ThommyW
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Posts posted by ThommyW
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Hello Tom,
just to confirm my guess:
I suppose, that each of the gas solublities gas(aq) is defined by:
gas(g) --> gas(aq)
even if it is not written. How are they calculated
internally, especially N2(aq) ?
Haven't they been calculated on the basis of basic species because gases are not
belonging to those ?
Also, in one file I saw the Eh reaction had a value of
-86.... meaning based on O2(aq) in another one it is -83....
meaning that it refers to O2(g).
What is the usual form you are using, the one based on
O2(aq) because it is basic species or the other one?
What does GWB need actually?
Thanks
ThommyW
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Hello Tom,
I edited my last response: the anwer text was hidden.
Also, I hope adding one coefficient for 1/T^2 is possible so that I can implement it already right now!
Thanks
Thomas
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Thanks for the information concerning the outdate format of Pitzer.dat. This means that I will implement the form of temperature dependence as in PHRQPITZ.dat
and (only 25°C) hmw.dat respectively for the case that a transformation of the equation is possible. This will be the case if you agree to add one term, as already requested by the GRS (Helge Moog).
Thanks
ThommyW
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Hello Tom,
Concerning the factor ten, I agree, the numbers were only written differently, thanks, it was my error.
Otherwise concerning parameters and equations, I am afraid you are in error:
In the new (blue) book Geochemical and Biogeochemical Reaction modelling the
equation 8.6 is
log(gamma) = aI + bI^2 + c*I^3
The values for neutral species (CO2(aq), O2(aq) etc. are given for 25, 100, 200 and 300°C only
in a table (on page 121), which contains only three parameters a,b, c.
So the data are given for the equation 8.6 (also three parameters), which is given for neutral species CO2(aq) etc.
That is why I wondered that there is one grid with only zero's .
(Is it a queston of simplicity for the program as for water there are 4 parameters ?).
In contrast to this the equation 8.8 is the one with four parameters and only refering to the activity of water
(I gave it above). In the table there are four parameters on page 122 and these are clearly refering to the equation 8.8.
Sincerely
Thomas Willms
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Hello Tom,
thanks for your answer and the given equation for the Pitzerdata given in the file phrqpitz
Ba++ Br-
beta0 = 0.31455 -0.33825E-3
beta1 = 1.56975 6.78E-3
beta2 = 0.0
cphi = -0.0159576
alpha1 = 2.0
alpha2 = 0.0
By the way: how do I know if missing coefficients mean that the coefficients of the equation are zero
or that there are no data given? Which means that you can or you cannot apply it for other temperatures.
What must I do if there are only data for 25°C to make this clear ?
Furthermore:
concerning data in thermo-Pitzer.dat :
H+ Cl-
beta0 = 0.1775 beta1 = 0.2945 beta2 = 0.0000
alpha1 = 2.0 alpha2 = 0.0
db0/dt = -0.308E-03 d2b0/dt2 = 0.000E+00
db1/dt = 0.142E-03 d2b1/dt2 = 0.000E+00
db2/dt = 0.000E+00 d2b2/dt2 = 0.000E+00
What about these data ? Is it the same equation or simply
beta = beta(25°C) + B * T
because there are only two constant numbers as derivations ?
Is this cited in the same article Plummer et al., 1988.? (I don't know this one)
In fact this was the file where all my questions refer to.
Does this mean there is only one linear dependence of T because
the second derivation is zero ? Validity ?
It seems that we cannot make parameter files with a dependence on
temperature because parameters of modern equations of the general form
x = a + b * T + c/T + + d*T^2 + e*ln(T) + f* 1/T^2
which are used for log(K), Pitzer parameters etc.
cannot neither be used nor calculated from the given equation by tranformation.
Will this change in future ?
Thanks for your answer in advance.
Sincerely
Thomas Willms
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Hi Thomas:
The equations used to calculate the activities of electrically neutral species and water are given in chapter 8 of Geochemical and Biogeochemical Reaction Modeling (or chapter 7 if you have the older Geochemical Reaction Modeling).
Be sure you also understand the importance of the ion size parameter which is described in the Thermo Datasets Appendix of the GWB Reference manual as follows:
Hope that helps,
Tom Meuzelaar
RockWare, Inc.
