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13. EQ !"!#R! $ $O% "E

&ig. 1. Equilibrium Module Menu. This module enables you to calculate multi-component equilibrium compositions in heterogeneous systems easily. The user simply needs to specify the reaction system, with its phases and species, and gives the amounts of the raw materials. The program calculates the amounts of products at equilibrium in isothermal and isobaric conditions. The user must specify the substances and potentially stable phases to be taken into account in the calculations as well as the amounts and temperatures of raw materials. Note that if a stable substance or phase is missing in the system definition, the results will be incorrect. The specification can easily be made in the !" program interface, and the input data file must be saved before the final calculations are made. The equilibrium composition is calculated using the #$%%! or !&'#(!M$) solvers, which use the #ibbs energy minimi*ation method. The results are saved in +.&#$ or +.&!# te,t files respectively. The post-processing -$"-program reads the result files and draws pictures of the equilibrium configurations if several equilibria have been calculated. The user can toggle between the equilibrium and graphics programs by pressing the buttons shown in .igs. /, 0, 1 and 2. The Equilibrium module reads and writes the following file formats3 1. '.(E$-&i)e &orm*t This file format contains all the data and formatting settings of each definition sheet as well as the phase names, etc. The equilibrium module always saves this

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file regardless of which file format is selected for saving the actual input file for equilibrium calculations. $f you want to use formatting settings, please use the O+en ,orm*) selection from &i)e menu, see .ig. 0. 2. '.!(!--i)e &orm*t This file format contains the data for calculations for the #$%%!-solver only and it can read these files. 3. '.!S(--i)e &orm*t This file format contains the data for calculations with the !olgasmi,-solver only and it can read these files. .. '.%A2--i)e &orm*t This file format contains the data for calculations for the "hem!(#E 4.5 only. The equilibrium module also reads +.6(4-files, but not if solution model parameters have been added to the file manually . Note that this equilibrium solver is not included in HSC 5.0. /. '.%AT--i)e &orm*t This file format contains the data for calculations for "hem!(#E 7.5 and 0.5 only. The equilibrium module also reads +.6(T-files, but not if solution model parameters have been added to the file manually . Note that this equilibrium program is not included in HSC 5.0. The equilibrium solvers #$%%!, !olgasmi, and "hem!(#E deliver their results in (!"$$ te,t-files. The -$"-module reads these files and generates graphics and tables as described in "hapter /7.2. There are three ways of creating an input file 8+.$#$, +.$!#93 /. -ress the to+ 0utton in the menu, see .ig. /. Then specify the elements which are present in your system, see .ig. 4. The !"-program will search for all the available species in the database and divide them, as default, into gas, condensed and aqueous phases. The user can then edit this preliminary input table. -ress the se1on2 0utton of the menu if you already know for sure the possible substances and the phases of the system, see .ig. /. -ress E2it O)2 !n+ut &i)e if you already have an input file which can be used as a starting file. Edit the input table and save it using a different name, see .ig. /.

4. 7.

$f you only want to calculate the equilibrium compositions with the e,isting +.$#$-files press C*)1u)*te, see .ig. /. $f you want to draw pictures from the e,isting +.&#$ files made by the #$%%!-solver press %r*3, see .ig. /. :sing 4rint you can get a paper copy of the +.$#$ and +.&#$ files.

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13.1

St*rting -rom 2e-ining the E)ements

&ig. 2. !pecifying the elements of the system. $f you do not know the substances of the system you may also start by specifying its elements, i.e. a selection of the system components. The elements selected will be displayed in the Elements ;indow, see .ig. 4. (fter pressing E)ements in the Equilibrium Menu, see .ig. /, you can continue with the following steps3 /. !elect one or more e)ements3 -ress buttons or type the elements directly into the bo,. Try for e,ample Ni, ", &, as given in .ig. 4. 6o not select too many elements, to avoid a large number of species. $n practice / - < elements is &= !elect the form of species from Se*r1h $o2e in which you are interested. >ou may specify up to ? 1*r0on )imits for the organic species, for e,ample 0, 1, 2. -ress O5 and you will see the species found, see .ig. 7. The !"-program will search for all species which contain one or more of the elements given, first from the &wn database and, if not found there, from the Main database.

4. 7.

%y decreasing the number of species you may increase the calculation speed and make the solution easier. Therefore select only those species, which you are sure to be unstable in your system and press %e)ete Se)e1te2. %e careful, because if you delete the stable ones the calculated equilibrium results will be incorrect. $f you are not sure of some substance then do not delete it.

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$f you want to use only some of the species in the calculations then select only these and press %e)ete nse)e1te2, which will remove the unnecessary species. Especially if you have selected " and@or among the other elements you will get a very large number of species for the calculation and you are advised to decrease the number of species. !ee "hapter /7.0 for selection criteria for phases and species.

&ig. 3. 6eleting undesired species. $f there are some odd species in the list then you can double click that formula in the list or press the -eep 6atabase button and see the whole data set of the species in the database. $f you want to remove it press Remo6e in the 6atabase ;indow. This will remove the species from the list but not from the database. ;hen making first time calculations it may be a good idea to take a paper copy of the species selected by pressing 4rint. Then you can also easily add or delete species in the following window, see .ig. 0. The species have been divided into rough reliability classes in the databaseA you may select the species available in the most reliable class / by pressing Se)e1t C)*ss 1. >ou may also set the sorting order for the species using the option buttons above the "ontinue button. The sorting order will determine the order of species in the Equilibrium Editor, see .ig. 0. ;hen you have finished deleting the species, press Continue and you will return to the

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13.2

(i6ing !n+ut %*t* -or E7ui)i0rium C*)1u)*tions

&ig. .. !pecification of the species and phases for the reaction system.

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&ig. /. !pecification of the calculation mode.

