Section 4 Thermodynamics Hendrick €. Van Ness, DiEnga, Howard P lerman Departnent of Chemical Eng teering, Reuselaer PolyecinicIntvute; Feline, American lstule of Chemica Engineers Member, American Chena! Socety Michael M. Abbott, Ph.D., Hosur! P Ine Department of Chemical Euginoering RensclacrFelyteclnic Intute: Member, American Tastitate of Chee Engineers intropucTION VARIABLES, DEFINITIONS, AND RELATIONSHIPS “aay al Ep at Pcs ad. Tater Ene and ato at Foetal a syst a abe Campion Prasad Mae per GibaDiaem Equation Fatal Malar Ca sy The eal Gus Sate an te Canpresity aor Tea pets " SOLUTION THERMODYNAMICS eal Gas Mists Fay and Fay Coven Fetal Nee Propet Relat ‘Teele Sate Fotis lan ‘mur of Pudaneat ries Hela Propet Changer of Mg Ter fan LS EVALUATION OF PROPERTIES esd Poesy Fagan epllNap Pie Tto Liq Phase Properties. Prism BT ving Atemitve Propet Formations nal Equations Generale Creation for ‘Bens Westin Eaton of Stat specu th Es iy Ears FquWeRIUM Wi ct ies " Fariet tie eat eect cohen fas ieee ee a he THERMODYNAMIC ANALYSIS OF PROCESSES Caton fel Work Li Wonk Ath Sy Sti Shai Pesce "Bungle La sku (Copyright © 1999 by The MeGaw-Hill Companies, In. All rights reserved. Use of this reduc is subje othe terms fits license aprement Clik ete View4-2. THERMODYNAMICS Nomenclature and Units Syl ited ta cola pti spec Symbol Deiat Stari ‘ite symbat Deiat Storit te ey Be a TY 2 OKESESESIS nines Bins er Neeyig) orton) “siete 1 ohekompentie A Baia en cova 1 Gage enplatn x t ety pac 1 SREPSSAESSonat — Patorpy Brat nl c ASE SESS, cot? ction cs in koa espn 4 Nel me se D—hinal ceiinn, tin ein Melee ntmass volume Sin fe at ‘hoy espn ein wala clicen, ws tos wo Work ie rept . MW, Shh ordopsese fe co SSkceie ews he Me Simereiaeacs fe Be prone pars Ti MEESSiein genta” incase Biren Sina ees hws wr he Sa tet cemnal——emtont sien clit 9 Niprtnesl tion Dinesh ‘cient ose Diners: Diners capt casent Yk) Baba R) See ft es isa Meerpety cant fax) Bitbpsiny J] Be Rites 1 be a fo ExieTeemtces |B a Beceemiia" fh ay of pes in kre ro F Denes ga pia Solar wats Gibbs Yio ag Bra mel Bena arid tence ge oe © Bee eta eee en ie Sart Kuban Kea 9, insects |) Ses © Ej comtustfoe——iersolest Dimenanle: | © Dette wae or aol heat reir eget con © Dots ae rte tate 4 teayrent we et ft Demteravabe bi afer beat sence Si BERS 7 Biber aed wake stay tee hp foe _ Demerara res Sate propery ef —Nw0__ te at Nol wins aes a seca oe : : HH, ral molar property af Rextioneondinte far tak Tomo au Piper te of ing >i 1 A mal uy Stat piper hae y eat aC Bink Dieses naga be hn F Natit ‘Bin Binns Mt & Me enthalpies fa th nt mt Numberaf moles {), Stacitomteneaumberol Dimensociess Dimensionless 5 SERS pens » Secdione mene See peau be i 2 sly smn’ et? Cee ee He f ASSIA demarcate fe Steer perpesue Et gs 1; fora heay poe, tending concentrate nthe Tigi ps, Ke "Empirical correlations for K-values fund inthe older Meratre have itl eon to thermodynamics, Tel proper vation comes dhe from Ba 4-303) When Raoul aw applies, this becomes K, = RV In gener, values are fonction of. composton, aa vapor compos ons mang thet diet and acewateSorelaon np. Phone onelations that do exist are approximate and severely lied spplcatzon The DePretter conclaton, for example, ges Keaes felight ijdsocarbons (Chem. Enge Prog. Sup Sex Na. 748, pp ‘sTiss3), Equation-of State Approach Although the ganna appraach to VEE i in pncple general appliable to sytems comprised of ‘ber spice, ptce le Towed we rman hte pre Ses are no more that afew bars, Moreover i most ststey Tor comeiion of constant temperature data Atenperture dependence forthe parmetr in expresons for G's acid ony ore loca conpostion equations sn # rat best only approximate ‘ATgeneralfy applicable allenalive to the” gamuna/pi approach sell uben both the lg] atl vapor phates dete bythe ‘Sine equation af sate. The delising sation for the fpacty coe det, 70), maybe applied teach pase: Liquide f= 0P Vapor i= deme iquation (4-276) now becomes sdl=uae 2X) 4-308) “Ths