ThommyW
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Posts posted by ThommyW
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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
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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
Vanadium calculations
in React
Posted
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.