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  • Distillation (Van Winkle)

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    Distillation (Van Winkle)

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    Distillation (Van Winkle)

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    © All Rights Reserved
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    2K visualizações341 páginas

    Distillation (Van Winkle)

    Enviado por

    Elizabeth Olivares
    Distillation (Van Winkle)

    Direitos autorais:

    © All Rights Reserved
    Baixe no formato PDF ou leia online no Scribd
    Sinalizar o conteúdo como inadequado
    de 341
    McGraw-Hill Chemical Engineering Series Haivortal Advisory Bowed James 1. Cubery,Asocate Profesor of Chemical Eisering, ‘nvry af Note Dame Max. Pots, Dear of Engineering, Unset of Colrado Willan R. Schomaier, Asciare Profesor of Chemial Enger Jammer Wei, Rewarch Asoite, Sacony Mobi Ol! Company ‘et agictings Bower out MvEss—Marentay, Ha an Mar anor CLAN SSO DIMISON Mona or Pees gine Catan Cons” High Preamre ‘minut Kote~Bove Syms a Cl ‘a ts and Scale hn Chee Eager Kare ‘Cowan, Kowsr sy Dons ann Etoase se Wessel Sara eire Sidi Brn ad at Panfrs Kove oo Rasen Pun, usc, to Law” Init Savona: Ne [herockimcol Enger, MeADsaes at Promina, MeCanr 2 So Jet Opes of Chena Ewing Mactan, Suwon, xD Reso fay (en) Chara Bes Rand ay En) -Cheml aes Hentot:" Peis lomo Chem Eger Pots Pant Des oh, comms: for Chel Ener, Rv nso Senecho—Fhe Propet of Cae on Ligniownson snp Gat Elen of Facto Dinan Sec Th ronal Nh i Eagring® "Seba so Matas Pricer of Pgh JEP terran Earcion? ise Ceti Pacers Inn, ‘Shen, B.D Desi of Eatin Suge Process: Shar. 3. M-Chemiel Pa ermine’: Taeviss- ipa simcnan, Teast” Messier Operation Teng ogte, maar x0, Dron Chm gma Pit Denne Nock dp Stn or Eggers: Watst Reach Rn for (Chemical agnor Wainen, Liv, MEADaWS ND CiLttcano—Prin pes of {Geman "Wnt un Kann” Sich or Chem Bac ‘eso an Rus of Choma! Egecng Themes bbb 20E Vera aa Se h das DISTILLATION Matthew Van Winkle Professor of Chemical Engineering ‘The tnieoatey of Fores 22690 UNIVERSIDAD NACIONAL mse oY ah McGraw-Hill Book Company St. Louis San Francisco Toronto London Sydney mr O-aicmoh. epeare te eye New York bCEF peeae sys 294303 Poetuce This bok wat writen to se 4 lew atonal Sin Theater hs ee mae tot he st ater such man a theuny" at wc at “Row ety cline." In ado, Sg ‘ethos common uae gen log mith workings tts ofa foc acotr deuge ct be ademas reese ‘Stauton wh ter books and sore mera Resonmende dig ‘ethos foreach he poi yor pe ceigate en, companied by the recommeded arab reed na lage accmutaton of Meru on he igea. | Obvosy. ine honk ipo oinnpert ven ira of Scnon stlotneiiorntonsvalabe, Therefor testinal ered tm wth he auth ath we hat Bs ad ote Bos he Stthors indus comsting an eases exper, ith gas Bh the underaading 0 te sist andthe prolcon of werahe 0d Tie hye th te ook wi er the ot Eetatns nd wy ater pa aio michineconpatuton toss for facial Saaon ig, ‘Ao, ene prog for sah altos soe vey Epo tote om the jot ae alse ceere Aen io thot who wh ‘oultoemchie computa, salable rte on he et Bs Nek "he stor hes express pectin Lo omnes wha ae in the fl of natal tation gn an engin forth geo, to prot gadtate sents who fv phen contac sug {ing he proton of th sujet ar, ad 10 end dy Shintheacadeic ll who ve genase ns work Parr HAPTER 1 ‘CHAPTER 2 CHAPIER 3 a a Comtentn Preface i Induction arora (QUID EQUILIBRIA. 6 PHASE EQUILIBRIA~BINARY SYSTEMS. 7 Rules and Laws Describing Ear 7 Vapor gid Equi Biry Sytem 16 Preiion of Binay Vaportigud Equilibrium Data rom ‘urecomponent Properties "30 meng Tso iy Vapor grim Nomencatre 42 Referens 33 MULTICOMPONENT VAPOR:LIQUID FQUILIORIA 46 Ideal Maticomponent Sytems 46 Weal Ternary Sime 2 ‘Novis Vapor LiguidEuiiia—Mullcomponent Apron: Reationship Between Li and oul nd Bonham VaporLiguid Equiliam Relations 117 Problems. 