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The Equilibrium Editor consists of two sheets for determining the conditions of the equilibrium calculations. $n S+e1ies and O+tions sheets, .igs. 0 and <, you give all the data required to create an input file for the equilibrium solvers and for calculating the equilibrium compositions. Equilibrium calculations are made in three steps3 /. 4. 7. The user gives the necessary input data using the !pecies and &ptions sheets in the Equilibrium Editor ;indow, .ig. 0, and saves this data as a te,t file. The equilibrium compositions will be calculated using the equilibrium solvers, which read the input-files and save the results in corresponding output-files. The results in the output-file can be further processed to graphical form by pressing %r*3 in .ig. / or 1 if several successive equilibria have been calculated.

The most demanding step is the selection of the species and phases, ie. the definition of the chemical system. This is done in the !pecies sheet of the Equilibrium Editor, .ig. 0. >ou can move around the table using the mouse, or Tab and (rrow keys. The other things which you should consider are3

1. S+e1ies :su0st*n1es, e)ements, ions...;

>ou may write the names of the species directly into the !pecies column, without a preliminary search in the Elements window. $f you have made the search on the basis of the elements you already have the species in the !pecies column. >ou can check the names and the data of the species by pressing the right mouse button and selecting 4ee+ %*t*0*se from the popup menu. $f you press the $nsert button you can collect species for the equilibrium calculations sheet. -ressing Remo6e will remove an active species from the equilibrium calculations. >ou can insert an empty row in the table by selecting Ro3 from the !nsert menu or pressing the right mouse button and selecting !ns Ro3 from the popup menu. Bows can be deleted by selecting Ro3 from the !nsert menu or by pressing the right mouse button and then electing %e) Ro3 from the popup menu. >ou can change the order of the substances by inserting an empty row and using the copy - paste method to insert substance in the new row. The drag and drop method can also be used. However, it is extremely important to move the whole row, because there is a lot of auxiliary data in the hidden columns on the right side of the sheet . -lease keep the Co+y $o2e selection on in the E2it menu when rearranging species. This will force the program to select the whole row. ;hen formatting the columns and cells, turn o-- the Co+y $o2e selection in the E2it menu. :se the 8l9-suffi, for a species only if you want to use the data of liquid phases at temperatures below its melting point. .or e,ample, type SiO2:); if !i&4 is present in a liquid o,ide phase at temperatures below the melting point of pure !i& 4. !ee "hapter 4C.4.

2. 4h*ses
The species selected in the previous step must be divided into physically meaningful phases as determined by the phase rows. This finally defines the chemical reaction system for the equilibrium calculation routines. 6efinition of the phases is necessary because the behavior of a substance in a mi,ture phase is different from that in pure form. .or e,ample, if we have one mole of pure magnesium at /555 D", its vapor pressure is 5.0< bar. owever, the magnesium vapor pressure is much smaller if the same amount has been dissolved into another metal.

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The phase rows must be inserted in the sheet using 4h*se selection in !nsert menu or using the same selection in the popup menu of the right mouse button. The Equilibrium module makes the following modifications to the sheet automatically when you insert a new phase row in the sheet and3 /. 4. 7. 0. (sks a name for the new phase, which you can change later, if necessary. $nserts a new empty row above the selected cell of the sheet with a light blue pattern. (ssumes that all rows under the new row will belong to the new phase down to the ne,t phase row. $nserts new E,cel type !:M formulae in the new phase row. These formulae calculate the total species amount in the phase using kmol, kg or Nm 7 units.

;hen the insert procedure is ready, you may edit the phase row in the following way3 /. The phase name can be edited directly in the cell. 4. The phase temperature can also be changed directly in the cell and it will change the temperatures of all the species within the phase. 7. Note that you can not type formulae to the amount column of the phase row, because the !:M formulae are located there. >ou can change the amount of species in a phase using kmol, kg or Nm 7 units, simply by typing the new amount to the corresponding cell. The program will automatically update the total amount and the composition of the phase. The first phase to be defined is always the gas phase, and all gaseous species must e,ist under the gas phase row. !pecies of the same phase must be given consecutively one after another in the table. (s default, !" "hemistry automatically relocates all the gaseous species, condensed o,ides, metals, aqueous species, etc. into their own phases if you start from the Egive ElementsF option, see .ig. /. The final allocation, however, must be done by the user. $f there is no aqueous phase, all aqueous species must be deleted. Note that if you have an aqueous phase with aqueous ions, you must also have water in the phase G $f you e,pect pure substances 8invariant phases9 to e,ist in the equilibrium configuration, insert them as their own phases by giving them their own phase rows or insert all these species under the last phase row and select the 4ure Su0st*n1es in the "*st 4h*se option, see .ig. <. .ormation of pure substances is possible especially in the solid state at low temperatures. .or e,ample, carbon C, iron sulfide .e!4, calcium carbonate "a"&7, etc. might form their own pure phases. &ne of the most common mistakes is to insert a large amount of relatively EinertF substance to the mi,ture phase. .or e,ample, large amounts of solid carbon at /<55 D" do not dissolve into molten iron. owever, if these both species are inserted into the same phase then the equilibrium program assumes that iron and carbon form an ideal mi,ture at /<55 D". This will, for e,ample, cause much too low vapor pressure for the iron. Therefore carbon should nearly always be inserted into its own phase at low temperatures.

3. !n+ut Tem+er*tures o- the S+e1ies

$nput temperatures for the raw material species are essential only in the equilibrium he*t 0*)*n1e calculations, i.e. if you provide some input amount for a species you should also give its temperature. The input temperature does not affect the equilibrium composition. >ou may select the temperature unit by selecting C from the :nits menu, see .ig. 0.

