loading of: V4O7 Loaded: 786 aqueous species, 493 minerals, 47 gases, 0 surface species, 26 elements, 20 oxides. Converged in 35 iterations, max. residual = 1.3e-011, Xi = 0.0000 Charge balance: Cl- molality adjusted from .1301 to .1294 Removing e- from basis vector Swapping HAsO4-- in for e- 2 supersaturated phases, most = Dolomite Swapping Dolomite in for H+ Swapping Fe++ in for FeO(aq) Swapping CuCl2- in for CuO(aq) Swapping VO++ in for HAsO2(aq) Swapping Mn++ in for MnO(aq) Swapping HZrO3- in for ZrO2(aq) Swapping MoO4-- in for HMoO4- Swapping Ca2UO2(CO3)3(aq) in for VO2+ Converged in 8 iterations, max. residual = 4.51e-013, Xi = 0.0000 Following reaction path. Converged in 149 iterations, max. residual = 2.76e-012, Xi = 0.01000 Dolomite is undersaturated Swapping HFeO2- in for Dolomite Singular matrix on 41-th iteration Cutting step size to find phase assemblage Swapping Dolomite in for HFeO2- Converged in 107 iterations, max. residual = 2.52e-012, Xi = 0.0000 Converged in 119 iterations, max. residual = 7.99e-013, Xi = 0.002500 Dolomite is undersaturated Swapping HFeO2- in for Dolomite Singular matrix on 22-th iteration Cutting step size to find phase assemblage Swapping Dolomite in for HFeO2- Converged in 97 iterations, max. residual = 2.59e-013, Xi = 0.0000 Converged in 101 iterations, max. residual = 8.12e-013, Xi = 0.0006250 Dolomite is undersaturated Swapping HFeO2- in for Dolomite Singular matrix on 24-th iteration Cutting step size to find phase assemblage Swapping Dolomite in for HFeO2- Converged in 92 iterations, max. residual = 1.31e-012, Xi = 0.0000 Converged in 91 iterations, max. residual = 9.72e-013, Xi = 0.0001563 Dolomite is undersaturated Swapping HFeO2- in for Dolomite *N-R didn't converge after 400 its., maximum residual = 1.39e+004, Xi = 0.0002 Cutting step size to find phase assemblage Swapping Dolomite in for HFeO2- Converged in 89 iterations, max. residual = 1.81e-013, Xi = 0.0000 Converged in 84 iterations, max. residual = 2.36e-012, Xi = 3.906e-005 Dolomite is undersaturated Swapping HFeO2- in for Dolomite Singular matrix on 14-th iteration Cutting step size to find phase assemblage Swapping Dolomite in for HFeO2- Converged in 82 iterations, max. residual = 1.37e-012, Xi = 0.0000 Converged in 77 iterations, max. residual = 7.99e-013, Xi = 9.766e-006 Dolomite is undersaturated Swapping HFeO2- in for Dolomite Singular matrix on 14-th iteration -- Can't find solution, giving up on path --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- I also tried about 6 values of Eh(V) but this does not work either. In the same way, using all species from Vanadium , there is a swapping Kareleite <--> H2. I was able to produce this several times under different conditions, but I didn't find a solution. ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Solving for initial system. ...suppressed loading of: Spent_Fuel Loaded: 803 aqueous species, 493 minerals, 47 gases, 0 surface species, 26 elements, 20 oxides. Converged in 33 iterations, max. residual = 6.25e-012, Xi = 0.0000 Charge balance: Cl- molality adjusted from .1301 to .1294 Removing e- from basis vector Swapping HAsO4-- in for e- 5 supersaturated phases, most = Dolomite Swapping Dolomite in for H+ Converged in 18 iterations, max. residual = 1.13e-012, Xi = 0.0000 Following reaction path. Converged in 168 iterations, max. residual = 1.33e-012, Xi = 0.01000 Dolomite is undersaturated Swapping Methane(aq) in for Dolomite Converged in 88 iterations, max. residual = 2.85e-013, Xi = 0.01000 147 supersaturated phases, most = Antigorite Swapping Antigorite in for HCO3- Converged in 151 iterations, max. residual = 2.81e-012, Xi = 0.01000 81 supersaturated phases, most = Bornite Swapping Bornite in for SO4-- Converged in 65 iterations, max. residual = 9.11e-013, Xi = 0.01000 74 supersaturated phases, most = Heazlewoodite Swapping Heazlewoodite in for CuO(aq) Converged in 56 iterations, max. residual = 1.55e-013, Xi = 0.01000 66 supersaturated phases, most = Chromite Swapping Chromite in for HCrO2(aq) Swapping H2(aq) in for HAsO4-- Swapping NH3(aq) in for N2(aq) Swapping AlO2- in for HAlO2(aq) Swapping HS- in for Ni++ Swapping FePO4- in for HPO4-- Swapping Mn2(OH)3+ in for MnO(aq) Swapping HFeO2- in for SiO2(aq) Swapping HZrO3- in for ZrO2(aq) Swapping MoO4-- in for HMoO4- Swapping V(OH)2+ in for VO4--- Converged in 15 iterations, max. residual = 1.1e-013, Xi = 0.01000 64 supersaturated phases, most = Daphnite-14A Swapping Daphnite-14A in for AlO2- Converged in 14 iterations, max. residual = 1.48e-014, Xi = 0.01000 52 supersaturated phases, most = Zirconolite Swapping Zirconolite in for Ti(OH)4(aq) Converged in 14 iterations, max. residual = 8.46e-015, Xi = 0.01000 47 supersaturated phases, most = Cronstedtite-7A Swapping Cronstedtite-7A in for FeO(aq) Converged in 26 iterations, max. residual = 1.13e-013, Xi = 0.01000 Daphnite-14A is undersaturated Swapping AlO2- in for Daphnite-14A Converged in 31 iterations, max. residual = 3.16e-013, Xi = 0.01000 Antigorite is undersaturated Swapping Mg4(OH)4++++ in for Antigorite Converged in 50 iterations, max. residual = 1.77e-013, Xi = 0.01000 44 supersaturated phases, most = Magnetite Swapping Magnetite in for Mg4(OH)4++++ Converged in 71 iterations, max. residual = 3.72e-013, Xi = 0.01000 65 supersaturated phases, most = Antigorite Swapping Antigorite in for HFeO2- Converged in 31 iterations, max. residual = 4.91e-014, Xi = 0.01000 Cronstedtite-7A is undersaturated Swapping Mn++ in for Cronstedtite-7A Converged in 19 iterations, max. residual = 5.19e-013, Xi = 0.01000 33 supersaturated phases, most = V3O5 Swapping V3O5 in for Mn++ Converged in 84 iterations, max. residual = 1.13e-013, Xi = 0.01000 30 supersaturated phases, most = Hydroxylapatite Swapping Hydroxylapatite in for V(OH)2+ Converged in 22 iterations, max. residual = 3.04e-013, Xi = 0.01000 28 supersaturated phases, most = As Swapping As in for HAsO2(aq) Swapping BO2- in for B(OH)3 Swapping U(OH)5- in for FePO4- Converged in 11 iterations, max. residual = 2.47e-014, Xi = 0.01000 24 supersaturated phases, most = Baddeleyite Swapping Baddeleyite in for U(OH)5- Converged in 26 iterations, max. residual = 1.64e-014, Xi = 0.01000 23 supersaturated phases, most = Uraninite Swapping Uraninite in for U(OH)4(aq) Swapping OH- in for HZrO3- Converged in 13 iterations, max. residual = 9.07e-015, Xi = 0.01000 19 supersaturated phases, most = Cast_Iron Swapping Cast_Iron in for H2(aq) Converged in 395 iterations, max. residual = 6.62e-014, Xi = 0.01000 18 supersaturated phases, most = Cassiterite Swapping Cassiterite in for Sn(OH)4(aq) Swapping SO4-- in for Methane(aq) Converged in 11 iterations, max. residual = 2.86e-014, Xi = 0.01000 16 supersaturated phases, most = Brucite Swapping Brucite in for Mg++ Swapping H2(aq) in for SO4-- Converged in 13 iterations, max. residual = 1.02e-015, Xi = 0.01000 14 supersaturated phases, most = Ilmenite Swapping Ilmenite in for OH- Converged in 15 iterations, max. residual = 2.65e-014, Xi = 0.01000 Zirconolite is undersaturated Swapping OH- in for Zirconolite Converged in 13 iterations, max. residual = 1.47e-015, Xi = 0.01000 11 supersaturated phases, most = Karelianite Swapping Karelianite in for H2(aq)* N-R didn't converge after 400 its., maximum residual = 1, Xi = 0.0100 Cutting step size to find phase assemblage Swapping Dolomite in for Brucite Swapping CuO(aq) in for Bornite Swapping SiO2(aq) in for Magnetite Swapping SO4-- in for Karelianite Swapping FeO(aq) in for Cast_Iron Swapping VO4--- in for V3O5 Swapping B(OH)3 in for BO2- Swapping Mg++ in for OH- Swapping Sn(OH)4(aq) in for Cassiterite Swapping N2(aq) in for NH3(aq) Swapping Ni++ in for Heazlewoodite Swapping HCrO2(aq) in for Chromite Swapping HAsO4-- in for As Swapping HAlO2(aq) in for AlO2- Swapping HAsO2(aq) in for HS- Swapping ZrO2(aq) in for Baddeleyite Swapping MnO(aq) in for Mn2(OH)3+ Swapping HPO4-- in for Antigorite Swapping U(OH)4(aq) in for Uraninite Swapping Ti(OH)4(aq) in for Ilmenite Swapping HMoO4- in for MoO4-- Swapping HCO3- in for Hydroxylapatite Singular matrix on 57-th iteration -- Didn't wake up, abandoning path --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- By the way there are often very strange swappings. Is this normal ? I have the impression that these strange swappings take place due to some other problem and whenever they take place they are the cause for an unsuccessful calculation. So what is the problem ? Are there missing phases ? Why are there no normal vanadate phases in the data base? I know many minerals eg. Vanadinite which are surely nearly not soluble. And it could be relevant due to the contents of lead. Are there no data on these? How is it possible that GWB doesn't work but ChemApp/Sage gives a reasonable result ? Are G minimizers better than mass action calculations ? Do any one have an idea ???? Thanks for any help Thommy