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ThommyW

Vanadium calculations

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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

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Hi Tommy:

 

Automatic basis swaps are covered in chapter 5 of Craig Bethke's Geochemical and Biogeochemical Reaction Modeling text (or the older "Geochemical Reaction Modeling", better known as the 'green book'). They are necessary over the course of a model if a mineral dissolves away completely or becomes supersaturated and precipitates. Automatic basis swaps may also be necessary in response to numerical considerations- for example, if one of the basis species occurs at extremely small concentrations, which can create numerical instability in the calculation.

 

As far as rules for swapping, you'll also want to take a look at chapter 3 of the text to see how reactions for minerals and species are written in terms of basis components; and take a look in the database at the reactions for Karelianite/H2(aq), Dolomite/HFeO2-, Hydroxylapatite/HCO3-, to get a better idea of what swaps are allowable.

 

The basis swap is not likely to be the cause of instability. It's probably more tied to defining an initial system that is too far out of equilibrium, issues with charge balance etc.

 

Similarly, there's a discussion on free energy minimization vs. mass action techniques in secion 1.1.1 (page 3) of Craig's book. In short, the two methods are computationally and conceptually equivalent.

 

Finally- I'm not an expert on Vanadate phases, but if the phases you desire are not in the database, you'll either want to use a different database, or add the phases to the database you are using.

 

I hope that helps,

 

Tom Meuzelaar

RockWare, Inc.

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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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Hi Thomas:

 

The reaction path message simply states that you've only defined a speciation model up to this point- you can add a reaction path model if you'd like (this is usually done in the Reactants tab). One reaction path model that you might try is a sliding pH model, given that you are interested in Vanadium speciation over a pH range.

 

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.

 

I hope that helps,

 

Tom Meuzelaar

RockWare, Inc.

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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.

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Hi Thomas:

 

Re-constructing the database is not just a matter of deleting extra species and minerals - the databases have to be constructed using the same basis species, same formation/dissolution reactions, and same log K values. For starters, I recommend that you take a look at the Appendix on Thermo Datasets in the GWB Reference Manual (you can access this as a PDF file from any of the module Help menus, or download this from the RockWare website).

 

A couple of other details will help you get going:

 

  • Always rename the database before you start modifications, in case it becomes corrupted
  • Increment or decrement the number of Minerals, Aqueous Species in the section header whenever you delete or add a species
  • Molar volumes, molar weights, log K values etc. must be carried out to the same number of decimal units shown for other species, or GWB will report an error
  • Be careful to keep the same formatting, or GWB will report an error

 

Unfortunately, there are no automated tools for doing this- formatting databases takes time and should be done only when you have scientifically valid reasons for doing so. Haphazard deletion or addition of species will result in compromising the integrity, internal consistency and validity of the database. Additionally, if you delete species upon which other reactions are built, you risk compromising the database beyond repair.

 

You can receive instant notification when someone replies to one of your posts, by adjusting your email settings. This is described in this section of the forum Quick Start guide.

 

I hope that helps,

 

Tom Meuzelaar

RockWare, Inc.

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Hi Tom

 

A couple of other details will help you get going:

  • <<<
  • Always rename the database before you start modifications, in case it becomes corrupted
    <<<
  • Increment or decrement the number of Minerals, Aqueous Species in the section header whenever you delete or add a species
    <<<
  • Molar volumes, molar weights, log K values etc. must be carried out to the same number of decimal units shown for other species, or GWB will report <<<an error
    <<
  • Be careful to keep the same formatting, or GWB will report an error

 

OK, I didn't know the last points: formatting and decimal numbers.

 

<<Re-constructing the database is not just a matter of deleting extra species and minerals - the databases have to be constructed using the same basis <<species, same formation/dissolution reactions, and same log K values. For starters, I recommend that you take a look at the Appendix on Thermo <<<Datasets in the

<<<Unfortunately, there are no automated tools for doing this- formatting databases takes time and should be done only when you have scientifically valid <<<reasons for doing so. Haphazard deletion or addition of species will result in compromising the integrity, internal consistency and validity of the database. <<<Additionally, if you delete species upon which other reactions are built, you risk compromising the database beyond repair.

 

The scientific trouble I will get in, not changing basic species and recalculating Log(K) is clear. That why I hesitate...

 

<<<<You can receive instant notification when someone replies to one of your posts, by adjusting your email settings. This is described in

<<<this section of the forum Quick Start guide.

 

Thanks, I have been looking under email settings. Now I wonder how I didn't see this item..... Anyway, default means that no email is sent ?