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.. Amount o- the S+e1ies

$n this column you give the input amounts of the raw material species. The most important thing for the equilibrium composition is to give the 1orre1t *mounts oe)ements to the system. >ou may divide these amounts between the species as you like. $f the 1orre1t he*t 0*)*n1e is required, you must divide the amounts of elements e,actly into the same phases and in a similar manner as in the real physical world. >ou may choose between kmol or kg@Nm7 units by selecting mo) or =g from the nits menu. Note that kilograms refer to condensed substances and standard cubic meters 8Nm79 to gaseous substances, see .ig. 0.

/. Amount Ste+ -or R*3 $*teri*)s

$f you wish to calculate several successive equilibria you give an incremental step for one or more raw material species. Then the programs automatically calculate several equilibria by increasing the amount of this species by the given step. -lease remember to select the !n1re*se Amount option, see .ig. <, and give also the number of steps. The ma,imum number of steps which can be drawn is 4</ for the #$%%! solver and <5 for !olgasmi, solver. !ome 4/ - </ steps are usually enough to give smooth curves to the equilibrium diagram. >ou may give step values for several species simultaneously. .or e,ample, if you want to add air to the system give a step value for both & 48g9 and N48g9. -lease do not forget to specify the number of steps, if a diagram is to be drawn from the results.

6. A1ti6ity Coe--i1ients :in (i00s-so)6er;

The simple definition of Baoultian activity is the ratio between vapor pressure of the substance over the solution and vapor pressure of the pure substance at the same temperature. *> +:o6er so)ution; ? +:+ure; @1A (ctivity coefficient describes the deviation of a real solution from an ideal mi,ture. (ctivity coefficient - is defined as the ratio between activity * and mole fraction B of the species in the mi,ture. -> *?B @2A !n *n i2e*) so)ution they *re there-ore 2e-ine2 *s * > B *n2 - > 1 . As * 2e-*u)t in (!##S *n2 SO"(AS$!C, the *1ti6ity 1oe--i1ient o- * s+e1ies in the miBture +h*ses is *)3*ys 1. owever, if non-ideal activity coefficients are available they may be introduced in the right column. &nly simple binary or ternary e,pressions can be utili*ed directly by the #$%%! solver within !", such as3 'n8f9 'n8f9 'n8f9 'n8f9 where3 T )40 f H H H H H H H C0?<@T-4.1<7 5.1?I<1.C+)40I<.0<+)4< -7?41@T -/.4/+)2J4-4.00+)CJ4 Temperature in = Mole fraction of the species with a row number 40 in the sheet. (ctivity coefficient.

.ormulae are written using the same synta, as in E,cel, the defined names T and - are available for temperature and pressure. Mole fractions are given as cell references to

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column ). -lease note that the returning values of the formulae are insignificant, because the mole fraction values in column ) are *ero, see .igs. /1 - /2.

8. He*2ing
>ou may add any kind of heading for the input file, see .ig. <. The ma,imum number of characters allowed in the heading is C5. The -$" post-processing program automatically adds the heading to the diagrams, see .igs. // and /2.

9. E7ui)i0rium Tem+er*ture
Equilibrium will be calculated at this temperature, and each equilibrium is isothermal and thus has a constant temperature throughout the system, see .ig. <. >ou may also give the temperature range if you wish to calculate several sequential equilibria. -lease remember to also select the !n1re*se Tem+er*ture option and give the ,um0er o- Ste+s, see .ig. <. !everal equilibria are needed in order to create graphics from the results. Temperatures in the !pecies !heet, .ig. 0, have no effect on the equilibrium compositions. They are only needed if the reaction enthalpy is necessary to calculate correctly, see "hapter /7.2./, .ig. /5 and >-(,is selections.

<. E7ui)i0rium 4ressure

Equilibrium calculations are always made in constant pressure or in isobaric conditions. Normally a total pressure of / bar is used, and it is also given as default in !". $n autoclave or vacuum furnace applications you may need to change the pressure. >ou can also increase pressure incrementally by giving a 4ressure R*nge, please remember to also define the !n1re*se 4ressure option for this selection, see .ig. < The total pressure 4D has effect on gas phase activity values *i in formula 7. The fugacity &i of gas species i may be calculated from this value with formula 0. *i > &i > 4D ' Bi *i ' 1 0*r @3A @.A

10. ,um0er o- Ste+s

$f you have defined increments 8steps9 for raw material species or specified a temperature or a pressure range then you should also give the ,um0er o- Ste+s required, see .ig. < The ma,imum number of steps in #ibbs solver is 4</ and for !olgasmi, the ma,imum available is </. :sually 4/ - </ steps give quite smooth curves in the equilibrium diagram. ( large number will only give more points to the picture and a longer calculation time. $f you have given an amount step for a raw material species, the calculations should be made using an increasing species amount. $f you have given a temperature or pressure range, then the calculations should be made by increasing the temperature or pressure. No simultaneous increments in composition, temperature and pressure are allowed. -lease do not forget to select the correct increase option, see .ig. <

11. Criss-Co00)e *n2 $iBing Entro+y o- A7ueous S+e1ies

!" will utili*e Criss-Co00)e eBtr*+o)*tion for the heat capacity of aqueous species at

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elevated temperatures 8K 4< "9 if the Criss-Co00)e option is selected, .ig. < Befer to the details in "hapter 4C.0. Note that3 A; $t is necessary to select the Mi,ing Entropy option for the #$%%! and !&'#(!M$) routines. $n this case, the activities of the results will be presented on the Baoultian scale which is based on mole fractions, see "hapter /7.7. $t is not recommended to select the Mi,ing Entropy option for the "hem!(#E or for the !&'#(!M$) if the conventional activity coefficients of aqueous species are to be given in the .("T&B subprogram.