intadccs the compositions and yo the equa equa tions, but ncter i exp, sce th are Funcom, nt nly of Tand ®t of companion. Ts Ey. (4308) represents N comple ‘ekionhipsconnecing thes, dh they, stable fr compte Soliton, Gren an approprite eqation of tate, one or spate of Ep: (618) thromght CISD provkesforexpesion ofthe a ne thon fF, andeompostion can ofeach enn Eg (221) and (4-999) the equate tate approach was sone ite o tems eating monet sud welled des ‘hot fram ideal slon behavior heh pase; or expt, to Sates containing Iydocazons and erogent ks, However, the iMtolacion by Wang tnd Sander (AICHE J. 38, pp 671-680 [igi2)) ofa new cs of ming rls for cubic equations af stat has realy expanded the wef appeation to VLE. ‘The Stwne/edlieh/Kwong TSRK) and the FengBabinsn (PR) xqstions of state, oth xpesse by Ex. (1290) and (42 oper specifically for VLE eats. The fuga implica thee equations are given by By (4-22) When combined ith the theoretically ase Wongandler ising ules for prune Terr and these equations prone the means fav acre corel Hon and prediction of VLE data "Theft ofthe Wng/Sandler mixing rls relates the ference sn nate quanties and aR tothe corresponding ilerences en tied by subse) for the pe specie b-LeS Sabon (ass) mee whey Een tsJacty am ary nection parantershy ae eermined foreach py pl p24) lem expertnentl data, Note thal ls = hy aid he = 2. icdlne sqm thet hand se of 0°30) resets second veal celicent ws predict by Eq (4280) the hss for Eq, (Se ln, ich eget depen tfc mateo il etn mele acon ‘ta et Wont mages ao ab (ason) (4305) 2 by an appropriate coeation for the ce tt erg fd Petree ale a we tre compostion, purl of whether the mitre hui orsapor ‘The comtantet spetiicto te equation of state The theoretical as foreseen can a oa in he erature (Wong an Sand, ‘op. Ind Eng Chere es 3, yp. 209-2039 (1553) Enh ct tnd Bag Cen fs, 34 yp 4-383 [1095)) nto fn ly (95) hy Eg (97) piesa expression for Ly Sane, r, (4-300) ra Mistre parameter then falls fon Eq, (407) a=bRN1-D) sto) iquations (4-233) and (4.234) may now be apple for the evaluation of bared paraneters aad by sn) and ase) For pure species Eg (4232) reduc to haga 2-1 te Rb , aA, Veto. 4.549) ee" V+eh, “hs eqn ay be pled spr tthe ig plead teva pn llth reopen or apo Wesel 4 kato gut pl pares a et prmteF a a G20) that ms hse vais st eli pi restr of preps Resorts fr) at tw Eg (4230) ae sige tno ae othe espera ch tla aelaine or Basa uncon pera ae a teeny pre sen Tha wen a fora ptr ee pect abba at th equate oy Feel vn Th rere oe Ey (403 fr ESS pre combing Re tn apeonein aed wh Ey ngi=tng? (Copyright © 1999 by The MeGaw-Hill Companies, In. All rights reserved. Use of this roduc is subject othe terms of i licese sprint. Click ete o view.“Theremin expression may be sled fro: (est) yr ebyvi ob) Pe a = PV 0 rach pe {ire Sings aie tha aio an eae Pech inet whan tna ae xa the ape Date correlation for Tye) “ “Th nay nro parameters ae vale eon liq phase G* correlations for Binary systema "The moet satisfactory proce Je istosplat tinted the elton Denyeen sttbap colon ands inketbang ply cet Heurangement ofthe ogni orn tls Inge=tny+ng (ws15) ers n° comes om the G crelaton nn gen by Ey S13] wen forthe hl pss Equation (4313 spies aa tr wich nn gd a Ey (4-80) tae elon inlet ork For binay stem Simp of cies» and Es (4233), and (1315) may be writen for specie pat fnite dation resin eto then eae oil wes of Vand VY come vege sing. ste Bt A ee Wah, 1 (I) 0b gain witha, (2. Itt usin 1 Fy 411 wate rape pani an nay psergwes ip ee ks sais) z iar Equation (316) and (4-18) rset equa, inte by Ea {naa sepa by hy ite a 5 Sotto re es Je gBg =A ota os) 2, 2aeh, (esi9) where Ing comes fom Eq. (4818) All ales in Eq, (4819) ae foe the liquid pave a P= he analogous equation fork, the ite lution ve of fy at 90 writen (4320) here Mya gen by an etn SMiscupt reversed all al he vantage ofthis proce tht ancy are ound diet ‘ie antag of hs procedure shat andy ae od dey fiom the pure species