The Predom module. Predom calculates and plots isothermal 1-, 2- and 3-metal predominance area diagrams. Predom accesses only compound databases.

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1 Section 1 Section 2 The module clcultes nd plots isotherml 1-, 2- nd 3-metl predominnce re digrms. ccesses only compound dtbses. Tble of Contents Tble of Contents Opening the module Section 3 Stoichiometric rections nd innce Are digrms Section 4 Specifying clssicl predominnce re digrm: Fe-S 2 (g)-o 2 (g) for T=1000 K Section 5 Grphicl output using the Figure module Section 6 Numericl results from predomince re clcultion Section 7 Using overlys (Cu-SO 2 -O 2 t different tempertures) Section 8 One-metl predominnce digrm with four elements: Fe-S-O-Cl Section 9 Vrious predominnce digrm with four elements Section 10 Bsic computtionl procedure in the construction of predominnce digrm 1

2 The module Click on in the min FctSge window. 2

3 Using the Rection progrm to identify the most probble rection Question: A gs mixture, 80% SO % O 2 t 1 tm, is equilibrted with Fe t 1000 K. The possible products re FeO, Fe 2 O 3, Fe 3 O 4, FeS, FeS 2, FeSO 4 nd Fe 2 (SO 4 ) 3. Which product is the most the stble? Answer: Although some SO 3 (g) forms, for simplicity we will ssume tht SO 2 nd O 2 re t equilibrium: i.e., P SO2 = 0.8 tm nd P O2 = 0.2 tm. In such cse, it cn be shown tht the equilibrium prtil pressure of sulfur is P S2 = tm. Although the vlue is smll, this chemicl potentil is useful for thermodynmic clcultions. From the Rection progrm, the following vlues of DG re clculted: (note: 1 mol Fe(s) rectnt in ll cses) 1 : Fe(s) O 2 (0.2 tm) = FeO DG= kj 2 : Fe(s) O 2 (0.2 tm) = 0.5 Fe 2 O 3 DG= kj 3 : Fe(s) + (2/3) O 2 (0.2 tm) = (1/3) Fe 3 O 4 DG= kj 4 : Fe(s) S 2 (10-29 tm) = FeS DG= kj 5 : Fe(s) + S 2 (10-29 tm) = FeS 2 DG= kj 6 : Fe(s) + 2 O 2 (0.2 tm) + S 2 (10-29 tm) = FeSO 4 DG= kj 7 : Fe(s) + 3 O 2 (0.2 tm) S 2 (10-29 tm) = 0.5 Fe 2 (SO 4 ) 3 DG= kj 3.1

4 Rection progrm: 7 possible isotherml isobric rections nd 7 vlues of DG Rection 1 Rection 2 Rection 3 3.2

5 methodology Rection 4 Rection 5 Rection 6 Rection 7 Fe 2 (SO 4 ) 3 is the stble product since DG is the most negtive. For exmple, FeSO 4 could not be the most stble since combining rections 6 nd 7, we hve: FeSO 4 + O 2 (0.2 tm) S 2 (10-29 tm) = 0.5 Fe 2 (SO 4 ) 3 DG = ( J) - ( J) kj This methodology is used by the progrm to locte the domins of stbility of ech phse s function of gs potentil. 3.3

6 Specifying clssicl predominnce re digrm: Fe-S 2 (g)-o 2 (g) t 1000 K 1. Specify the metllic nd the non-metllic elements. 2. Press Next >> to ctivte the clcultion. 3. Select the vribles: Prmeters: Pressure Constnts Axes Lbels nd Disply Species: gs, liquids nd solids Clculte: digrm All exmples shown here re stored in FctSge - click on: File > Directories > Slide Show Exmples 4. Press Clculte >> 4.1

7 Figure disply of the predominnce re digrm of Fe-S 2 (g)-o 2 (g) t 1000 K The rrow is pointing to the Fe 2 (SO 4 ) 3 domin where: x = log 10 P O2 = P O2 0.2 tm y = log 10 P S2 = P S tm Figure cretes predominnce digrm tht cn be edited, mnipulted nd stored in vriety of wys. 5.1

