REVIEW OF ENGINEERING THERMODYNAMICS
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1 Deprtment f Mnng nd Mterls Engneerng REVIEW OF ENINEERIN HERMODYNMICS Ferrus pplctns Engneerng hermdynmcs 1
2 bbs energy = H S; : bbs Energy, H: Enthlpy, S: Entrpy 1. Fr pure elements r pure cmpunds (l, O 2, l 2 O 3, etc. H S H H K C d S S 298 p 298 K 298 enthlpy f cmpund t 298 K wth reference t pure stble elementl speces t 298 K, 1 tm (, unknwn H 0 K K K C p d : C p = + b + c -2 + d + s knwn (mesurble stndrd entrpy t 298 K ( S 0 0 K Stndrd stte fr H : ΔH 0 298K fr ll stble elements t 1tm nd 298K. Fe(bcc, Fe(fcc, Fe(l, H 2 O(l, H 2 O(g, H 2 (g, O 2 (g, O(g, CO, FeO, C(s, CO 2, CO,. * In FctSge cmpund dtbses, ΔH, S 298K 298,, C K p re stred bslute bbs Energy f cmpunds reltve t elementl speces. Ferrus pplctns Engneerng hermdynmcs 2
3 bbs energy 2. Chemcl rectn between pure cmpunds (N slutns n + mb = n B m rxn ( n m n B m B H rxn S rxn In mny thermdynmcs bks, H, S re gven. rxn rxn hese vlues re nt bslute vlues, but dependent n ech chemcl rectn. In FctSge, therefre, bslute bbs energy f ech speces (reltve t elementl speces s stred. hen, the rectn bbs energy fr ny rectn cn be utmtclly clculted frm the bbs energy f ech speces. Ferrus pplctns Engneerng hermdynmcs 3
4 bbs energy 3. Chemcl rectn nvlvng gs n + mo 2 (g = n O 2m ( n m rx n O O n 2m 2 R P fr del gs speces mr PO 2 t Equlbrum rxn 0 R ( 1 m P O 2 Ferrus pplctns Engneerng hermdynmcs 4
5 bbs energy 3. Chemcl rectn nvlvng gs (cntnued t equlbrum In generl, fr + bb(g = cc + dd(g R ( P P d D b B R K K: Equlbrum cnstnt FctSge Rectn mdule cn gve ths knd f nswer quckly. Rectn mdule s nly fr stchmetrc speces (N slutns re nvlved n the Rectn mdule clcultn Ferrus pplctns Engneerng hermdynmcs 5
6 bbs energy 4. Chemcl rectn nvlvng sld r lqud slutns R ( ( n s ( pure : ctvty Defntn f ctvty chnge f bbs energy f n slutn by nterctng wth surrundng speces Pure s p s Mxture p P P x Pure Lqud n slutn s the ctvty f speces n slutn: hgher ctvty mens hgher chnce f evprtng. Ferrus pplctns Engneerng hermdynmcs 6
7 ctvty bbs energy 4. Chemcl rectn nvlvng sld r lqud slutns 1 ( p / p (+ devtn x (+ devtn: repulsn between nd ther speces : mre ctve chemcl rectn f x del (- devtn 0 x 1 (- devtn: ttrctn between nd ther speces : less ctve chemcl rectn f x In generl, fr + bb(g = cc + dd(g t Equlbrum R rxn ( c C prducts P P d D b B rectnts * FctSge slutn dtbses cntn mdel prmeters t clculte Ferrus pplctns Engneerng hermdynmcs 7
8 bbs energy mnmztn In mst thermdynmcs texts, ne clcultes equlbrum cndtns rxn 0 R In rel clcultns, we wnt t knw the drectn f rectn nd the fnl prducts K eq m + nb Inputs (ntl cndtn mny pssble utputs fnl, P fnl 2 B (m-2 (n-1b B 2 (m-1 (n-2b 2 B (m-3 B 2 (n-3b (m-x (n-yb (x-ybs Fnl equlbrum stte? Ferrus pplctns Engneerng hermdynmcs 8