#;

$f the "riss-"obble and Mi,ing Entropy options are not selected for the #$%%! or !&'#(!M$) programs, then the activity coefficients of aqueous species may be set to <<.<5?@)8 4&9, which will convert the Baoultian activity scale to the aqueous activity scale. This trick will also give the activities of the results on an aqueous scale, where the concentrations units are e,pressed as moles per liter of 4& 8mol@l9.

12. (!##S, SO"(AS$!C *n2 ChemSA(E &i)e &orm*t

;ith this option you can select the input file formats accepted by the #$%%!, !&'#(!M$)7 or "hem!(#E0 #ibbs energy minimi*ation routines, .ig. < $f you save the file in #$%%! format you can carry out the calculations in !" "hemistry with the #$%%!-solver by pressing (i00s. $f you have selected !&'#(!M$) format you can carry out the calculations with a modified !&'#(!M$)-solver by pressing S($, see .ig. < "hem!(#E is a separate software product, which is not included in the !" "hemistry package. Note3 the activity coefficients and formulae specifications, see .ig. 0 are valid only in the #$%%!-solver. Non-ideal mi,tures for !&'#(!M$) and "hem!(#E must be defined separately.

13. 4ure Su0st*n1es :E!n6*ri*nt +h*sesF;

The !&'#(!M$) and "hem!(#E solvers require information on the number of pure substances defined in the system. The internal name for pure substances in the programs is the invariant phase, referring to the fi,ed or invariant composition of a pure substance. (ll species in the last substance group can be set to be pure substances with the 4ure Su0st*n1es in the "*st 4h*se option, see .ig. <

1.. &i)e S*6e *n2 &i)e O+en

>ou must first save the input data for the calculations, see .igs. 0 and <. ;hen this is done you may activate the equilibrium program and carry out the calculations. ;ith &i)e?O+en you can read an old input file for editing. Note that from &i)e menu you can easily select file types for O+en and S*6e. Note also that the +.$#$, +.$!# and +.6(T file types do not save edited phase names and formatting settings. The Equilibrium module always saves automatically a +.#EM file which can be used to return these settings.

1/. EBit
$f you want to return to the previous menu press EBit. Bemember, however, to save your input data first G

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13.3 A7ueous E7ui)i0ri*

Equilibrium calculations of aqueous solutions can be made in a similar manner as presented previously for non-electrolyte solutions. owever, some points need special attention 8see also "hapter 4C.0 for information of aqueous species93 /. 4. (lways remember to add water to the aqueous phase. .or e,ample, <<.<5? mol 8H / kg9 is a good selection if the amount of ions is some 5.5/ - < moles. (dd some charged species 8electrons9 to the system, for e,ample, by 5.55/ mol & 8-a9 and the same amount of 8Ia9. %e sure to maintain the electronic neutrality of the system if you will carry out the calculations with the #ibbs solver. $f you are calculating, for e,ample, the dissolution of / mole of "a"& 7 into water and you have stoichiometric raw material amounts, please also add a small amount of &48g9 to the gas phase, for e,ample, /E-< moles. $f you have stoichiometric Na"l in the system please add a minor amount of "l 48g9 to the gas phase 8/E-< mol9. These tricks help the #$%%! and !&'#(!M$) solvers to find the equilibrium composition in cases of fully stoichiometric overall compositions. !" converts the entropy values of aqueous components from the molality scale to mole fraction scale if the $iBing Entro+y option is selected, .ig. 77. Therefore, the entropy values in the input files are not the same as in the !" database. $dentical results will be achieved if the Baoultian activity coefficients of the aqueous species are changed to <<.<5?@)8 4&9 which converts the Baoultian activity scale to the aqueous activity scale. .or some aqueous species only # values are available at 4< D". These can be saved in the database as values if ! H 5. Note, however, that these can only be used in the calculations at 4< D". >ou may check the equilibrium results by doing simple element balance checks or comparing the equilibrium constants. .or e,ample, you can calculate the equilibrium constant for reaction /C using the Beaction Equations option at 4< ", see .ig. /43 H2O > H:G*; G OH:-*; 5 > 1.020E-1. @/A

7.

0.

<.

1.

>ou may also calculate the same equilibrium constant from the equilibrium results of the #$%%! program using equation /5 in "hapter 8. Introduction. >ou can read the necessary molal concentrations, for e,ample, from the equilibrium results L !"7L"a"&7.&#$ file, see Table /. This calculation should give nearly the same results as the Beaction Equation option. M 8Ia9N + M& 8-a9N 5 > H M 4&N 0.27<E-/7 + 4./<?E-4 <<.01C@<<.<5? H 1.023E-1. @6A

- (!E /3 N48g9 4&8g9 &48g9 "&48g9

$N-:T (M&:NT EO:$' (M&:NT M&'E .B("T ("T$P$T> ("T$P$T> mol mol "&E..$"$ /.5555EI55 /.5555EI555 ?.1C7E-5/ /.55EI55 ?.1C7E-5/ 5.5555EI55 7.412CE-554 7./10E-54 /.55EI55 7./10E-54 /.5555E-5< /.5555E-55< ?.1C7E-51 /.55EI55 ?.1C7E-51 /.5555E-57 /.<?C1E-5/7 /.<0CE-/7 /.55EI55 /.<0CE-/7

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Total 3 - (!E 4 3 H2O "&78-4a9 "4&08-4a9 "a8I4a9 "a& 8Ia9 H:G*; "&48-a9 "&78-a9 &48-a9 OH:-*9 Total 3