prmeters a, a, band by To addition, the id as a at nd npr {EES he py nary ote oloponent ofthe cor exper Soo wed tr slogous to Eq, (4317) but ith te in Eq (480) ae fe the gid pase EQUILIBRIUM, 1-29 A second advantage i tha the proce tion of each species yes two valves of tdependentFinlion ean be ge pronog falysatsbcioge pst ite lee thy 1) “het ales anaes terra i a ‘Moe composion depen Neve he quai ep ‘ce ob wR on cmon ally 9) Say pressed Sac he tty tru sed war cot Sion cya vale preted ly ele eatin ste sr ‘fhat'apenete ir wage togenet the tompastn ‘Topenent ky lead to beter ess than does we fa constant ve ic june tonsa the SRK an FY etna vent fhe litigate mm Tapa a hares foots ‘i Ontined below ave the steps requite for of a VLE eaeultion of ssponphase competion and prestre, gen the quad phase ona ‘oe and lemperature. A chawe west be nade of an equation of He: Only the SomevfedilyKwong and Peng Robison ations, te represented by Ege (4-290) aad (4231), are considered bere ‘Thea to equations Gaualy gh commptable vel A chose tat aso be uade ofa two-puraneterconelatng eresion to repetent the lgud-pave composition dependence of GF lor each py binary. ‘he Wilon, NRT. (wih fsed), and UNIQUAC equate of general appealaly; for binary ayitems, the Marples snd van Lear uations nay also be used. The equation seloetel depends on ev ‘Bee of ity suitability to the particular sytem lead. Resse ‘timate ofthe prarters tae equations be town a the tenpertare of etre These parheters are deel elitd toi ‘tection vals ofthe actly cofficints fr exc py binary. Taput information icles he known vale of ad fe a the Squsion ofatite and expression parsneter Estas ae ako needed of P an (the quantities fo be evaluated, and these ‘exe sone prelninaty calculations: For th chosen equation of state (wih appropriate values of €, gan), al vals of and prelaninry values ofa for ea species ram dhe norination flowing E.-250) 2 I the vapor presure Bi for species § at temperate T is Anown, determi shew valu fora by ig (4311) and (4250), ‘3 Evaluate Ky atk, by Eas. (4319) and (1-390) for each poy biany 1.” Ath pressure P isto be determined, an extinate i 1 andor Vick a al suleitaa Bie such of the parespeces vapor pressures, cach weighed by is open i aa oat THe vajorphate compotion sls to be deterined, and it too, sequel nite culations. Assn oth thei ae ‘Sporphates to eal solitons, Egy (08) and (1304) combine to ae Evaluation of the pur-species values and by’ Ba. (4313) then provides values fry, Since thas ae at enna 6 stan foun, {ie shoul be novilized to eld an inal vapoe pss compostion ‘stimates far Pan yh an ierative frocedre cane it sta At the kncwn liuidphase comperition, eshte D by Eq (a-Sshb and aly Bs (dbo) and (510, anf a a) by Ege (431) and 813) (Copyright © 1999 by The MeGaw-Hill Companies, In. All rights reserved. Use of this roduc is subject othe terms of i licese sprint. Click ete o view.4-30 THERMODYNAMICS 2 Evalate fl). The iste volume V i dterined from the fsqation of sates Py, (1-231, applied othe Lid pase a the gave ‘snnpostion, Tad Repeat ihe tion, ths evaluating | 1 [300 wt receding tems forthe eqprphase compas “The values fy, 4 belated are norman by division by 5.4 5." Recalculate the ad cota this tera procedre wate converges to Bxed ale for 7, y. This sum i appropriate to the {ress Pfr which the cleo have been nade, Us the Erin he preemie teadjated andthe Herston process repeated Systematic adjestment of pressce P contin wall prs adap copention of ar th een ae Fer the given toperatare and iqusdhave composbn a predicted bythe aqation of sate “ ° ° {Awa sore of Kd hase exces property data for aay sytens ot enperatures net 20°C and some higher anable othe ‘ature, Eflecine nse ofthese data toeatend G™ correlations tiger teaperatunes f extialto the procedure considered here. The hey reliins see By (1118), (constant 2.x) at ans) (ir).