 

 

By the way, the dissociation of vanadium species is in general not defined using the same species, e.g. V(III), VO<2+> are also used in the data base I am using. But looking at other species, this is the same: Also redox species are used. Could this be a problem ???

Would it be better if I only use basic species ?

 

Also I wanted to to get you to know another observation: If I calculate only with vanadium it works. Adding solution ions (Na, K, Ca, Mg, Cl, SO4) it works, also using B(OH)3, Ti(OH)4, Al , SiO2 and other non reducing species.

No problem at all.

 

Adding Ni it crashes with the first trial: no converging after 400 ....

but it rebegins with smaller paces and it works.

 

Using any reducing ion it crashes and it doesn't work at all.

So now we know that there is some problem with reducing species.

Any idea how to manage this problem ???

 

 

Thanks

 

Thomas

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Hello Tom,

 

I just found out that, using Fe and V only, the calculation works with solutions

with high concentrations of sodium Chloride (and Eh(V) and pH).

So the problem is not as easy as it seemed.(see below)

By the way, the swapping where it crashes in the case of the multicompound mixture

used in the beginning is the same Kareliante <--> H2 but this works in this case !!!!!!

If the other compounds are present it doesn't work.

 

 

Another observation:

 

If I use only traces of Chloride, Fe, V then it fails:

------------------------------------------------------------

Solving for initial system.

 

Loaded: 50 aqueous species,

18 minerals,

5 gases,

0 surface species,

5 elements,

4 oxides.

 

Residuals too large, 672-th interation

Largest residual(s):

Resid Resid/Totmol Cbasis

--------------------------------------------------------

Cl- 0.01583 1.353e+200 5.848e-207

--------------------------------------------------------

 

These observations just as additional comments to the last posting.

 

Thomas

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Hello Tom,

 

I just saw that my last posting disappeared, I don't know how....... (I clicked Addreply... can this be the reason ?)

 

Just to mention that I made a calculation with V and many non redox species as well as Ni.

The calculation did not converge on the first run (message "didn't converge") but afterwards cutting step size the process converged finally. I also posted it because I wanted to know how this is possible. But now I found it out myself: If I change change Eh(V) from -0.1 to -0.25 to eliminate missing "faradays" (reported at the end of the calculation) the first message "didn't converge" disappears and the calculation is completed without errors.

Adding Fe the calculation fails with the message "non converging". But as the posting above shows: This cannot be the only reason.

 

Thomas

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Hello Tom,

 

the calculations are very strange. If I don't suppress Cast_Iron and especially Iron and some other minerals the calculation doesn't work.

 

I get the result : "all iron dissolved"

but afterwards there are nearly 90 % of the iron is in the system as the "mineral" IRON !!!

I think that this is not normal. By the way if I change the way to build the system and I take vanadium in the beginning, then some other elements and finally Iron, the calculation (including 20000 kg water) the calculation only works up to 23.1 mol Fe! Even only 0.1 mol more, the calculation doesn't converge.

Also using no V and all the rest as given above, only Fe appears as mineral.

I will discuss with my collegue who uses ChemApp if there is any difference to the calculation in Eh(V) or in the config this concerning.

He gets V2O4 instead of V3O5.

 

 

 

 

Step # 100 Xi = 1.0000

Time = 3.15576e+013 secs (3.6525e+008 days)

 

Temperature = 25.0 C Pressure = 1.013 bars

pH = 9.581 log fO2 = -91.416

Eh = -0.6467 volts pe = -10.9329

Ionic strength = 0.191431

Activity of water = 0.994876

Solvent mass = 16559.250554 kg

Solution mass = 17190.127351 kg

Solution density = 1.017 g/cm3

Chlorinity = 0.156403 molal

Dissolved solids = 36700 mg/kg sol'n

Rock mass = 18592.936336 kg

Carbonate alkalinity= 3910.59 mg/kg as CaCO3

 

moles moles grams cm3

Reactants remaining reacted reacted reacted

----------------------------------------------------------------------------

Al 1.066e-013 128.8 3475. 1288.

As -6.384e-015 16.18 1212. 209.8

B 1.656e-012 998.5 1.079e+004 4379.

C -1.387e-012 1021. 1.227e+004 5411.

Corundum 8.515e-014 62.67 6390. 1603.

Cr -3.872e-012 4188. 2.177e+005 3.028e+004

Cu 2.898e-014 83.48 5305. 593.8

Fe 8.481e-011 1.447e+005 8.079e+006 1.026e+006

Mn -1.066e-013 2373. 1.304e+005 1.745e+004

Mo 3.092e-014 39.49 3789. 370.7

N2(g) -6.189e-014 43.28 1213.