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/.55/5EI55 /.5742EI555 /.555EI55 M&'E .B("T /./.69EG001 ?.??0E-5/ /.55EI55 ?.??0E-5/ 0.2<52E-552 C.<15E-5? /.55EI55 C.<15E-5? C.5<15E-51/ 5.555EI55 /.55EI55 5.555EI55 /.52?2E-554 /.?0<E-50 /.55EI55 /.?0<E-50 /.01<1E-5/5 4.10/E-/4 /.55EI55 4.10/E-/4 ..83.9E-013 C.<7/E-/< /.55EI55 C.<7/E-/< C./</0E-50C 5.555EI55 /.55EI55 5.555EI55 0.?52/E-55? C.C04E-// /.55EI55 C.C04E-// /./<0?E-545 4.5C/E-44 /.55EI55 4.5C/E-44 2.1/<3E-002 7.C?5E-50 /.55EI55 7.C?5E-50 <.<<5/EI55/ /.555EI55

<.<<55EI5/ 5.5555EI55 5.5555EI55 /.5555EI55 5.5555EI55 5.5555EI55 5.5555EI55 5.5555EI55 5.5555EI55 4.5555EI55 <.C<55EI5/

T*0)e 1. ( part of the equilibrium result file L !"<L#$%%!L"a"&7.&#$.

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13..

(ener*) Consi2er*tions
(lthough equilibrium calculations are easy to carry out with !" "hemistry, previous e,perience and knowledge of the fundamental principles of thermodynamics is also needed. &therwise, the probability of making serious errors in basic assumptions is high. There are several aspects, which should be taken into account, because these may have considerable effects on the results and can also save a great deal of work. .or e,ample3 /. %efore any calculations are made, the system components 8elements in !" "hemistry9 and substances must be carefully defined in order to build up all the species and substances as well as mi,ture phases which may be stable in the system. -hase diagrams and solubility data as well as other e,perimental observations are often useful when evaluating possible stable substances and phases. 6efining all the phases for the calculation, which may stabili*e in the system, is as important as the selection of system components. >ou may also select a large number of potential phases Qust to be sure of the equilibrium configuration, but it increases the calculation time and may also cause problems in finding the equilibrium. The definition of mi,tures is necessary because the behavior of a substance 8species9 in a mi,ture phase is different from that in the pure form. The microstructure or activity data available often determines the selection of species for each mi,ture. Many alternatives are available even for a single system, depending on the solution model used for correlating the thermochemical data. Note the same species may e,ist in several phases simultaneouslyA their chemical characters in such a case are essentially controlled by the mi,ture and not by the individual species. 0. $f you e,pect a substance to e,ist in the pure form or precipitate from a mi,ture as a pure substance, define such a species in the system also as a pure 8 invariant! phase. This is often a valid appro,imation although pure substances often contain some impurities in real processes. (ll species in the last phase can be set to be pure substances using the 4ure Su0st*n1es in the "*st 4h*se option, see .ig. < The raw materials must be given in their actual state 8s, l, g, a9 and temperature if the correct enthalpy and entropy values for equilibrium heat balance calculations are required. These do not affect the equilibrium compositions. #ibbs energy minimi*ation routines do not always find the equilibrium configuration. >ou may check the results by a known equilibrium coefficient or mass balance tests. !&'#(!M$) provides a note on error in such cases. $t is evident that results are in error if you get random scatter in the curves of the diagram, see .igs. //, /2 and /?. >ou can then try to change species and their amounts as described in "hapter /7.4 84. -hases, 0. (mount of !pecies9. !ometimes when calculating equilibria in completely 1on2ense2 systems it is also necessary to add small amounts of an inert gas as the gas phase, for e,ample, (r8g9 or N48g9. This makes calculations easier for the equilibrium programs. $t may also be necessary to avoid stoi1hiometri1 r*3 m*teri*) *tom r*tios by inserting an additional substance, which does not interfere with the e,isting equilibrium. .or e,ample, if you have given / mol Na and / mol "l as the raw

4.

7.

<.

1.

2.

C.

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materials and you have Na"l as the pure substance, all raw materials may fit into Na"l due its high stability. The routines meet difficulties in calculations, because the amounts of all the other phases and species, e,cept the stoichiometric one, go to *ero. >ou can avoid this situation by giving an additional /E-< mol "l 48g9 to the gas phase, see .ig. 01.
?.

Ouite often the most simple e,amples are the most difficult ones for the #ibbs energy minimi*ation routines due to matri, operations. owever, the new #$%%! 0.5 version usually finds the solution for the simple systems too, such as the two phase 4&8g9 - 4& -system between 5 - 455 D". !ometimes a substance is very stable thermodynamically, but its amount in e,periments remains quite low, obviously due to kinetic reasons. >ou may try to eliminate such a substance in the calculations in order to simu)*te the =ineti1 :r*te; +henomen*, which have been proven e,perimentally. $t is also important to note that different basic thermochemical data may cause differences to the calculation results. .or e,ample, use of !" Main6%0. !" or Main6%<. !" database files may lead to different results.

/5.

//.

The 2e-inition o- +h*ses *n2 their s+e1ies is the 1ru1i*) ste+ in the e7ui)i0rium 1*)1u)*tions *n2 it must 0e 2one 1*re-u))y 0y the user. The program is able to remove unstable phases and substances, but it can not invent those stable phases or species which have not been specified by the user. The definition of phases is often a problem, especially if working with an unknown system. :sually it is wise, as a first appro,imation, to insert all gas, liquid and aqueous species in their own mi,ture phases, as well as such substances which do not dissolve into them, for e,ample, carbon, metals, sulfides, o,ides, etc. in their own invariant phases 8one species per phase9, according to basic chemistry. $f working with a known system it is, of course, clear to select the same phase combinations and structural units for the system as found e,perimentally. These kinds of simplifications make the calculations much easier and faster. The user should give some amount for all the components 8elements9 which e,ist in the system for #ibbs solver. owever, !olgasmi, solver is also able to reduce the number of components 8elements9 automatically if a component is absent in the raw materials. $t is also important to understand that due to simplifications 8ideal solutions, pure phases, etc.9 the calculations do not always give the same amounts of species and substances as found e,perimentally. owever, the trends and tendencies of the calculations are usually correct. $n many cases, when developing chemical processes, a very precise description of the system is not necessary and the problems are often much simpler than, for e,ample, calculation of phase diagrams. .or e,ample, the user might only want to know at which temperature Na 4!&0 can be reduced by coal to Na4!, or how much o,ygen is needed to sulfati*e *inc sulfide, etc.3 The Na4!&0.$#$ e,ample in the L !"<L#$%%! directory shows the effect of temperature on Na4!&0 reduction with coalA the same e,ample can be seen also in the !" color brochure, page 7. The calculated compositions are not e,actly the same as found e,perimentally, but from these results we can easily see that at least ?55 " will be needed to reduce the Na4!&0 to Na4!, which has also been verified e,perimentally.