8 Revised digrm displyed in Figure for Fe-SO 2 (g)-o 2 (g) t 1000 K Chnging the X nd Y xes. And Clculte >> revised digrm. Note: The Fe-S 2 (g)-o 2 (g) digrm (previous pge) nd the Fe-SO 2 (g)-o 2 (g) digrm (here) re topologiclly equivlent, i.e. the sme combintion of species coexists t the invrint points. 5.2 Intersection t: x = log 10 P O2 = P O2 0.2 tm y = log 10 P SO2 = P SO2 0.8 tm

9 Invrint points of Fe-SO 2 (g)-o 2 (g) t 1000 K. Phse Rule: F = C - P + 2 F : degrees of freedom C : number of components P : number of phses Univrint line (/): FeS/Fe 3 O 4 /gs. From the phse rule, F = 2. Hence, t 1000 K only one of SO 2 or O 2 cn be fixed. At the rrow, C = 3 (Fe,S,O) nd P = 4 (3 solids nd 1 gs); hence F = 1. At 1000 K, the system is invrint. (Note tht the totl pressure is not specified.) 6.1

10 Detiled point clcultion t P SO2 =0.8 tm nd P O2 =0.2 tm for Fe-SO 2 (g)-o 2 (g) t 1000K 18 gs species, 6 liquid species nd 21 solids species (totl: 46 species) in the FACT compound dtbse contining Fe, S nd/or O. Click on Dt Serch to include or exclude dtbse in the serch. Here, only the FACT compound dtbse is included. Point clcultion dt entry: P SO2 = 0.8 tm, P O2 = 0.2 tm 6.2

11 Detiled point clcultion t P SO2 =0.8 tm nd P O2 =0.2 tm for Fe-SO 2 (g)-o 2 (g) t 1000K Fe 2 (SO 4 ) 3 (s) is the stble species: unit ctivity, C p vlues not extrpolted A/P/M: Activity/Prtil pressure/mollity «T» indictes extrpolted dt Minly SO 2 (0.8 tm), O 2 (0.2 tm) nd SO 3 (0.65 tm, see code 39). 6.3

12 digrm for Cu-SO 2 (g)-o 2 (g) t 1000 K 1. Specify the metllic elements (Cu) nd the nonmetllic elements (S nd O) in the Elements frme. 2. Press Next >> to serch through the selected Compound dtbse(s) (here, FACT ) nd ctivte the clcultion. 3. Specifying n isobr, P = 0.01 tm, t T = 1000 K. 4. Select digrm 5. Press Clculte>> 6. In Figure, edit the digrm nd sve it. 7.1

13 Figure: Superimposed digrms for Cu-SO 2 (g)-o 2 (g) t 1000, 1100 nd 1200 K 7. Repet steps 3 (but uncheck the isobr checkbox), 5 nd 6 for T=1100 K nd 1200 K 8. Use the superimpose figure function in the Figure progrm to edit this predominnce re digrm t 1000 K, 1100 K nd 1200 K. 7.2

14 One-metl predominnce digrm with four elements: Fe-S-O-Cl Specifying the isotherml predominnce re digrm for: Fe-S 2 (g)-o 2 (g)- S 2 Cl 2 (g) t 1000 K nd P S2 Cl 2 = 0.1 tm 1. Enter the elements. This is one-metl Fe system with S, O nd Cl non-metllic elements. 2. Press Next >>. 3. Note: you must enter 2 constnts. T = 1000 K Z = P S2 Cl 2 = 10-1 tm 4. Select wht you wish to clculte nd press Clculte>>. 8.1

15 Invrint points tble nd predominnce digrm for Fe-S 2 (g)-o 2 (g)-s 2 Cl 2 (g) Appliction: Chlorintion of FeS At 1000 K nd P S2 Cl 2 = 0.1 tm 8.2

16 Two-metl predominnce digrm with four elements: Fe-Cr-C-O Fe-rich side of the iron-chronium 2-metl predominnce re digrm Appliction: Pssivity of Fe-Cr lloys 9.1

17 Two-metl predominnce digrm with four elements: Fe-Cr-C-O Cr-rich side of the iron-chronium 2-metl predominnce re digrm Appliction: Pssivity of Fe-Cr lloys 9.2