Ni -3.045e-012 2083. 1.222e+005 1.372e+004

P -1.837e-014 42.11 1304. 724.3

S -1.141e-014 21.78 698.5 340.0

Si 1.224e-012 1069. 3.002e+004 1.289e+004

Sn -1.021e-013 187.7 2.228e+004 3057.

Ti -1.019e-013 189.5 9075. 2015.

Uraninite 1.970e-011 2.052e+004 5.541e+006 5.380e+005

V -3.514e-014 29.75 1516. 248.4

Zr 1.484e-011 1.527e+004 1.393e+006 9.333e+005

 

Minerals in system moles log moles grams volume (cm3)

----------------------------------------------------------------------------

As 16.18 1.209 1212. 209.8

Baddeleyite 1.527e+004 4.184 1.882e+006 6.274e+005

Chromite 2094. 3.321 4.687e+005 9.215e+004

Cu 83.48 1.922 5305. 593.8

Daphnite-14A 127.1 2.104 9.066e+004 2.712e+004

FeO 1.405e+005 5.148 1.009e+007 1.686e+006

Greenalite 343.9 2.536 1.278e+005 3.955e+004

Hydroboracite 31.25 1.495 1.292e+004 5878.

Ilmenite 189.5 2.278 2.876e+004 9585.

Mn(OH)2(am) 1836. 3.264 1.633e+005 4.106e+004

MnHPO4 42.11 1.624 6356. 2119.

Mo 39.49 1.597 3789. 370.7

Ni 2083. 3.319 1.222e+005 1.372e+004

Sn 187.7 2.273 2.228e+004 3057.

Troilite 251.4 2.400 2.210e+004 7367.

Uraninite 2.052e+004 4.312 5.541e+006 5.380e+005

V3O5 9.917 0.996 2309. 486.0

_____________ _____________

(total) 1.859e+007 3.094e+006

 

Aqueous species molality mg/kg sol'n act. coef. log act.

---------------------------------------------------------------------------

H2(aq) 11.18 2.171e+004 1.0000 1.0484

Cl- 0.1542 5265. 0.7105 -0.9604

Na+ 0.1491 3303. 0.7342 -0.9606

Methane(aq) 0.06192 956.9 1.0000 -1.2082

BO2- 0.03041 1254. 0.7342 -1.6511

Mn2(OH)3+ 0.01431 2217. 0.7342 -1.9787

B(OH)3 0.009760 581.3 1.0500 -1.9893

NaB(OH)4(aq) 0.004516 443.0 1.0000 -2.3452

Ca++ 0.003679 142.0 0.3369 -2.9068

NH3(aq) 0.003157 51.79 1.0000 -2.5007

CaB(OH)4+ 0.002481 284.2 0.7342 -2.7396

NH4+ 0.002071 35.98 0.6971 -2.8406

NaCl(aq) 0.002004 112.8 1.0000 -2.6980

Mg++ 0.001942 45.47 0.3906 -3.1200

MgB(OH)4+ 0.001807 179.5 0.7342 -2.8773

Mn++ 0.001162 61.49 0.3369 -3.4074

K+ 0.0009722 36.62 0.7105 -3.1607

CaCl+ 9.429e-005 6.860 0.7342 -4.1597

MgCl+ 8.296e-005 4.776 0.7342 -4.2153

OH- 5.303e-005 0.8688 0.7228 -4.4164

MnOH+ 4.852e-005 3.362 0.7342 -4.4483

MnCl+ 4.245e-005 3.696 0.7342 -4.5063

MgOH+ 8.136e-006 0.3238 0.7342 -5.2238

Fe++ 6.994e-006 0.3763 0.3369 -5.6278

FeOH+ 5.892e-006 0.4135 0.7342 -5.3639

CaCl2(aq) 3.379e-006 0.3612 1.0000 -5.4713

NaOH(aq) 2.591e-006 0.09981 1.0000 -5.5866

HFeO2- 1.091e-006 0.09335 0.7342 -6.0965

CaOH+ 9.393e-007 0.05165 0.7342 -6.1614

HSnO2- 5.943e-007 0.08685 0.7342 -6.3602

SnO(aq) 3.812e-007 0.04946 1.0000 -6.4189

MnO(aq) 3.557e-007 0.02431 1.0000 -6.4489

FeCl+ 2.429e-007 0.02136 0.7342 -6.7487

Mn2OH+++ 2.330e-007 0.02848 0.0686 -7.7961

KCl(aq) 2.205e-007 0.01583 1.0000 -6.6566

FeO(aq) 1.338e-007 0.009263 1.0000 -6.8734

MnCl3- 1.184e-007 0.01839 0.7342 -7.0609

AlO2- 3.821e-008 0.002171 0.7342 -7.5520

HS- 2.341e-008 0.0007459 0.7228 -7.7715

Fe(OH)3- 1.748e-008 0.001799 0.7342 -7.8917

Sn(OH)4(aq) 1.243e-008 0.002235 1.0000 -7.9056

(only species > 1e-8 molal listed)