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The real Na-!-&-"-system is quite complicated. $n order to describe this system precisely from 5 to /555 ", solution models for each mi,ture phase would be needed to describe the activities of the species. =inetic models would also be necessary at least for low temperatures. To find the correct parameters from the literature for all these models might take several months. owever, with !" "hemistry the user can get preliminary results in Qust minutes. This information is often enough to design laboratory and industrial scale e,periments.

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13./

"imit*tions
The present version of the #$%%! program has no limitations as to numbers of substances and phases because it uses dynamic arrays. owever in practice, 7 - 4<5 species and / - < phases are suitable numbers to carry out the calculations within a reasonable time. (lthough the ma,imum number of rows in the spreadsheet editor used in .ig. 0 is /17C0, the practical ma,imum number of species is much smaller. The ma,imum number of equilibrium points, which can be drawn on the Equilibrium diagram, is 4</. owever, a much smaller number of equilibrium points usually give smooth curves to the diagram. The modified !&'#(!M$) provided in the !" package has the following limitations3 ma,imum number of components 45 ma,imum number of mi,tures 7/ ma,imum number of pure substances 8Einvariant phasesF9 75 ma,imum number of species in the mi,ture phases /<5 ma,imum number of "p ranges in input files 2 !#M neglect phase transitions R 4?C./< = The most important limitation of the old #$%%! 4.5 was that, in some cases, only one pure substance was allowed. &therwise the program provided unpredictable results. $f pure substances 8invariant phases9 do not, however, contain the same elements, several of them are usually accepted. >ou can avoid this limitation by putting a minor amount of dissolving species into such a pure substance and defining it as a solution phase. $n any case, the new #$%%! <.5 is much more reliable in these situations. (t least a tiny amount for all elements defined in the system must be given as input if you use the #$%%! routine. .or e,ample, if you have any .e-containing species in the system, you must also give some .e to the raw materials. !&'#(!M$) can handle systems with several pure substances usually without difficulty. $t also can calculate equilibria in systems smaller than originally defined in !". The !&'#(!M$) routine can therefore treat systems with less components than defined in its input file and thus a certain system component may be absent in the raw materials. The !&'#(!M$) provided with the !" package is a modified version of the original code from the :niversity of :meS, !weden. The modification allows the use of grams as input and in this case the result is given both in molar fractions and moles as well as in weight percentages and grams. The input file has therefore additional rows for each system components 8elements9. The locations and contents of these rows can be found in the input file listing in "hapter "#. $quilibrium samples. $f you have an aqueous phase with ionic species you should also be sure to maintain electric neutrality in the system, because the #$%%! solver treats electrons in the same way as elements. !&'#(!M$) can usually handle a small deviation from the electron neutrality.

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13.6

C*)1u)*tion Routines

13.6.1 (!##S E7ui)i0rium So)6er

&ig. 6. #$%%! equilibrium solver. Equilibrium calculations in the #$%%! routine are made using the #ibbs energy minimi*ation method. The #$%%! program finds the most stable phase combination and seeks the phase compositions where the #ibbs energy of the system reaches its minimum at a fi,ed mass balance 8a constraint minimi*ation problem9, constant pressure and temperature. This method has been described in detail elsewhere <. O+er*tion !nstru1tionsH /. 4. !elect +.$#$ file for calculations by pressing &i)e O+en, if the file is not already selected. se +re6ious resu)ts *s the initi*) guess option will slightly speed up calculations, but it is recommended to disable this option, because sometimes #$%%! does not give valid results with this option. The default setting is o--. &*st 1*)1u)*tions option will speed up the calculations - the default value is on. -ress C*)1u)*te and wait for the (ll "alculated message. -ress %r*3 %i*gr*m if you want the results in graphical form. -ress EBit to return to !".

7. 0. <. 1.

A26*n1e2 options belong to properties not supported yet, these may be available in the ne,t !" version as tested and supported form.

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13.6.2 SO"(AS$!C E7ui)i0rium So)6er

&ig. 8. Message bo, of the !&'#(!M$) program. The !&'#(!M$) equilibrium routine has been integrated in the !" "hemistry package in a different way to the #$%%! routine, because it is not a ;indows-based program. No own icon is provided, but the program has been connected with the !" interface through a direct data link using files. The !&'#(!M$) routine uses a similar #ibbs energy minimi*ation calculation method as the #$%%! program. (ll its mi,ture phases can be defined as non-ideal mi,tures in the .("T&B subroutine, but this option is not supported by !" interface. .or further reference, the original input guide and the thesis of #unnar Eriksson should be consulted1. The original !&'#(!M$) code has been modified to accept grams instead of moles as input amounts. The equilibrium composition in the gram mode is given both as a conventional table with moles and mole fractions and also as grams and weight percentages. The alterations in the input files due to this modification can be found in "hapter "#. $quilibrium samples. !&'#(!M$) can also be activated in the !" directory as an independent, stand-alone equilibrium solver. $n this case, its input file name created in !" must be defined as $N-:T. The equilibrium calculations results will be stored with the file name BE!:'T. Equilibria calculated as a function of temperature, pressure or other process variables can be later post-processed to graphics using the -$"-module by !" "hemistry. >ou may run !&'#(!M$) by pressing S($ when S($ -orm*t has been selected, see .ig. <, or by selecting So)g*smiB in the "alculate menu. ;ait for the calculations until %r*3 %i*gr*m is activated, see .ig. 2. (fter calculations you can draw a diagram from the results by pressing %r*3 %i*gr*m or return to Equilibrium ;indow by pressing EBit.