Hello Tom,
For CO2 the given data correspond to the equation for neutral species log gamma = a* I + b * I^2 + c* I^3
and the given data to those given in the book, discussing this equation for the b-dot model.
But it is not clear to me why there is a fourth grid with only zero's.
This does not make sense if these parameters refer to an equation with 3 parameters.
Furthermore, if I understood you right, the H2O data refere to the B-Dot equation (8.6) with 4 parameters:
phi = 1 - 2,303 A/(a^3 * I) (b - 2 ln(b ) - 1/b ) + B* I/2 + 2 C* I^2/3 + 3D* I^3/4
because 4 data sets are given. What is striking is, that all data given in the book are higher
by a factor of 10. What value is used ? Why is there a factor of ten ?
Thanks for your help
Sincerely
ThommyW
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Hello Tom,
What are the values tabulated in the thermo file,
and given below ? For which species exactly and which
reaction or/equation these values below are valid ????????
* c co2 1
0.1224 0.1127 0.0934 0.0802
0.0843 0.0989 0.1371 0.1967
* c co2 2
-0.0047 -0.0105 -0.0036 -0.0015
-0.0118 -0.0104 -0.0071 -0.0181
* c co2 3
-0.0004 0.0015 0.0001 0.0005
0.0031 0.0014 -0.0029 -0.0025
* c co2 4
0.0000 0.0000 0.0000 0.0000
0.0000 0.0000 0.0000 0.0000
* c h2o 1
0.500000E+03 0.145397E+01 0.500000E+03 0.155510E+01
0.162250E+01 0.500000E+03 0.500000E+03 0.500000E+03
* c h2o 2
0.500000E+03 0.223570E-01 0.500000E+03 0.364780E-01
0.458910E-01 0.500000E+03 0.500000E+03 0.500000E+03
* c h2o 3
0.500000E+03 0.938040E-02 0.500000E+03 0.643660E-02
0.452210E-02 0.500000E+03 0.500000E+03 0.500000E+03
* c h2o 4
0.500000E+03 -0.536200E-03 0.500000E+03 -0.713200E-03
-0.831200E-03 0.500000E+03 0.500000E+03 0.500000E+03
In looked in the archive but I found only one item of 2004 what was not sufficiently exact.
I also looked in the reference but only a general description is given. (see below )
-------------------------------------------------------------------------------------
......
Following the temperature table are tables giving pressure, coefficients for calculating
parameters in activity coefficient correlations, and so on, at each of the principal temperatures.
The tables look like:
Thermo Datasets
..................
...
----Coefficients for calculating the activity coefficients for CO2 and some other electrically neutral species,---
WHICH SPECIES /REACTION /equations / type of VALUES FOR ALL OF THE 4 GRIDS ????????????????????
Coefficients for calculating the activity of water,
WHICH SPECIES/ REACTION /equations / type of VALUES FOR ALL OF THE 4 GRIDS ????????????????????
--------------------------------------------------------------------------------------------------------------------------------
I need to know all this exactly because I need perhaps to recalculate these values by our own thermodynamic data, depends....
Thanks very much
ThommyW
PS: What about log(K) for H2O(liq) --> H2O(g)
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Hello Tom,
as you asked me, I am bringing the question to the forum and I added some very important details (!!!)
1) may you explain me what the temperature derivations in the pitzer.dat file mean ?
What is the function supposed behind this ?
2) What is the validity ?
3) How to calculate a value for let's say 100 °C ?
4) Why is the value constant ? Is it just a function f = a + b*T ?
Here an abstract :
------------------------------------------------------------------------------------------------------------
l- NO3-
beta0 = 0.0160 beta1 = 0.0000 beta2 = 0.0000
alpha1 = 99.0 alpha2 = 99.0
dt0/dt = 0.000E+00 d2t0/dt2 = 0.000E+00
dt1/dt = 0.000E+00 d2t1/dt2 = 0.000E+00
dt2/dt = 0.000E+00 d2t2/dt2 = 0.000E+00
-end- end of theta set, begin with cphi set of mu-s
H+ Cl- H+
mu = 0.000133 dmmx/dt = 0.104E-04 d2mmx/dt2 = 0.000E+00
---------------------------------------------------------------------------------------------------------------
The standard equation for the dependance of temperature is eg. like that:
f = a + b *T + c * T^2 + d/T + e*ln(T) + f/T^2
5) Wouldn't it be preferalble to let the user define the equation to apply ?