9 bbs energy mnmztn (cntnued We hve t fnd ut whch phse ssemblge s mst stble t gven f nd P f fr gven mss bce (nputs. bbs energy mnmztn rutne. (ChemSge, Slgs-mx, etc. he mst stble phse ssemblge s the ne wth the lwest bbs energy. In FctSge Input munts Select ll pssble prduct phses (sld cmpunds, sld slutns, lqud slutns, gses Set fnl nd P fnl v Clcultn (bbs energy mnmztn rutne v Equlbrum phse ssemblge clculted Ferrus pplctns Engneerng hermdynmcs 9
10 Δ (kj / mle f O 2 Elghm dgrms ( - Cllectn f Δ vlues fr xdtn rectns m + O 2 = m O 2 (reference: 1 ml f O 2 - Only cnsder pure cmpunds. (N slutns re cnsdered. (B + O 2 = O 2 R ( ( O 2 ( p O 2, ( 0 : Equlbru m R p O 2 ( R p O 2 (K Ferrus pplctns Engneerng hermdynmcs 10
11 Slutn thermdynmcs -B slutn, (Sld r lqud slutn x g s lu t n ( m l r g g R g : prtl mlr bbs energy f n slutn g slutn g B g g R g Δ g mx g B B R g X B : Chemcl ptentl f ( x g x g R ( x x B B B B Ferrus pplctns Engneerng hermdynmcs 11
12 1. Idel slutn: Slutn thermdynmcs -B slutn, (Sld r lqud slutn s (m l r ( x g x g R ( x x B B B B 1, B 1 s (m l r ( x g x g R ( x x x x x B B B B 2. Regulr slutn: R B x 2 B Ω: Regulr slutn prmeter s (m l r ( x g x g R ( x x x x x x B B B B B B Ferrus pplctns Engneerng hermdynmcs 12
13 Slutn thermdynmcs -B slutn, (Sld r lqud slutn s (m l r ( x g x g R ( x x B B B B 3. enerl slutn: f ( x, x e x s (m l r ( x g x g R ( x x x x B B B B Plynml mdel : e x j j x x R ( X X, j1 B B B B * FctSge supprts mny cmplex slutn mdels. Slutn dtbses (Fxd, FSlt,... cntn ptmzed mdel prmeters reprducng bbs energes f slutns. Ferrus pplctns Engneerng hermdynmcs 13
14 bbs Energy nd Phse Dgrms phse dgrm shws grphclly the mnmum bbs energy ssemblges f system. 1 Prter, D.., nd Esterg, K.E., Phse rnsfrmtn n Metls nd llys, 2 nd Ed. CHMN & HLL (1992 Ferrus pplctns Engneerng hermdynmcs 14
15 bbs Energy nd Phse Dgrm phse dgrm shws grphclly the mnmum bbs energy ssemblges f system. 2 Prter, D.., nd Esterg, K.E., Phse rnsfrmtn n Metls nd llys, 2 nd Ed. CHMN & HLL (1992 Ferrus pplctns Engneerng hermdynmcs 15
16 bbs Energy nd Phse Dgrm phse dgrm shws grphclly the mnmum bbs energy ssemblges f system. 3 Prter, D.., nd Esterg, K.E., Phse rnsfrmtn n Metls nd llys, 2 nd Ed. CHMN & HLL (1992 Ferrus pplctns Engneerng hermdynmcs 16
17 bbs Energy nd Phse Dgrm phse dgrm shws grphclly the mnmum bbs energy ssemblges f system. 4 Prter, D.., nd Esterg, K.E., Phse rnsfrmtn n Metls nd llys, 2 nd Ed. CHMN & HLL (1992 Ferrus pplctns Engneerng hermdynmcs 17
18 hermdynmc Dtbse Develpment: FctSge Pure cmpunds H S H H 298 K S C 298 K p d C p S K d S K 298 K K K C p d Clrmetry emf Knudsen cell Vpr pressure Slutn ex, j 1 j B x x j B emf (ctvty Knudsen cell (ctvty Vpr pressure (ctvty Slutn clrmetry (enthlpy Phse dgrms Ferrus pplctns Engneerng hermdynmcs 18
19 Dlute Slutns 1 (+ devtn del (- devtn slpe 0 x 1 x : Henry s lw Cnstnt slpe Henrn ctvty ceffcent * In FctSge, yu cnnt see the Henrn ctvty ceffcent (n generl, ctvty ceffcent vlue drectly, but f yu clculte the ctvty n the Equlb mdule n the very dlute cmpstn regn, yu cn clculte the Henrn ctvty ceffcent usng ths reltnshp. Ferrus pplctns Engneerng hermdynmcs 19