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13.8

%r*3ing E7ui)i0rium %i*gr*ms

&ig. 9. !electing the ,-a,is for an Equilibrium 6iagram.

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&ig. <. !electing the ,-a,is for an Equilibrium 6iagram.

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The -$" post-processor draws diagrams on the basis of the output files of the #$%%! program 8+.&#$-files9, as well as from the !&'#(!M$) 8+.&!#9 and "hem!(#E 8+.BE!9 result files. These diagrams can be drawn, for e,ample, as a function of a specified reactant amount or equilibrium temperature. !tart the -$" program by pressing %r*3 in .ig. 1 or 2 and follow these instructions3 /. 4. !elect the +.&#$ file for diagram by pressing &i)e O+en if not yet selected, see .ig. C. This file contains the results of the equilibrium program. !elect the species or temperature for the B-*Bis by clicking the desired item in the list bo, using the mouse. The program shows the recommended selection with an arrow, which is the variable used in the calculations, see .ig. C. -ress O5. !elect the species for the y-*Bis by keeping Ctr) 5ey down and clicking with the mouse. !ometimes it is convenient to select only those species, which contain the same element, for e,ample Ni, for one diagram. This can easily be done using the element list, see .ig. ?. $n standard cases you can get more illustrative diagrams by drawing all gaseous species on one diagram and all other species on another. The number of selected species is not limited. (ll species included in the calculation can be selected to the diagram. <. 1. -ress O5. Note3 >ou can return to !" by pressing C*n1e) or EBit.

7. 0.

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13.8.1 Se)e1ting %*t* Ty+e -or the C- *n2 I-*Bis

&ig. 10. !electing data type for the ,- and y-a,is. $n this menu you can select the data type for the diagram. :sually you may accept the default selections by pressing %i*gr*m, but the output may be modified. .or e,ample, you can draw the composition of a gas phase by clicking E7ui)i0rium Com+ositions option for the y-a,is instead of E7ui)i0rium Amount. (ll the species in one phase must be selected if composition of this phase will be drawn to the diagram. $f you are working with an aqueous system you will get a p This option will draw the results as a function of p . $f you only want the results in tabular format, press T*0)e. >ou can also sort the species in descending order, or leave them in the original order using Sorting Or2er o- S+e1ies option. This selection will determine the order of species in the results table. Temperature and amount units may be selected using the Tem+er*ture and Amount options. The number of species is not limited, and all the species included in the equilibrium calculations can be selected to the diagram. option for the ) - (,is.

%y pressing S+e1ies you will return to the previous window, see .ig. ?.

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13.8.2 Resu)t (r*+hi1s :E7ui)i0rium %i*gr*m;

&ig. 11. Equilibrium 6iagram. ;hen you press %i*gr*m in the (,is menu, .ig. /5, then the -$" post-processor module reads the equilibrium results from the file and draws the diagram using default scale, font, line width, etc. selections, see .ig. //. Note that the program inserts the species labels automatically above the ma,imum point of the curve using the same color for the curve and label. $f the line is not within the selected ,- and y-range or it is on the border then the program will not draw the line or the label. >ou can edit the diagram, .ig. //, by using several formatting options3 /. 6ouble click the ,- or y-scale numbers or select C-ABis or I-ABis from the &orm*t menu to change, for e,ample, the minimum and ma,imum values of the )- and >-a,is, see .ig. /4. $n some cases it is also advantageous to change the ya,is to logarithmic scale in order to display the large variations in amounts or concentrations. .rom the same window you can change the number format of ,- and y-a,is numbers as well as their font si*e, color, etc. ;hen the scales are &=, you can relocate any )*0e) 8species, ,- and y-a,is heading, etc.9 by mouse using the drag and drop method. .irst select the label, keep

4.

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the left mouse button down and drag the label to a new location, release the mouse button and the label will drop. 7. The )ine 3i2th of curves, species label font, etc. may be changed by double clicking the species labels or selecting the label with mouse and selecting &orm*t "*0e) from the menu. >ou cannot do this by double clicking the line. The label and curve editing window is shown in .ig. /7. Note that other line styles than solid are available only for line widths smaller than 5.7 mm.

&ig. 12. "hanging scales, scale number format and font settings.

&ig. 13. "hanging label and line specifications. 0. >ou can edit any label and heading on the screen by simply clicking the te,t in the

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label by mouse and starting to edit. .or e,ample you can change the label ENiF to a non-abbreviated form ENickelF. <. >ou can create new labels by selecting "*0e) from the !nsert menu. These new labels can be deleted using the 'abel selection in the 6elete menu. 6efault labels cannot be deleted, and the only possibility is to remove all te,t from them. The first time you use !" "hemistry it may be necessary to change the default fonts by selecting the %e-*u)t &ont from the &orm*t menu, because the available fonts vary from one computer to another. :sually Times New Boman, bold, si*e // font is a good selection. The selection will be automatically saved in the !".$N$file in your ;indows directory. ;hen you are satisfied with the diagram you can print it by pressing 4rint #JK. $f you have a color printer press 4rint Co). The print dialog gives several useful options for a hard copy, see .ig. /0.

1.

2.