Will there be any possibility to apply such an equation, to enter the corresponding coefficients a to f
and when ?
As I have the equation and its coefficients as given before. I may try to calculate the correponding
coefficients for the equation for which GWB coefficients are given, but what about its validity range ??????????????
Thanks
Thomas Willms
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Hello Tom,
I finally foud out that there is one definitive problem with the calculation which results in the error messages "ionic strength out of range" and "charge to large".
If I incorporate this spezies in the data base:
(UO2)4(OH)7(SO4)4-------
* formula= (UO2)4(OH)7(SO4)4
charge= -7 ion size= 4 A mole wt.= 1583.42 g
4 species in reaction
4.0000 UO2++ 7.0000 H2O 4.0000 SO4--
-7.0000 H+
500.0000 19.0100 500.0000 500.0000
500.0000 500.0000 500.0000 500.0000
as an aqueous species, then any calculation crashes, with or without Pitzer-parameters.
Can you check why this happens and where is the problem ?
Thanks
Thomas Willms
Dear Thomas:
I'd be happy to take a quick look at your script- but since you use a proprietary database, I cannot reproduce your problem. Can you email me your database? Send to gwb@rockware.com - I will keep it in confidentiality.
Regards,
Tom Meuzelaar
RockWare, Inc.
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Hello ,
I just remarked that in "thermo-hmw.dat" the alpha2 values
of a big number of species is given with zero ?
H+ SO4--
beta0 = 0.0298
beta1 = 0.0
beta2 = 0.0
cphi = 0.0438
alpha1 = 2.0
alpha2 = 0.0
K+ Cl-
beta0 = 0.04835
beta1 = 0.2122
beta2 = 0.0
cphi = -0.00084
alpha1 = 2.0
alpha2 = 0.0
K+ CO3--
beta0 = 0.1488
beta1 = 1.43
beta2 = 0.0
cphi = -0.0015
alpha1 = 2.0
alpha2 = 0.0
K+ HCO3-
beta0 = 0.0296
beta1 = -0.013
beta2 = 0.0
cphi = -0.008
alpha1 = 2.0
alpha2 = 0.0
K+ HSO4-
beta0 = -0.0003
beta1 = 0.1735
beta2 = 0.0
cphi = 0.0
alpha1 = 2.0
alpha2 = 0.0
K+ OH-
beta0 = 0.1298
beta1 = 0.32
beta2 = 0.0
cphi = 0.0041
alpha1 = 2.0
alpha2 = 0.0
K+ SO4--
beta0 = 0.04995
beta1 = 0.7793
beta2 = 0.0
cphi = 0.0
alpha1 = 2.0
alpha2 = 0.0
where I expect normally 12.
Might this a reason for high ionic strength ?
Thomas Willms
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Hello GWB Users,
since 5 days I am in great trouble with my GWB calculations. Without knowing it, it seems that, despite all Pitzer parameters present, the data bases were titled with activity model = "Debye Huckel" instead of "h-m-w". So every time it worked, it was just because the D H model was used. Finally, thanks to Tom, I found out that the activity model was "debye-huckel" and when I put 'h-m-w' the calculation doesn't work anymore.
Instead of the calculation I get a message "bad beta Pitzer pair'. the worst: This is true for any data base ever produced since last year ago... and we added very much data....
The only parameters working were finally those of the file thermo_hmw.dat. So using an input file for 'sea water' (and eliminating SiO2) together with thermo_hmw.dat the calculation works (but is boring). If I add any element of our data base in a small concentration (as I also did for the D - H files) and a small quantity of the pure solid element as reactant, I get another error:
"calc_hmw: max charge too large". This is true for any element and any big or small quantity of it.
Considering that in the h-m-w file it is written, that the parameters are parsed "word by word and no aligning of parameters is necessary", I don't understand why I get the message "bad pitzer pair". At first we thought of point ('.' ) - Comma (',') - problem, but there are no commas in the numbers.
Considering that there is no problem with the data base using the debye huckel model, the problem has to be somewhere in the Pitzer block.
In the best case, varying the Eh(V) value and the concentration or reactant quantities I get the following message (the order of magnitude varying slightly) :
Ionic strength out of range.