- want ctar 4322) 4323) Tnadation, we may write ack Integration fon Ts to yields Lr Combining this equation with Eqs (422) and (1-525) ead to f(r). (aa 3) cr wie ot LL “This general equation makos use of excess Cbe-onergy data at teenporn exerecnhahy(hes-of-og dao yl encess Haein data at Ts Bsa ofthe integral! rules norma tion wi respect tothe temperate dependenes of CF. Hecate of the relative panty of exces heat-eapcly data the next resonable sumption tht tis quantity costa, pendent of To this tet the integral exo andthe her Tan Tart the les the infeace of thi assmption. When information salable with respec to CF and exes enthalpy data ae avalible at only a-snge fetipeatire ihe excess heat copay mst be assed ee, In Cs Casco the Bist to terms the igh side of Ea (034) ate ‘tained an nore apy Becomes inprcke aT increases. ‘ue primary interest in Ey (4324) sts apheaton fo binary 9 temsat fate dition af ne of the conti species. Portis pr pose we dvd Eq, (4324) bythe product sas For CF independent SPF an ns walt =0), ten comes ° &(e Jeeta). C= cf, 2 (tye wF (21) 5] lon) 4 As shown by Saith, Van Ness andl Abbut (Uatroduction 40 Engieoring Thermodynamics, 5th el, Chap. 11, Me York Se . (claw ‘The preceding etation may therefore be weten (i “(Slade ‘The methanel(Vacetonel2) system serves a a speciic ample in ‘conjunction wah the Peng/Robinaon equation of site. Ata ase len pesature T, of 333.15 K (30°C), bth VEE data (Van Ness al Att Iie DATA'Ser, Ser A Sel Duta Mixtures, L978 p. 1 (1078) sul ‘exces nay data (Mor tal, J Chem. Ena, Bote, 20, pp 03- 405 (1975) are aval From the former, ny i=06281 and (nye, = 06557 sud ro theater (Seat 8 (Sane raked sa the eameten forte gc Ae “This information allows prediction of VLE at 923.15 K a at the ligher temperatures, 3725, 307-7, and 432.6 K. for which rneasitel ‘VEE values are pen by Wika et a (lua Phase Eur, 28, p. 15-37 (1986) Vales of la yr aad hence of ee Mangus parameters a the higher temperatures are gven by Eq, (4325) with €7 0. The Ppurespecies vapor presere tall ctes ‘are dhe ensured valies Foported th the datasets, Ress of ese caleulation are dgpliyed ie 1 tee he pene edn vais th tal ph apprenel ss reported i the papers cited ite ens at 38315 K (S81 67 1) sow both dhe sual of the Margules equation for corzlaton of data for thi sytenn ad the cap Inliy of thequatinn-o state meth! to prince the dts Hess far the thre higher tempersties indica he quality of predictions Insed oaly on vaporpestare data forthe pure cies snd nature data 32315 KSI 67 R). Estrapalations based onthe sae dato ‘sf higheriernperatures ean be expected to become progressively ket accurate. When Fa. (1.935) can o longer be expected 4 pre Teter rents are obtained forhigher temperatures ‘hon fad do no change Fther at strhigher temperatures Talay te cours te fa pation to superna temperatures ‘Onl the Wikom, RTL. an UNTQUAC eats are suited tothe treatment of mutconporent ystems For auch ate, the parte tervare determined for pais f species exaly as for binary ystems, ‘Examples treating the caulatin af VLE are given i Sth Va [Nes atl Abbot latveduction to Chenical Buginering There namie, Se Chap. 12, MeGra-Hl, New York 1096, Ml, New by we Inye and LIQUID/LIQUID AND VAPOR/UIQUID/LIQUID EQUILIBRIA iqution (1-273) the bass for bth haus igud euibia (LE) an sporfiguiduideulbeia (VILE) Tha, for LEE wth super Seip cand B denoting the tow phases, Ey. (4275) is itten (Copyright © 1999 by The MeGaw-Hill Companies, In. All rights reserved. Use of this roduc is uct othe terms of is license sprint Click hte viewEQUILIBRIUM, {TABLE 4-1. VLE Results for Methonol(1)/Acetone(2) Tea B & Dae | Ree | fra y) (436) Su MA (ess) lining gars in ve of acti coelicents ges San ol of hae tc el they on toque io the change stytedyh G=12...N) (4-327) | ina ainge quantity fy called the rection coordinate fr reaction For molt LE api he lt of pao th Cee et et ce Beer i scrum aeadgeec! able i bah Chobe Ss aneaeareeS cor USAGUAC tn stan ene Ee it rae UM ed Acted tec eee ee ees: tet tad ae Che Bonn De Bea pe St Sh ‘ vial i Epic S-So Pa ae ‘4p. 