 

Mineral saturation states

log Q/K log Q/K

----------------------------------------------------------------

Spent_Fuel 18.5304s/sat Fe(OH)2 -0.3749

Cast_Iron 7.6502s/sat Romarchite -0.6582

Karelianite 4.2515s/sat Chrysotile -0.9318

Fe 1.6565s/sat Colemanite -0.9363

Baddeleyite 0.0000 sat Fayalite -1.0081

Uraninite 0.0000 sat Herzenbergite -1.0673

Cu 0.0000 sat Brucite -1.0726

Mo 0.0000 sat Sn(OH)2 -1.1379

Daphnite-14A 0.0000 sat Ripidolite-14A -1.1583

As 0.0000 sat Wustite -1.1961

FeO 0.0000 sat Cronstedtite-7A -1.2754

Mn(OH)2(am) 0.0000 sat Tephroite -1.4137

Sn 0.0000 sat Zircon -1.4816

Greenalite 0.0000 sat Alabandite -1.6435

Ni 0.0000 sat Hydroxylapatite -1.7567

Hydroboracite 0.0000 sat Boric_acid -1.8310

Chromite 0.0000 sat Gibbsite -1.8980

Ilmenite 0.0000 sat Goethite -2.0925

MnHPO4 0.0000 sat Clinochlore-14A -2.4179

V3O5 0.0000 sat Manganosite -2.6116

Troilite 0.0000 sat Diaspore -2.6861

Magnetite -0.0544 Borax -2.7674

Pyrrhotite -0.0991 Ferrosilite -2.8757

Ice -0.1409 Rutile -2.9820

Cassiterite -0.3327

(only minerals with log Q/K > -3 listed)

 

Gases fugacity log fug.

-----------------------------------------------

H2(g) 1.424e+004 4.153

CH4(g) 43.86 1.642

H2O(g) 0.02584 -1.588

NH3(g) 5.043e-005 -4.297

H2S(g) 4.202e-010 -9.377

HCl(g) 1.423e-017 -16.847

N2(g) 1.516e-027 -26.819

C2H4(g) 1.872e-035 -34.728

CO(g) 5.920e-038 -37.228

CO2(g) 1.325e-038 -37.878

Sn(g) 2.289e-047 -46.640

Na(g) 2.157e-049 -48.666

K(g) 2.607e-052 -51.584

Cu(g) 7.079e-053 -52.150

S2(g) 1.944e-053 -52.711

SO2(g) 5.840e-059 -58.234

Cl2(g) 5.780e-072 -71.238

NO(g) 5.243e-075 -74.280

Mg(g) 8.868e-080 -79.052

TiCl4(g) 1.446e-083 -82.840

UO2Cl2(g) 8.134e-088 -87.090

UO3(g) 9.791e-090 -89.009

O2(g) 3.836e-092 -91.416

UCl4(g) 4.335e-094 -93.363

UO2(g) 3.221e-097 -96.492

Ca(g) 2.148e-102 -101.668

UCl3(g) 4.741e-103 -102.324

TiO(g) 9.099e-112 -111.041

NO2(g) 1.532e-114 -113.815

Phenol(g) 1.622e-121 -120.790

UCl5(g) 2.081e-122 -121.682

Al(g) 7.358e-125 -124.133

UCl2(g) 2.721e-129 -128.565

Meta-Cresol(g) 1.427e-131 -130.846

Ortho-Cresol(g) 3.515e-132 -131.454

B(g) 8.068e-133 -132.093

Para-Cresol(g) 2.891e-133 -132.539

C(g) 7.094e-134 -133.149

Si(g) 2.529e-135 -134.597

UO(g) 4.219e-136 -135.375

Ti(g) 2.169e-143 -142.664

UCl6(g) 1.859e-145 -144.731

UCl(g) 3.416e-153 -152.466

U(g) 1.326e-175 -174.878

U2Cl8(g) 4.721e-177 -176.326

Zr(g) 3.018e-191 -190.520

U2Cl10(g) 8.637e-218 -217.064

 

In fluid Sorbed Kd

Original basis total moles moles mg/kg moles mg/kg L/kg

-------------------------------------------------------------------------------

Al+++ 254. 0.000633 0.000994

B(OH)3 999. 811. 2.92e+003

Ca++ 135. 104. 242.