18 One-metl predominnce digrm with four elements: Fe-Cr-C-O Fe-Cr-C-O with Fe s the 1-metl element, Cr(s) = 1 Appliction: Pssivity of Fe-Cr lloys 9.3

19 One-metl predominnce digrm with four elements: Cr-Fe-C-O Cr-Fe-C-O with Cr s the 1-metl element, Fe(s) = 1 Appliction: Pssivity of Fe-Cr lloys 9.4

20 Chromium-Crbon-Oxygen innce Digrm Appliction: Decrburiztion of Chromium Use of the surimpose function of Figure (see Figure help, section 14) mkes it esy to compre the Cr-Fe-C-O digrm (previous slide) with this Cr-C-O digrm to show the role of Fe in the formtion of FeCr 2 O 4 9.5

21 Bsic computtionl procedure in the construction of predominnce digrm The following five slides give detiled explntion on the stoichiometric reltionships of the rections tht govern the phse boundries in predominnce re digrm. In principle there is no limittion in this pproch s to the number of system components. However, there is one mjor restriction in the entire pproch of using stoichiometric rections: it is not suited for the tretment of systems with solution phses. 10.0

22 Bsic computtionl procedure in the construction of predominnce digrm Isotherml predominnce digrm estblishes t ech log P S2 nd log P O2 prticulr compound MS O b with the lowest DG of formtion (bsed on 1 mole of M). M S O M S O b b log P S2 M 2 S t MSO 4 D G D G R T M S O b b o M S O ln M S O b b 2 2 P P M S O 2 2 M 2 O p log P O2 At point p, DG (for formtion) of M 2 O is most negtive (per mole of M). At point t, DG (for formtion) of M 2 O, M 2 S nd MSO 4 re eqully negtive. Notes: It is not necessry to identify possible equilibri mong phses by this method. The user my set MS O b or P MS O b to other thn 1 for some species. Useful especilly when MS O b is gseous species. 10.1

23 Compounds s species represented on xes Use of species other thn elements for prtil pressure ssocited with the xes. Select S-O species with different rtios of S/O for ech xis. For exmple SO 2 nd SO 3 : S O O S O S O 2S O S At ny coordinte, p, on the digrm, the prtil pressure or chemicl potentil of elementl species O 2 or S 2 my be determined. The bsic lgorithm on the previous pge cn now be pplied: log P SO3 M 2 S t M 2 O p MSO 4 log P SO2 Notes: Species on xes must not contin the bse element M Combintion of species t triple point is independent of choice of S/O species for xes 10.2

24 Point clcultion At ny prticulr point such s p in known domin ctivity of M cn be determined. M S O M S O b b log P S2 M 2 S Insert M from bove into eqution below t M 2 O MSO 4 p DG R T ln M S O b b 2 2 P P M S O 2 2 log P O2 To find the ctivity of ech MS O b : M S O M S O b b Activities nd prtil pressures of bse-element-contining species t ny point in the digrm. The ctivity of the prticulr species MS O b identifying tht domin is the set vlue (usully 1). 10.3

25 More thn 3 Elements Involved in Digrm 2 wys to proceed: ) Fix dditionl chemicl potentils (eg. P Cl2 ) Formulte formtion rections to construct the predominnce re digrm shown in 15 s follows: M S b O c C l M S O C l b c One cn specify P Cl2 for entire digrm, or s in 15, specify prtil pressure or ctivity of ny Cl-S-O species (eg. S 2 Cl 2 ) S ( g ) C l ( g ) S C l ( g ) By this equilibrium, one cn find Cl 2 for ny S 2 prtil pressure 10.4

26 More thn 3 Elements Involved in Digrm b) Introduce n dditionl bse element (eg. N) 1 r M rn S O g M N S O h M N S O b w x c d y z e f Bse elements (specify rnge in which r my be found) Combintion of two M nd N contining compounds which stisfy the mss blnces with non negtive vlues for g nd h for specified vlue of r Note: In the cse of two bse element digrm ech domin is doubly lbelled. In the specil cse of there being no compounds contining both M nd N, the two bse element digrm my be regrded simply s the superimposition of the two one bse element digrms for M nd N. 10.5

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