12) Nomenclature, 123, Reference 12 ‘COMPLEX SYSTEM VAPOR-LIQUID EQUILIBRIA 127 “Teboting paint Cuve 127 ASTM or Enlerspe Disilation 129 aii fa Vpoiatin FY) Caren 190 Determination of EFY Curves Seperatmorperi 36 CHAPTER 4 4 4a Parr 2 CHAPTER s 52 3 sh 55. CHAPTER 6 aa 6 CHAPTER 7 Aumospei and Svbstmospbere EFV Relaonships fom ‘ASTM and THP Dat 138 ‘characterises of Equiv Vapor and Liga 183 EQUILIBRIUM AND SIMPLE DISTILLATION 160 Eguiirivm Disilition 160 Diferental Vaporiation-Condensation 170 Problems 187 References 189 JONAI, DISTILLATION. 192 GENERAL CONSIDERATIONS 198 Rex 194 “The Frtionaing Column 198 The Contact Stage-Plste or Tray 196 Disign Comideratons ia Fractonuting Provesce 197 guise Staper-Cneal Considerations 202 Problems 2 NNomencatre 248 Reterences 47 BINARY FRACTIONATION-NUMBER OF [EQUILIBRIUM STAGES. 248 Analytical Determination of Number of Equi Suge 209 Graphical Metieds 256 Prafiems 20 Nomendatre 28 Reterences 85 TERNARY AND MULTICOMPONENT SYSTEM FRACTIONATION-NUMBER OF STAGES. 286 Preliminary Caeaations 289 Design Procure 290 Shortt Methods 33 18 CHAPTER PARTS on ‘CHAPTER 10 02 a. ni Computer Rigorous Calelton of Number of Theoret Puts 304 (Graphical Evaluation ofthe Number of Theol Stages Tor Ternary Systems 321 Problems 39) Nomencatre 330 Referens 332 COMPLEX SYSTEM, FRACTIONATION—ESTIMA- HON OF NUMBER OF EQUILIBRIUM STAGES. 334 ‘readocomponent Design Method 336 Probleme 6 Nomenclature 377 Refstenss 378 AZROTROPIC. AND EXTRACTIVE FRACTIONAL DISHLLATION 380 TECHNIQUES OF SEPARATION OF AZEOTROPES ‘AND OTHER DIFFICULT TO SEPARATE MIXTURES BY FRACTIONAL DISTILLATION 381 ‘Teelniques for Separation 382 Nomencitre 39 SELECTION OF ADDITION AGENTS FOR IAZEOTROMG AND EXTRACTIVE DISTILLATION. 390 Relative Vola san Economie Factor 390 Prediction of VaporLiguid Equllbium Daca 392 Nomencatre 31 Retrenss 32 AZFOTROPIC AND EXTRACTIVE FRACTIONAL DISTILLATION. 4 Mestanim of Relive Vouiy Change 434 (Choke of Eatiners or Salven 36 Section of un Azcotepieoe Extractive Process 437 us its CHAPTER 12 1 2 is. is CHAPTER 13, Ba. 83 1. ns CHAPTER 14 M4 Design ofan Austrpie Dilation Process 437 Design ofan Exrsive Dilton Process 486 Sohvent Reenery 40? References 475 FRACTIONATING PLATE AND COLUMN FRACTIONATION DEVICES—FQUILIBRIUM STAGES 43) The Bubblecup Pate 480 Perforated Pate 8 Variable orice Perforated Pltes 492 Other Fgaltbismstage Trays 92 Ruttcomgesn PLATE AND COLUMN HYDRAULICS ‘AND EFFICIENCY 502 low-energy Losses in Plate and Corin 52 station of Presure Drop and Lia Rockup in ‘Downcomer 508 Flow Condtons Catsng operability 21 [Eiency Fvaltion and Prediion $33, Prediction of Fen 590 References 56, PLATE-FRACTIONATING-COLUMN DESIGN METHODS. 570 General Column Design $11 Babolecap Tray Dein 575 afraid ay nd Colum Design 4 Vatuetay Devan Methods 98 Problems References 602 CHAPTER 15 PACKED COLUMN DESIGN. 604 ise 159 Packings 608 Peevdoeuibium Stage” Devices 613 Une of Picked Columns 613, Dire Mass Tear “616 Eni Design Relstionhipe 620 (Capucty Desi of Pasked Tower 620 Design of Packed Towers for Dilton 638 Problems 683 Nomencre 644 References 46 Appendic A! Tables, 669 ANppoti B: Vapor Presa at Various "Temperatures "653 Name des 69 . Subj Index 675 Introduction ‘Tie use of aisitaion as a separation and purieation proves is ey ld Eglo and Lowry [and Underwood [17} delved ino the eal hsorcl rings peaining to alee and scene ofthe past Yo Br where the rovers of diltion originated and when, and bow it detloped foi Breve state of we. Through the wings of ery Rintorian (Hester (10, Kopp Ii Bertolet (2) was nat thatthe rs reorde description (€t batch dilation oocured n Copa’ tine in Egypt around $0 However became of ther, oder hstneal desrpins of oduct, eet ‘ls perfumes, medicines, beverages, ce, ean be deduced tht dstilation J Some form was known probly as enc a5 1000 to 2000 years before that time.” Fresh water was prodoed by dilaton of ca water by wang a Sponge a a condenser around 300», and about these me arpeatne ‘wae distilled from rosin i and condensed int woo! mat. "A-smple condemer contig of To the exposed to the sit and Jending to a ecser nar desi the fourth cetay, ad nthe ceenth etary theft record of lcbel by datlaton was ade. ‘The beverage ‘cohol proces became the fist fn dition press during