Cl- 2.59e+003 2.59e+003 5.34e+003

CrO4-- 4.19e+003 3.11e-011 2.10e-010

Cu++ 83.5 3.60e-013 1.33e-012

Fe+++ 1.45e+005 0.238 0.773

H+ -5.37e+005 -303. -17.8

H2AsO4- 16.2 1.01e-007 8.26e-007

H2O 1.38e+006 1.11e+006 1.16e+006

HCO3- 1.03e+003 1.03e+003 3.64e+003

HPO4-- 42.1 0.000188 0.00105

K+ 16.1 16.1 36.6

Mg++ 94.8 63.6 89.9

Mn++ 2.37e+003 495. 1.58e+003

MoO4-- 39.5 1.35e-008 1.26e-007

NH3(aq) 86.6 86.6 85.8

Na+ 2.58e+003 2.58e+003 3.45e+003

Ni++ 2.08e+003 5.62e-011 1.92e-010

O2(aq) -1.46e+005 -9.46e+004-1.76e+005

SO4-- 251. 0.000389 0.00217

SiO2(aq) 1.07e+003 0.000176 0.000614

Sn++ 188. 0.0164 0.113

Ti(OH)4(aq) 190. 3.87e-009 2.61e-008

UO2++ 2.05e+004 6.69e-006 0.000105

VO2+ 29.8 0.000134 0.000644

Zr++++ 1.53e+004 0.000108 0.000571

 

Elemental composition In fluid Sorbed

total moles moles mg/kg moles mg/kg

-------------------------------------------------------------------------------

Aluminum 254.1 0.0006332 0.0009939

Arsenic 16.18 1.008e-007 4.391e-007

Boron 998.5 811.0 510.1

Calcium 134.9 103.6 241.6

Carbon 1025. 1025. 716.4

Chlorine 2590. 2590. 5341.

Chromium 4188. 3.111e-011 9.411e-011

Copper 83.48 3.597e-013 1.330e-012

Hydrogen 2.221e+006 2.215e+006 1.299e+005

Iron 1.447e+005 0.2380 0.7731

Magnesium 94.83 63.59 89.91

Manganese 2373. 494.5 1580.

Molybdenum 39.49 1.354e-008 7.555e-008

Nickel 2083. 5.620e-011 1.919e-010

Nitrogen 86.56 86.56 70.54

Oxygen 1.153e+006 9.220e+005 8.581e+005

Phosphorus 42.11 0.0001880 0.0003388

Potassium 16.10 16.10 36.63

Silicon 1069. 0.0001757 0.0002871

Sodium 2578. 2578. 3447.

Sulphur 251.4 0.0003888 0.0007253

Tin 187.7 0.01636 0.1130

Titanium 189.5 3.867e-009 1.077e-008

Uranium 2.052e+004 6.688e-006 9.260e-005

Vanadium 29.75 0.0001336 0.0003958

Zirconium 1.527e+004 0.0001076 0.0005708

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Thanks, I have been looking under email settings. Now I wonder how I didn't see this item..... Anyway, default means that no email is sent ?

 

By the way, the dissociation of vanadium species is in general not defined using the same species, e.g. V(III), VO<2+> are also used in the data base I am using. But looking at other species, this is the same: Also redox species are used. Could this be a problem ???

Would it be better if I only use basic species ?

 

Using any reducing ion it crashes and it doesn't work at all.

So now we know that there is some problem with reducing species.

Any idea how to manage this problem ???

 

Hi Thomas:

 

Yes, I believe that is the default setting for the forum software- I am not exactly sure why- maybe the assumption is that people prefer to come back and check the forum for responses automatically and don't like getting the extra emails.

 

Regarding the additional valence states for Vanadium and other reducing/oxidizing species- this is a critical issue that could be affecting solution stability. When you define your starting system, you want to define a system that is initially not too far out of equilibrium. For instance, if you have a large amount of Fe component in your system, and the system is initially oxidizing, it is better to specify your Basis species in terms of the oxidized species, Fe+++. Or, if you have a system that contains Uranium that's initially reducing, specify the Basis concentration in terms of U++++, and not U++++++.

 

This is probably why you are running into trouble with adding certain components to your configuration.

 

I hope that helps,

 

Tom Meuzelaar

RockWare, Inc.

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Hello Tom,

 

I just saw that my last posting disappeared, I don't know how....... (I clicked Addreply... can this be the reason ?)

 

Just to mention that I made a calculation with V and many non redox species as well as Ni.

The calculation did not converge on the first run (message "didn't converge") but afterwards cutting step size the process converged finally. I also posted it because I wanted to know how this is possible. But now I found it out myself: If I change change Eh(V) from -0.1 to -0.25 to eliminate missing "faradays" (reported at the end of the calculation) the first message "didn't converge" disappears and the calculation is completed without errors.