151-163 [1980 Data LLE are collected a three-part set Sn ete te tee tare basen Calne Bech fam Stag 1180 Farndale Eg (427) es ft: 2.2.) (4-328) ere anf dng het la ase Wh ety eh chs a rt re ce Sporn cq tquons scl VLE ae =v capable of epresentiog quid ‘aporphase equation of dale cat oa) shen Asfor LE an epson or ‘se ting pared as or VE Brconputing the Sanne CHEMICALREACTION STOICHIOMETRY (Consider a phase in which a chen rection occurs accondig tothe equation Its where the Iv are stsichionetric coffe ad the A, stand for ‘chet fornlis, The v theresa called stoichiometric Der and ascated wi ther sign convention suc thatthe ale i pte fora produc! an negative for aveactat: More general fora stem eoatining N chenical species any or all of which ean pavtcate tar chowiel ventions, the session can be represented Pye equations: = Sy, Sills + wa (4330) shen sexe ram te “rr rod pees A species des no partite in ration then, =0. ‘Fre schionetse sumo provide selon athong the angen ia mole numbers of chemical Species which occur as the result of hme reaction. Thus for reaction (Copyright© 1999 by The MeGra-Hil thereby iby N . (a) Since the total change in mole auber An is just dhe sun af dhe changes Bn eesuling roa the vos reactions Lane D was the inital umber of males of pecs isp ane the coment is tte tha = foreach eect in thi state, then Swe Eaton (430 hake een of mate aa fo ceditsnit ntce’ Note sentar ae ee ‘leprae cheap eae tone Sp Me pmigoniaicha cient Coe eer edt la eu Hat the chanel mr of ah co Hla Ny (4a) 2X) (ba) CCHEMICALREACTION EQUILIBRIA ‘The general erterion of chemical rection equi is gen by Ea. (4270), Forasysteminwhich jst singe reaction occur Ba (134) Becomes Substitution fr dain Bg, (1-274 ead to Dvm=o (4335) Generalization ofthis raul to nip reactions prodices Svmeo Gy ” (4336) standard Property Changes of Resction A seudard property lunge foe the estion 4ASb89lL emt ‘defined asthe property change that cers when a tole of Aa 2 ‘oles of in thet Manor ates of fnperatare rect to fort ‘oles of Zand m ces of Min ei standard states alu a tempera tre A siandard tate of species st el or ipothieal sas. pte spciesattemperotare Tada standard-date presare Pe, The Rui property Change of reaclion jt ghen the sol AN? ad Atsgeneralnaematicaldfinition aye Swat (4337) Compan lc. Allright eserved. Use of this reduc is subje othe terms fits license aprement Clik ete View4-32 THERMODYNAMICS For species presenta gsi the actual eactive system, the standard fate the fuse ideal Gur at presse Forge ad sold, is “ally the tate of pe el yd or soil at PE The starlandstate prestre P= fived At LOO KPa Note tht the standard sates aay wep Feseat diferent physical states for illeent species any oral the ‘ies maybe gases, uid slid, "The most commonly wed standard property changes of action age Yvar=S wae 4.338) ane Swe 4330) ace Se 4340) “The standard Cheney change fron AG? i wei thee Calation of equilbeian compositions. The staxdard heat of reaction ‘tries th eatin the heat eects fem esto, tl th danar! het capasy change of reason tise fore olin Ai and AG® wih E Numeric aus AD and AC) ar Ee el olan da C4 er frog enpiaal expresdons ore T dependence ofthe Coe eg . * ‘equllbram Constants For praca aplication, a, (36) smate etre The nal dope elite of the an ver Wages pation (for specs inital eae sy trated fron Ey (7 forspeceat athe egal ste, hing w=Ge+Arln 43a) were, by dein, 4, fan scald an at. Substation of ‘Ris eqution iat (S41) upon reagent, Diy Seven enrS wa Swen Tas “The ight shana side ofthis equation ica fanetion of temperate only fa gen eeuctions ad gh standard states. Convenionce suggests silage toa Re whence 430) 4349) ‘ may age ren ee (455) Ath cess "Kaan ‘Sa tong oe NO "he acts n Ey, 4-42) pve the connection beten the ‘Ties wich aa resealable The sand ‘at aa he lig temperate: Ana th sta SE SOP gc Bap es "bef sites yt sl hap he ‘The apn of E42) ros emp nodctn of compen sso. Ph ugha fost he scarp tig the aly son a fife =yoe