Largest residual(s):
Resid Resid/Totmol Cbasis
--------------------------------------------------------
Cu+ 1.695e+014 1 4.498e-006
--------------------------------------------------------
Finally I found out, that all this trouble only concerns our big data bases (even though working with the D H model). Just starting with thermo_hmw.dat and adding one element (Cu), one redox species (Cu+), some aqueous species and some minerals, the data base works for a saline solution with this one element added and some traces of it as ion.
Does anybody know that penomenon ??
Thanks
Thomas Willms
Finally I found out the reason for the message 'Bad Pitzer Pair'. Now I have the same problem as 'Stephan' :
Ion strength out of range. In contrast to him I have a system being much more complicate:
# React script, saved Tue Aug 11 2009 by wim
data = "D:\Gemeinsame Dokumente\Geochemical-work-bench\Eigenes\DB--Rechnung_geht\_Rechnung1\ZusatzChemapp-Cu\Fe-thermo_hmwZementUran3.dat" verify
time start = 0 days, end = 1e6 years
temperature = 25
decouple HS-
H2O = 20007.8 free kg
Na+ = 2577.67 mol
K+ = 16.103 mol
Mg++ = 94.8337 mol
Ca++ = 134.881 mol
Cl- = 2604.5501 mol
SO4-- = 229.602 mol
HCO3- = 4.03732 mol
pH = 7.9
swap e- for O2(aq)
Eh(V) = -.1
swap Cu+ for Cu++
Cu+ = 1 umolal
swap Al(OH)4- for Al+++
Al(OH)4- = 1 umolal
swap Fe++ for Fe+++
Fe++ = 1 umolal
SiO2(aq) = 1 umolal
swap (UO2)2(OH)2++ for UO2++
(UO2)2(OH)2++ = 1 umolal
balance on Cl-
TDS = 35000
react 1 mol of Cu
react 1 mol of Fe
slide fugacity of H2(g) 2
react 1 mol of Al
react 1 mol of Si
react 1 mol of U
suppress CO2(aq) Delafossite
delxi = 1 linear
The calculation works without Uranium, but with Uranium the error depends on the species
UO2<2+> <--> U(OH)4 : Program crashes directly : calc_hmw: max charge too large
UO2<2+> <--> (UO2)2(OH)2: (see below)
Solving for initial system.
...suppressed loading of: CO2(aq)
...suppressed loading of: Delafossite
Loaded: 70 aqueous species,
166 minerals,
4 gases,
0 surface species,
14 elements,
7 oxides.
Ionic strength out of range.
Largest residual(s):
Resid Resid/Totmol Cbasis
--------------------------------------------------------
(UO2)2(OH)2++ 1.035e+010 1 9e-007
--------------------------------------------------------
this is the same with all other species I have. And concerning the comment of Tom to the post of Stephan:
If it is to far from equilibrium, it causes problems... What can I do more than trying all species ?
Thanks
Thomas Willms
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Hello GWB Users,
since 5 days I am in great trouble with my GWB calculations. Without knowing it, it seems that, despite all Pitzer parameters present, the data bases were titled with activity model = "Debye Huckel" instead of "h-m-w". So every time it worked, it was just because the D H model was used. Finally, thanks to Tom, I found out that the activity model was "debye-huckel" and when I put 'h-m-w' the calculation doesn't work anymore.
Instead of the calculation I get a message "bad beta Pitzer pair'. the worst: This is true for any data base ever produced since last year ago... and we added very much data....
The only parameters working were finally those of the file thermo_hmw.dat. So using an input file for 'sea water' (and eliminating SiO2) together with thermo_hmw.dat the calculation works (but is boring). If I add any element of our data base in a small concentration (as I also did for the D - H files) and a small quantity of the pure solid element as reactant, I get another error:
"calc_hmw: max charge too large". This is true for any element and any big or small quantity of it.
Considering that in the h-m-w file it is written, that the parameters are parsed "word by word and no aligning of parameters is necessary", I don't understand why I get the message "bad pitzer pair". At first we thought of point ('.' ) - Comma (',') - problem, but there are no commas in the numbers.
Considering that there is no problem with the data base using the debye huckel model, the problem has to be somewhere in the Pitzer block.
In the best case, varying the Eh(V) value and the concentration or reactant quantities I get the following message (the order of magnitude varying slightly) :
Ionic strength out of range.