Adding Fe the calculation fails with the message "non converging". But as the posting above shows: This cannot be the only reason.

 

Thomas

 

Hi Thomas:

 

Charge balance issues may be one reason for non-convergence. A second may be that reaction path increments that are too large, or too small- this is especially true for kinetic models. For example, if you trace a reaction path over a million years, that includes a kinetic reaction which completes in a few days, GWB will likely run into numerical difficulty. You have the option to increase or decrease the default number of reaction path steps via the Config - Variables - delxi setting. Additionally, for kinetic simulations, React may choose the decrease reaction path intervals (thereby increasing the total number of reaction path steps) in order to come to a solution.

 

Regards,

 

Tom Meuzelaar

RockWare, Inc.

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the calculations are very strange. If I don't suppress Cast_Iron and especially Iron and some other minerals the calculation doesn't work.

 

I get the result : "all iron dissolved"

but afterwards there are nearly 90 % of the iron is in the system as the "mineral" IRON !!!

I think that this is not normal. By the way if I change the way to build the system and I take vanadium in the beginning, then some other elements and finally Iron, the calculation (including 20000 kg water) the calculation only works up to 23.1 mol Fe! Even only 0.1 mol more, the calculation doesn't converge.

Also using no V and all the rest as given above, only Fe appears as mineral.

I will discuss with my collegue who uses ChemApp if there is any difference to the calculation in Eh(V) or in the config this concerning.

He gets V2O4 instead of V3O5.

 

Hi Thomas:

 

Without seeing your scripts, databases, model assumptions and configuration, it is really impossible to comment on the results.

 

Regards,

 

Tom Meuzelaar

RockWare, Inc.

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Hello Tom,

 

I have another problem. As I get some different ühases with ChemApp compared to GWB

and another pH (9,5 instead of 7,4), I ask myself if this is due to pressure differences,

because the calculation with chemApp is made under 40 bar hydrostatic pressure.

 

I don't see any possibility to influence pressures in a system.

 

If the system builds up pressure, what can I do to change the pressure in the system or to select different

scenarios (pressure constant, volume constant ). What is the default ?

 

How is it poossible to apply a defined (hydrostatic pressure) on the system ?

 

Thanks

 

Sincerely

 

Thomas Willms

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Hello Tom,

 

I have another problem. As I get some different ühases with ChemApp compared to GWB

and another pH (9,5 instead of 7,4), I ask myself if this is due to pressure differences,

because the calculation with chemApp is made under 40 bar hydrostatic pressure.

 

I don't see any possibility to influence pressures in a system.

 

If the system builds up pressure, what can I do to change the pressure in the system or to select different

scenarios (pressure constant, volume constant ). What is the default ?

 

How is it poossible to apply a defined (hydrostatic pressure) on the system ?

 

Thanks

 

Sincerely

 

Thomas Willms

 

Hi Thomas:

 

You would need to compare equilibrium constant data between the databases for ChemApp and GWB. The GWB default database is compiled at 1 atm pressure. It is possible to create databases for higher confining pressures, but in most cases, doing so will not result in new log K data that exceed the inherent error of the database at 1 atm.

 

I hope that helps,

 

Tom Meuzelaar

RockWare, Inc.

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Hello Tom,

 

If I wanted to use a different pressure, how can this be done ?

Simply change the data base with the new pressure written inside

somewhere ?

 

But how is a pressure increase treated inside the system during the calculation ?

I suppose, if for example H2 is generated, it will it stay in solution under one bar.

Is there a defined gas volume in the system with an aqueous solution ?

 

Thanks

 

Thomas

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Hello Tom,

 

If I wanted to use a different pressure, how can this be done ?

Simply change the data base with the new pressure written inside

somewhere ?

 

But how is a pressure increase treated inside the system during the calculation ?

I suppose, if for example H2 is generated, it will it stay in solution under one bar.

Is there a defined gas volume in the system with an aqueous solution ?

 

Thanks

 

Thomas

 

Hi Thomas:

 

You can model the partial pressure of any gas by simply swapping the gas in for the component it constrains and specifying its fugacity. You cannot model changes in confining pressure during a simulation. You could modify a thermodynamic database (using SUPCRT) for a different confining pressure, and model at that specific pressure.

 

GWB does not calculate/track gas volumes.