However the standard state fr gases the deal ya tate atthe tan ddabtate pressure, for which [>= > Therefore an(2) tuar(p) TT ee ee a ‘orelaton or from an equation of state “ acon hen the phase canbe stun an del ga. ka Kal vent cain Tom (Z)=% up nthe general case the evaluation of the seguir ay teratve roves: Ai itil step t to atthe 6, equal to tity and fo save the problem by By. 4:345). This provides ct of, values, allowing ‘valtaton of the by oe sample, Bg. (1-198) (200) oe (4231 Equation (434) cxt then be sored Gor new st oy values, and the Jppeen confines to convergence Forkgie eats Eq (940) odie yt ofthe at coelient = ff weve x5 he hgua-phave mole ction Tatty thea ue Kall usa) a) Bat fan represet fii of pre gud al tempera but a prunes Pad Ps eget Eacept ne cel elo, pro Siac le ett ont properties of an the ato fo ‘Men taken ss nt. venti wt aceptle this rato evened By the eration wet fo er i the to i ae ‘ys and Eq, (432), Tees" 436) Here the ifielty isto determine the whic depend om the x This profits has sot heen soled forthe feneal ease. Too courses ae ‘pen the fis experitent he second, assumption of solution de fy the latter ee, = 1, awl a, (4346) ethers to Te cay uae) the law of mass action, The sgiicant feature of Bg. (4-945) ad (64) the gat epee acon ‘equim, thatthe temperatures pressure? and compotion ‘pendent terms are distin! and separate Kay) Example 2: Single-Reaction Equilibrium situa 10 tmp pt re sider the ele tthe ed steam itn 3 CO, 1m HL a 2 0. ores tokcf pesca inna stn a he ao aan, Fert ection Fa (4-390 eons om, ¥8 Whee (Copyright © 1999 by The MeGaw-Hill Companies, In. All rights reserved. Use of this roduc is subject othe terms of i licese sprint. Click ete o view.A 100K, 42°=-258 J pr mak faction when by Fg (34) ‘egies tpi, exes) kop. hence “ha firth eptisim mstre ‘The effect of temperature on the equi constant fllows from Bg. (1106) alagrie _-any “. (esis) a ar “The total derivative i aproprate here acme property changes of Teacton are functions of tesipeature ony a conation with Ea, 1343) ths ges dink ane ar Rr For an endotherne reaction AH? is positive; for an exter eae tion tis negative The temperature dependence of Allp given by da ar Integration of Ea, (4350) fron reference temperate T (usally 20818} totempeftare T goes ° (4s) oe (4350) Ci op R ere for sly sabe as be Ibert fro ay (4-50) =AG* _ ants sc RD RE where A/T gen by Ea, (435. inthe one exensve Compt of at, vals of AG” and AH fot ovation ean aren a de Cage ftp ter anit at the erence tempers of 298.15 (Se ear 10 Theodanle Tee Hiyrceront al HC Her unkante Talar-Sonbdartone see pubeatons of the ‘Thetis Rearch Cento Toss 4 M Unhersy yt College Sta Tex. "The NBS Tee of Chel Then Properties) Pptical and Chemical Reference Data Uy sap 2 {HORS Wide dase bing eto eit ar ca {se ie reve y Red Prasat ad Pali The Properties of Gis nd Pay, sec, Chap. Metra tl, New Nek 1st Foran etingion pensar bated on elo drach so Co ‘etn and Gal, Fad Phase Eri, 103, pp 11-23 [5 Seraio see 3) ‘Gompies Chemical Reaction Rquibria When the compa tion cellars tree deterined hy number of ai tn tn aston edo en sts fe ner computer soliton) ia based on minisization of the total Gib energy Cia second ith Eq (971). The treatoent ere snppresied. A convenient ar ar T nk: EQUILIBRIUM, linnte to gascphase reactions for whic he problem i to al the libtool en and an rage et H. Formulate the costaning mater dunce equations, based com conservation ofthe oa nbs of sons of cack element fa ya tem comprised of w elements. Let subst tently a prtedar Stow an fine As the ttl aor tome ass the kt tlemeat inthe feed Further tay be the numberof toms ofthe Rh slement present in each moleule of chemi species The mate falc frlement kis then Sonam, o Sneu Ay (4353) a Senmed aver k,thee equation give Ya (Snena 2. Rowsna function Fy alin ofthis su to reo (Yan-a) Frnction Feil with G, ae the sation tm mr, However, the partial deine of Fan with apt edi fret becaae fon Facts the conus of