20 Dlute Slutn Mst refnng prcesses nvlve mpurty elements (dlute slutes Henrn ctvty s mprtnt Fr exmple, l-dexdtn prcess n steelmkng, 2 l 3O l O ( s 2 3 l R ( ( 2 l l 2 O 3 ( 3 O R ( s the Henrn ctvty ceffcent f l n pure lqud Fe l ( X 2 l l 2 O 3 ( O X 3 O Nw, f we hve ther elements n Fe such s O, Mn, C, etc. there s nterctn between l nd these elements. Chnge f frm : nterctn ceffcents l l l l l l x l O l x O C l x C... * FctSge Fmsc-FeLQ dtbse cntns these Henrn ctvty ceffcents nd nterctn prmeters fr lqud steel. Ferrus pplctns Engneerng hermdynmcs 20
21 g ( wt.% g ( H bbs Energy Chnge f Stndrd Stte Chnge f stndrd stte s lke temperture scles, K, C (tht s, just the zer pnt f s chnged. g ( R g ( g R ( R R R ( H ( wt % ( R ( wt.% R R ( R ( wt.% ( H R ( H Rultn stndrd stte Henrn stndrd stte ( R H R ( H f x f x j x j k x k... Rultn stndrd stte 1 wt.% stndrd stte ( R wt % R M 100 M Bulk = f [ w t% ] (w t.% lg f e [ wt % ] e j [ wt % j ] e k [ wt % k ]... FctSge desn t prvde stndrd stte cnversns. Users must d the cnversns usng the frmule bve. Ferrus pplctns Engneerng hermdynmcs 21
22 bbs energy f rectn rectn ( n g ( prducts n g rectnts g g R ctvty f Stndrd stte shuld be checked crefully When the rectnts r prducts re - Pure speces (nt n slutn: ctvty = 1 - Speces n slutn: requres n ctvty vlue (cn be clculted frm FctSge N drect wy t d ths type f clcultn n FctSge. In FctSge, rectn (between pure speces cn be clculted frm the Rectn mdule, nd the ctvty f ech slutn speces n the rectnts r prducts cn be clculted usng the Equlb mdule. hen, usng the bve frmul, we cn clculte rectn Ferrus pplctns Engneerng hermdynmcs 22
23 Het (enthlpy Het evlutn clcultn H = H fnl - H ntl = (L H fnl C P (l H m (meltng (s C P (s H ntl prcess Ferrus pplctns Engneerng hermdynmcs 23
24 Het (enthlpy Het evlutn clcultn (s H f = het f frmtn (r rectn frm (s + B(s t B(s (typclly negtve vlue B(s H f Negtve H mens genertn f het B(s prcess Ferrus pplctns Engneerng hermdynmcs 24
25 Het (enthlpy Het evlutn clcultn (L B(L B(s (s B(s prcess -B slutn (lqud In FctSge, the H ntl nd H fnl re drectly clculted becuse the H f ech phse s clculted frm the thermdynmc equtns (dtbse f ech sld r lqud phse. It s mprtnt t select prper ntl nd fnl mterls sttes nd tempertures Ferrus pplctns Engneerng hermdynmcs 25
26 Het evlutn clcultn Mny ndustrl prcesses requre mss nd het bce clcultns. FctSge cn prvde very esy wy t d such clcultns. Fr exmple, the fllwng clcultn wuld tke severl hurs r dys (r mre mnully, but t tkes less thn 1 mnute wth the FctSge Equlb mdule. CCO 3 (25 C Fe-Mn-S melt (1600 C Fe-C ngt (500 C Het lss Fnl prducts temperture pressure Ferrus pplctns Engneerng hermdynmcs 26
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