Largest residual(s):
Resid Resid/Totmol Cbasis
--------------------------------------------------------
Cu+ 1.695e+014 1 4.498e-006
--------------------------------------------------------
Finally I found out, that all this trouble only concerns our big data bases (even though working with the D H model). Just starting with thermo_hmw.dat and adding one element (Cu), one redox species (Cu+), some aqueous species and some minerals, the data base works for a saline solution with this one element added and some traces of it as ion.
Does anybody know that penomenon ??
Thanks
Thomas Willms
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Hi Thomas:
Attached is a working script that appends the input data to the output file.
Have a look at the script in a text editor to see how the code is written.
Let me know if this helps you.
Regards,
Tom
It seems that you sent me a file for another program SpecE8. I don't know it very well, but if I use the file temp.spec8 with it, there is no line added of the script .
I used the line $type temp.sp8 >> SpecE8_output.txt
By the way I don't work with this program, so what I need is this function for REACT and not for Spec8.
I tried $type input_script.rea >> Reac_output.txt
because this is the name of the used output file. Will the program recognize inputscript as the present script ?
Please send me a file proven to work.
Thomas Willms
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Hi Thomas:
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.
Can you email your input file and database to me at gwb@rockware.com?
Thanks,
Tom
Hello Tom,
I sent you the input file and the data base. Can you please tell me how to put all input conditions in the given input file and without starting the calculation on loading and resend it ?
It still doesn't work as I would like it. There is a "dos window" and a message "file not found". What is "inputscript.sp8" ? A variable, the name of the present file? I added the line exactly as given, but it didn't work. I have all files, input file and data base in a private working directory. Do I need to give the path of that *.sp8 file ?
Sincerely
Thomas
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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:
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,
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 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,
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
-
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
-
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
-
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
-
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
-
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
- <<<
Thermo data coefficients CO2 H2O ... URGENT !!!!
in Activity models
Posted
Hello Tom,
concerning part 1 of the anwers:
I know that there is a gas section, but I am speaking of the solubilities in the first part of the parameter file thermo.dat
which are generally based on the equation (and where no reactions are given)
X2(g) --> X2(aq)
--------------------------------------------------
* log k for eh reaction
-93.701 -86.003 -77.117 -68.972
-60.928 -54.559 -49.374 -45.037
* log k for o2 gas solubility
-2.6610 -2.8990 -3.0580 -3.1250
-3.0630 -2.9140 -2.6600 -2.4100
* log k for h2 gas solubility
-3.0240 -3.1120 -3.1440 -3.1120
-3.0520 -2.9420 -2.7300 -2.4400
* log k for n2 gas solubility
-2.9740 -3.1830 -3.3210 -3.3330
-3.1740 -2.9960 -2.7480 -2.4530
---------------------------------------------------------
As gases are no basic species in GWB, for this equation there is no ln(K) available directly.
That is why I asked. Now there are several possibilities:
1. Values are only implemented as values for each temperature, calculated elsewhere taken of a reference etc.
2. Values are calculated internally by combination of ln(K)'s of several reactions.
3. Values are calculated internally by the Gibbs energies of formation for each reactant.
concerning part 2:
Same thing, but I am not speaking of genereal procedures but of the reaction of the species N2 in case it has been
calculated by the second way given above (combination of reactions)
concerning part 3:
I am refering to the parameter files as e.g. the thermo.dat file.
By the way - as always - I looked at the book, but it was not clear to me from the book.
Your log(K) for Eh is identical with ours which is for H2(g) + O2(g) --> 2H2O.
Are you using the same equation although H2(g) and O2(g) are no basic species ?
Also values are different in different files. Why are there equations with different
basic species ?
in thermo_hmw.dat (as it seems : H2(g) + O2(g) --> 2H2O)
* log k for eh reaction
-91.0454 -83.1028 -74.0521 -65.8632
-57.8929 -51.6850 -46.7266 -42.6842
in thermo_phrqC (as it seems : H2(g) + O2(aq) --> 2H2O)
* log k for eh reaction
-92.2863 -87.5026 -83.1200 -78.3227
-73.9641 -69.9865 -66.3420 -62.9906
Why are there different equations (and values) in those files ?
In fact: I can sum up naealy all my questions (except for the last one) with one only question:
The values given in the very first part of the parameter file, giving Eh-values and solubilities etc.
are they basing on equations using directly or indirectly reactions with basic species or not ?
(which ones?)
Thanks very much
ThommyW