he sei tein The ms dette of su yale of bth Fan Gis foun when the pati ih espe! ton ae set qual 60 240 (aa =o The it en on th gt the di fhe ip ne Daee0 228) ease) However, the chemical penta ge by (1-240) for ga pase ‘actions and standard sates a the pure sea gues at P, this equ seri P 6G i abit set equa to zero forall ements in thee standard sates, then for compounds C= AGP. the stanlard Cibbs-ene chi lomo pcs Ian, the cy ian ‘ated in aver ofthe gue coeicent by Ey U0), =p With these substitutions, the epion fri becomes 1 waagy tari 2h ro Combination with Bi. (4-354) goes species isan clement, AGP oro. There ae N equlirivm equa ts [Eg [4-355] ne for each chemical species al here rete auateril balance eations (Ea, [1353], one fr each element a total of N+ w equations The eaktowns i Hse equations are the Coote that yy maf which there ate Nand the Ryo which tere ae wea total of N+ unknowns, Ths, the nuinber of equ mts aufficent forthe determination af al uaauowns. uation (4.355) is devi om the presumption Hat the & are to pose sap tel then 8 oy te pte sn ideal solution each becontes dca at east he extinated. For fal gates, each ra finetion ofthe y, the qaities being ele lated Ts an Weraive procedae sidicated tiated with cach (Copyright © 1999 by The MeGaw-Hill Companies, In. All rights reserved. Use of this roduc is subject othe terms of i licese sprint. Click ete o view.4-34 THERMODYNAMICS set equa to wily Solution ofthe equations then prides tet lg, For bw pressures or high temperatures this re tdeqnate. Where &tsnosatsfacloy at tation of ate withthe n'y, ghera new and wore noaty cect st of for eae (4355) Then anew ato yt detennined. The proces repeated 60 fsmverpence All elculaion are well ited to corner solution, "n dis procedure, the quesion of whal cherie ructions are ‘volved never enters direct nt any of the equations. However the thoi of ust of pecies entirely euvalent to the choice af asl of independent reactions amoug the species, In any event, 8 act of species or an equivalent ae of independent acto mus vans be sumed, and dierent sumptions produce diferent results Example 2: Minimization of Gibb Energy Cals the snare tak ant taeda ice sie ‘poses Ci 110,00. CO, avd athe nl uncle Preset 2 il Cian do HO. also SC 10D Ka '=19520 Jnl 192420 fl 7 =-200240 fl |8G}_.=-295700 jn “The weird values of Ac are determine rom the inital numbers of soles, and the ves af ag come drely fou the chee Boras tthe specs These ae shown ia the acoonpenyig abl ith Ta At ar and 1,000 K the assumption of del gies susie, ad the Stave allunty. Since P (455) ites ASE in MS Kano ar Sq, RP ‘THERMODYNAMIC AN. ea ives proces nb sbjoct to henna ay 6 The ula he ity ey an cn to dua how enon louis apportioned sang the spe af joven. The tcatsahere i tt to stacey df frocess bean of te predominance in dra techaoly. ‘CALCULATION OF IDEAL WORK In any stead state, sea Alow process requiring work, a minimum tsnount ma be expended to ring about a pec change of tte in the flowing fit Tt a proses prefucing wor: maxima an wane cf chang ite thao ‘se, the lining value obtains when the specie chang os cecemplshed completely reversal. The ut pheations of ts we “Te proces i internally revere within the coat vlue 2 Heal transfer external fo the control vltne reversible “The second ie means that let exchange between syatern ands soundiog tas ccural the tepersinecf the sumaundigs preetned to eonathte a beat resect a constant a wnfon empertre (Copyright© 1999 by The MeGra-Hil this product is subject othe terns of “The five equations fr the five species then become: ens I te 0 RE RT hho. ptt, hn, Bo Son" ar Rr “o Jay co. dono Ms “The theee material-balanee equations (Ea, [4353 ar: +R Hen He dae + Btn + Bay. = 0: go he +o =9 Simultancouscompatr solution of these eight equations ith T= S08 anol and " ponies the ellowing resus, =n en=00196 #207635 ar ono ore 055 yoos=00 mwcoe e101 * ar Sas 1000 “The values of ART ae of sigitcance, but are inl o ake Ae emt