ThommyW

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

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

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

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

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

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

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

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)

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

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

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

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

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

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

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