 

I hope that helps,

 

Tom

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Hello Tom,

 

allow me a, probably, last question or conclusion:

 

1. If hydrogen is develloped during the reaction, will it stay all in solution if H2(aq) is specified and cause a very reducing Eh so that iron precipitates as iron ? (whereras in ChemApp the pressure can be held constant defining "undefined volume": only Fe3O4 precipitates )

 

If Hydrogen is develloped during the reaction, but H2(aq) is not specified, will this cause to stay at a more oxidizing Eh as it should and will precipitate as FeO or another oxidized phase ?

 

As I need to reproduce the conditions of reaction and the results obtained with ChemApp I would like to have your opinion.

 

In your opinion what can I do other to prevent the reducing effect of H2.

 

I suppressed some species, including iron to have the same effect, but this seems a little bit strange to me.

 

2. Another point: I think it is quite dangerous to create calculation outputs with no hint on the exact conditions which are used to get the result.

 

So I would suggest to verify that all conditions are mentionned, especially (that is why I tell you this) e.g. the number and sort of species suppressed, but perhaps other

parameters as well (data base/ file used, number of phases etc. would be great as modification for version 8.00 which we will buy soon I suppose)

 

Thanks

 

Thomas Willms

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Hello Tom,

 

allow me a, probably, last question or conclusion:

 

1. If hydrogen is develloped during the reaction, will it stay all in solution if H2(aq) is specified and cause a very reducing Eh so that iron precipitates as iron ? (whereras in ChemApp the pressure can be held constant defining "undefined volume": only Fe3O4 precipitates )

 

If Hydrogen is develloped during the reaction, but H2(aq) is not specified, will this cause to stay at a more oxidizing Eh as it should and will precipitate as FeO or another oxidized phase ?

 

As I need to reproduce the conditions of reaction and the results obtained with ChemApp I would like to have your opinion.

 

In your opinion what can I do other to prevent the reducing effect of H2.

 

I suppressed some species, including iron to have the same effect, but this seems a little bit strange to me.

 

2. Another point: I think it is quite dangerous to create calculation outputs with no hint on the exact conditions which are used to get the result.

 

So I would suggest to verify that all conditions are mentionned, especially (that is why I tell you this) e.g. the number and sort of species suppressed, but perhaps other

parameters as well (data base/ file used, number of phases etc. would be great as modification for version 8.00 which we will buy soon I suppose)

 

Thanks

 

Thomas Willms

 

Hi Thomas:

 

You can certainly constrain the oxidation state of the system by swapping dissolved hydrogen in for oxygen- this would be one way to set up reducing conditions. You might review the sections on redox equilibrium and disequilibrium- by default, all redox reactions in the system are constrained via the master redox species, Oxygen.

 

You can see all of your model constraints by looking at your saved model script in an ASCII editor, like Notepad.

 

Best regards,

 

Tom

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Hello,

 

Thanks Tom. Off course I know that all conditions are in the model script, but they are not in the reaction output file. I mean I would prefere if all conditions to produce a result are also a part of the output file. Like this, reaction output files would be independent from model files. Because, as in our case, the model file will be modified all the time to get an adequate model, the reaction outputfiles cannot be related to the model file. Therefore it would be better if a part of the output file contains all conditions of the reaction. As you said, all data are in the model file. Therefore it should be easy for the program GWB to copy the lines of the model file and copy them at the end of the reaction output file for example.

 

Thanks

 

Thomas

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Hello,

 

Thanks Tom. Off course I know that all conditions are in the model script, but they are not in the reaction output file. I mean I would prefere if all conditions to produce a result are also a part of the output file. Like this, reaction output files would be independent from model files. Because, as in our case, the model file will be modified all the time to get an adequate model, the reaction outputfiles cannot be related to the model file. Therefore it would be better if a part of the output file contains all conditions of the reaction. As you said, all data are in the model file. Therefore it should be easy for the program GWB to copy the lines of the model file and copy them at the end of the reaction output file for example.

 

Thanks

 

Thomas

 

Hi Thomas:

 

You can accomplish this by appending the line:

 

$type Input_script.sp8 >> SpecE8_output.txt

 

after the 'Go' statement in your input script.

 

Hope that helps,

 

Tom Meuzelaar

RockWare, Inc.

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Hi Thomas:

 

You can accomplish this by appending the line:

 

$type Input_script.sp8 >> SpecE8_output.txt

 

after the 'Go' statement in your input script.

 

Hope that helps,

 

Tom Meuzelaar

RockWare, Inc.