complete IALYSIS OF PROCESSES ‘Te This my require Carnot engines or het pune tera t the y- ‘ei that provide forthe revere ane of felon the empertre ‘ofthe Bowing id to tat ofthe surroundings. Since Carma egies ul eat pumps are cyl they udengy no net change sate "The entropy change ofthe surrunings, found by integration of By (U3) AS, = QaTy whence r= Tess (4.356) Sie hat taser eet te sands wh eet tae tema pe aa ogni sg 420 Me in eee eee ee ee Pa ncRantany changes ‘of system ad suerouuing be equal bt of epposte sign AS, = "AS. hertone Dewrtien Qe Teas) Interns of ates Eiguation (456) Ais becomes = MAIS as) ste of heat raf with respect to the system as eae of May of id Tn ation, & denotes the difference between ext and entrance streams anf nicates hat he ter apis to all owing streams Companies, nc. Alleights eserved. Use of i ieee agosment, Click here Yo view“The energy balance for a steals steadyAlow proces eng fromthe lw of thermody " * sectoesb]-o- eit eth of ning id hc of Rang hd Jeaton of fig id above dtu evel pel accleraon galy fatten (455) where Ww Ehninating Q ia Bq, (4355) by By. (4357) ges lee derse Want The preceding equations then expresed Ww A work nasa ges each ofthe individual work terms. the right as action of W. +2 Wie (4375) (Copyright © 1999 by The MeGaw-Hill Companies, In. All rights reserved. Use of this roduc is uct othe terms of is license sprint Click hte view4-36 THERMODYNAMICS TABLE 4-2. States and Values of Properties forthe Process of Fig. 4-12" owe Fe TK Conpeston Tift] Som aan Sipe For a work-podueing process, W, and Wang ae negative, aed IW > AV. Bauation (4374 nis ate bet writen ial =WiL+ SW A work analss here expresses cal ofthe india work terms on the ight aya rston of Ma work aalss cannot he arid ont in the ene where a proces i 3 inefficient tha Waa eglive ind +378) ‘ating that the procee should prince work, but Ws postive in A ntowork oF fsting Hae the ‘ep generatio Example 4: Lo dept a Fg 418 Table ate et (lel pants ft dag et tt te and ot he sng TJ as in Fak eres” wrk si aly pale Work Analy sad 31 nl Oy By x ate ‘whence falanee on the trogen, 696 ma of sitrgen product 1964 mol of exygen of ldeal Work F cuges in kinetic and potential gece ate meget (80 plea Fr the ae ‘Ts, by Eq (4360), rode ay A153 Jk Calculation of Actual Work of Compression For sismpliciy, the work of compression ealelaed by the equation for an ea gt Insatheestag weiprocting sackine with complete itercoking tl wid bentrope compreaion in each stage The work so calculated is tase to represent 9 percent ofthe actual work. The follwing ound in ny nub of testbocks on therwednane wa gt (| sir lle, numberof tages, here taken a3 aloof heat paces, hee taken at 1A ial abot temperate, 200 K ‘ven presure rat, ives gas conta, 4 Ylbk) ‘The efficeney factor of 08 is lal incied in the equation. Sub sittin ofthe remaining vakes ges SLL Fg gpmos_s fois] “The heat transfered to the surroundings daring compression as a result of itereoling ad aflercolng to 0) Ks own ron the ist be the (Copyright © 1999 by The MeGaw-Hill Compan this reduc is subj othe terms fits cen trot as of Noa Sli, US Dr Ms Tah Pap) Fo. 412 Digan of spl Linde te fora separation (0 = nat) -W, = (12,046 12.407) — 15,71 =-15502) Calculation of Lant Work Eqqution (4367) may be applied to ‘och of the major unite of the proves, For the conpresorcodes, Wie = (00) [(82.9)(2)— (1473590) (15532) Loy For the exchanges, Wa = (200 ((18.48)(0.1964) + (114.300.8696) + (52.08), 20.68) (3.60. 1968)-(9.98)1)] 7 =2053.4) ally; forte rectifier, Wa. = (075.8990. 8696) + (5169)0.1960) —(52.09N1)] = 147 ory Mork Analy Sth ras ees or, E75) sppedh ax eaten the falling abe, and areon the bass of Tol renter wie Compresontodee saz] ott Slinger Som Ba es iano} ist Tino) woo ‘The thermodynamic efeoncy of this proces a gven by Eq, (4-963) isonly 29 poroent Siguicat inelfidencies rede with eat of the itary waits ofthe process, lc. 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