&ig. 1.. !" print dialog for graphics. C. ?. $f you want to see the diagram in a tabular format or use the data of the diagram in other programs, such as M! E,cel, press T*0)e. >ou can copy the diagram to the "lipboard by pressing Co+y, and paste the diagram to other ;indows programs. The Co+y command uses the ;indows Metafile format, which enables you to resi*e the diagram in other ;indows applications in full resolution. ;ith S*6e you can save the diagram into a file using the ;indows Metafile format. -ress ABis to return to the previous (,is menu, .ig /5. -ress EBit to return the !pecies window, .ig. C, or to e,it the -$" program.

/5. //. /4.

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13.8.3 E7ui)i0rium %i*gr*m T*0)e

&ig. 1/. Equilibrium 6iagram Table. >ou can display the equilibrium results in a tabular format by pressing T*0)e the (,is menu, .ig. /5, or in the 6iagram window, .ig. //. The Table window has several E,cel type features in a similar way to the other spreadsheets in !". The most important features are3 /. ;ith Co+y A)) you can get the whole table into the "lipboard, and paste this table, for e,ample, to M! E,cel. >ou can also copy and paste smaller cell ranges using the Co+y and 4*ste selections in the E2it menu, see .ig. /<. >ou can also save the table using different formats, such as (!"$$ te,t and E,cel by selecting S*6e from the &i)e menu. The Table window has two sheets. The S+e1ies sheet contains the data of the diagramA the figures in this sheet can be edited, if you are not satisfied with the results. The &orm*t sheet contains the format specifications of the diagram. $t is not recommended to edit the .ormat sheet.

4. 7.

There are several formatting options in the .ormat menu, which can be used to create representative tables for printing. The table can be printed using the 4rint selection in the &i)e menu, .ig. /<. There are also available options !etup and -review for printing. The ABis button will open the (,is menu, .ig. /5, and %i*gr*m will draw the diagram, .ig. //.

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13.9

,on-i2e*) miBtureH (*As EB*m+)e 3ith A1ti6ity -ormu)*e

&ig. 16. $nput data of an activity formula e,ample.

'&#f8/9 H88/-)/9J49+8-4<<57.1-0.7/5?+TI</20.2+8/-0+)/99@8C.7/07/+T9 '&#f849 H88)/9J49+8-4<<57.1-0.7/5?+TI</20.2+87-0+)/99@8C.7/07/+T9

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&ig. 18. Besults as a function of arsenic amount. 6ifferent colors have been used for species, but these do not show up well in this %T; copy.

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13.<

C*CO3 EB*m+)e :A7ueous so)ution eBists;

&ig. 19. $nput data of e,ample "a"&7.$#$.

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&ig. 1<. Besults as a function of added "& 48g9. 6ifferent colors have been used for the species, but these do not show up well in this %T; copy.

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&ig. 20. Besults on logarithmic scale, the default e,ample is shown in .ig. /?.

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&ig. 21. Besults as a function of p , the default e,ample is shown in .ig. /?.

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13.10 L*+or 4ressures

!" Equilibrium module may be used to calculate vapor pressures for substances. UPapor-ressure-b!.igiU sample case is available in your L !"<L#ibbs- folder, see .ig. 44. $t is made for 40S 6*+or +ressure calculation. This case has been created with the same procedure as described in "hapter /7./. Note that3 /. 4. 7. Nearly all -b- and !-containing species have been selected to the chemical system. !ome nitrogen has been added to stabili*e the gas phase. !ome e,tra sulfur has been added to make the case easier to solve for #ibbs.e,e. :sually this trick is not needed but it may be used Qust to be safe. 0. "alculations are made from 5 to 4555 "D. <. !election of /55 bar total pressure makes possible calculation of vapor pressure up to /55 bar. Total pressure / bar would give vapor pressures up to / bar. 1. The equilibrium module calculates the equilibrium composition of the phases. $n this case, the equilibrium composition of the gas phase. 2. (ll gas species have been selected to the diagram in the species dialog, see .ig. ?. 6o not select -b! G C. UEquilibrium "ompositionU has been selected to >-a,is in the (,is dialog, see .ig. /5. ?. The calculation results are shown in .ig. 47. The default >-scale of the diagram is 5 - /55 mol-V, but is has been changed to 5 - 4 mol-V. /5. -b!8g9 composition at /775 "D is / mol-V. -b!8g9 partial pressure is then 5.5/, this means that -b!8g9 vapor pressure is 5.5/ + /55 bar H / bar, see .ig. 47. //. The total pressure of -b! is the sum of all the partial pressures of the gas species formed of -b!, ie. sum of3 -b!8g9, -b8g9, !48g9, -b4!48g9, -b48g9, etc. !" <.5 can not calculate the total vapor pressures automatically. owever, this may be carried out, for e,ample, in M! E,cel. -ress the Table button in the diagram menu 8see .ig. 479 to see the diagram data in tabular form and use the "opy - -aste procedure to transfer this data to M! E,cel. >ou may also save this table in E,cel format. $n E,cel you may calculate the sum of all the partial pressures, see the Papor-ressure-b!.)'! e,ample in your L !"<L#ibbs-folder. !" database reference =nacke ?/ gives /7/0 "D for -b! boiling point and Wanaf ?C gives /745 - /700 "D depending on the measurement or calculation method. These values are in reasonable agreement with the calculated -b! boiling point of /742 "D in Papor-ressure-b!.)'!. The gas phase above -b! contains mainly -b!8g9. owever, in many cases the gas above pure substances may be composed of many different species. $n these cases it is important to note that the total vapor pressure is the sum of the partial pressures of all the different gas species formed of the evaporating susbstance 8not N48g99.

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&ig. 22. "hemical system specification for -b! vapor pressure calculations.

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&ig. 23. Besults of -b! vapor pressure calculations.