 

 

1) Problem :

Thanks, but I don't find any "Go" in the input sript,which looks

like that:

 

# React script, saved Fri Jun 19 2009 by wim

data = "M:\m\projekte\770230 Chemotox\Arbeitsergebnisse\Rechnungen\CTDP_corr_GRS_mod_RW_new_uraninit.dat" verify

time start = 0 days, end = 1e6 years

temperature = 25

H2O = 20007.8 free kg

Na+ = 2577.67 mol

K+ = 16.103 mol

Mg++ = 94.8337 mol

Ca++ = 134.881 mol

Cl- = 2602.55 mol

SO4-- = 229.602 mol

HCO3- = 4.03732 mol

pH = 7.9

swap e- for O2(aq)

Eh(V) = -.1

swap FeO(aq) for Fe+++

FeO(aq) = .001 umol

B(OH)3 = .001 umol

Ti(OH)4(aq) = .001 umol

swap Sn(OH)4(aq) for Sn++

Sn(OH)4(aq) = .001 umol

swap N2(aq) for NH3(aq)

N2(aq) = .001 umol

swap CuO(aq) for Cu++

CuO(aq) = .001 umol

swap HCrO2(aq) for CrO4--

HCrO2(aq) = .001 umol

swap HAsO2(aq) for H2AsO4-

HAsO2(aq) = .001 umol

swap HAlO2(aq) for Al+++

HAlO2(aq) = .001 umol

Ni++ = .001 umol

HPO4-- = .001 umol

swap MnO(aq) for Mn++

MnO(aq) = .001 umol

SiO2(aq) = .001 umol

swap U(OH)4(aq) for UO2++

U(OH)4(aq) = .001 umol

swap ZrO2(aq) for Zr++++

ZrO2(aq) = .001 umol

swap HMoO4- for MoO4--

HMoO4- = .001 umol

swap VO4--- for VO2+

VO4--- = .001 umol

balance on Cl-

reactants times 3

react 14.4274 mol of N2(g)

react 48220.2 mol of Fe

react 340.443 mol of C

react 356.318 mol of Si

react 790.942 mol of Mn

react 14.0376 mol of P

react 7.26058 mol of S

react 694.25 mol of Ni

react 42.9271 mol of Al

react 5.39444 mol of As

react 1395.86 mol of Cr

react 27.8255 mol of Cu

react 62.5615 mol of Sn

react 63.1753 mol of Ti

react 332.837 mol of B

react 6840.63 mol of Uraninite

react 5091.48 mol of Zr

react 20.8903 mol of Corundum

react 13.1645 mol of Mo

react 9.91726 mol of V

 

suppress Spent_Fuel V Cast_Iron Zr

suppress Fe Karelianite V3O5 V4O7

suppress Sn As Cu Daphnite-14A

suppress FeO Ilmenite Hydroboracite Mo

suppress Chamosite-7A Chalcocite Chromite Colemanite

suppress Realgar Magnesiochromite Bornite Hydroxylapatite

suppress Daphnite-7A Chalcopyrite Ripidolite-14A Ripidolite-7A

suppress Whitlockite Amesite-14A Delafossite Mn3(PO4)2

suppress Clinochlore-14A Clinochlore-7A Cuprite Covellite

 

 

Tell me please where you mean exactly.

 

 

2. Problem:

 

I get the message "Bad Beta Pitzer pair", although I did nothing change at my data bases and pitzer parameters.

I cannot find any species which is present in Pitzer parameters but not in species list, also, normally I got another message with this problem.

What might this be ? Before, It only occured with one input files, but now nothing works.

 

All data bases which worked before do not work anymore.

Any idea how this is possible ???

 

 

Thanks

 

Thomas Willms

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Hello Tom,

 

we found a Log(K) = 499.0000 for the solid phase Zr by reduction from Zr++++ at 25°C.

 

Can you tell us that this is not an error ?

 

Thanks

 

Thomas

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Hi Thomas:

 

1) Problem :

Thanks, but I don't find any "Go" in the input sript,

 

Tell me please where you mean exactly.

 

You can simply add the "Go" statement to the end of your script (open the script in Notepad, add the statement "Go" as the last line, and re-save the script). It simply tells React to execute the script after loading.

 

2. Problem:

 

I get the message "Bad Beta Pitzer pair", although I did nothing change at my data bases and pitzer parameters.

I cannot find any species which is present in Pitzer parameters but not in species list, also, normally I got another message with this problem.

What might this be ? Before, It only occured with one input files, but now nothing works.

 

All data bases which worked before do not work anymore.

Any idea how this is possible ???

 

Can you email your input file and database to me at gwb@rockware.com?

 

Thanks,

 

Tom

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Hello Tom,

 

we found a Log(K) = 499.0000 for the solid phase Zr by reduction from Zr++++ at 25°C.

 

Can you tell us that this is not an error ?

 

Thanks

 

Thomas

 

Hi Thomas:

 

Which database did you find this data in?

 

Regards,

 

Tom

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