the Feviod teiween the eleventh and fourteenth ceiuy, and it only Became Signteant when the poblems of sain he inti the til nd evsing a ‘watercoled condenser were sed. Thi ws nesiary to abn ean {ble eof proce consining ih alcohol contents nthe early wxeeth cesar dilation was being spied separation and vecover of lesbo, wale, inegar, sence, ol, apd numerous ober Product. Books appeased onthe suet of Jaton in the ety pat of thesisee centr. Brunschwig) and Andrew (ined infomation fon distiltion proses develope up to that tine, which esently covered Sallie tach diiltions Maving pricy no reise uti taht {13} darted un siccooled tl head wih water-cooled condenser Tes meeting to vote that Liavies (12) deseibed a til provide with i a eee Many sing engines tay consider the side-tea topping clu 1 teat oven In 24 Donets erent 7 desed a bth Si wha aconating stl en, ad Ue (12) dred bath ts with Teboee and rcioning hess. Bole 3] dtd ood lobo Und vieprand reo ros actions ering to et oligos ‘Ts was prota th east dition ‘punt sat centr the tl were of te dere ach pe si tba They wee sal 8 (0300 deter snd 104 Tigh induding ces" Toe yds weve apparent enon ih aad Uh prdactsesble Cooper [of doce he nade ing eves ted in hi tin ‘ear he end ofthe ight etry innovations wee inode wich advance sheath dls at essay 1800 Rud [3] Sodom at sing agent The frre ofthe present ay SSbug pce let n 123 fy Peter [These aps were ed 3 Conte. dices for sa inodaced flow the pate on which the ape ‘Ste ytd ie was cidated ound he ae othe pt and he tem Sonpped is ekool fom th wine in 160 Cae deve com: ines ll she wed peor lt, ed post and intra re “han intresing adh n 88 was ete tat peony toda pa of ik inuor were made inthe Brith wile only 3160000 pl ne ng ed Dual sins wa a onthe pero oft aly development vehi econ out 3500 f 40 eur "The invention af Buble ppv plate, water-cooled condenser, ef fen eet a {Be adaptation of the proses to continuo operation Tonk pe ove the Febinely shor psig of 30 yar Dar te nite pend Homese, iinrewaseputeynoatonpoejima apy quoiatvepes {0 sain pre. ite in thet cvtry Hashrand (9 and Sore 16) neoduced tne ir onde guartative athena eons apple a onan sil dig Srl developed a aid mathemati fetons {othe factional sprain ot tiny mney those compre [talkool and wee and incor sich comidraone ovale teiupandovefon, vars mu sath, hat oss rm he cole ins enlace opin ate re, and presare es “Thos tbebepsingl the prsntcenary,SorelandHausbran exo shat ations spn wich sl den dion incline ‘ce andall metho wed ody ae cspnson and moderns ofthe ‘gal mode “fe tauonazaton and orgriatin of memati aplstins to rows fctonaon dag fame up the mey for stay In mer Pisted aan These mek eke thermodymcaies af capers gla and pase behaie in Binary and multicomponent moist systems 00- {tet age inprovement indesign o obtain te bs pov prose to a8 ulibrum stoge plate ad clams Pyrauc study aod the stay of the ‘iiables which at efiekeney and operability of he rctionting clara: 4nd the ‘atonalation of deign methods to enable opinenton of ‘acsonating process dsen fom the sani of econ. “Thee sbjts form the ass for he dausion inthe following capers. REFERENCES 1 Ate rig he ne ea Diagn fe Was Goo, "To Comte De" 25, Lt, 2 Bo tee Nap 1 Lit As Alem Freer 18 Rnd BT Eye, Poe, mam an epi 1, sr AB me a Che gr an 1 8S, part chapter Phase equilibria—binary systems Taste sisitron proces the separation of iste of ates to ota one or more Good produce a achcyed hy sletlon of conditions of {Grpertue sod prensa ao thai ei vapor and a gui phase coxlst nda dfeenc relative concettion ofthe material tobe sparta in {he two phasis HEIRS. When the wo (or ore) phases arena state of psa equlviam, the maximum flat diffrence in coeerrtion of {he mater inthe phaser cocure Therefore tune oem ondition is desable in the dsllation proces, and most Sexgn methods ‘he equim ss one ofthe houndary condone for quanttive deg ‘selon, Becae ofthis, eure data must be able for sch seasons fobemade, Such data may be obsined fro esha iterate they ay ‘be elermined experiment, or they maybe obtained though the se of lions, thera! or empl eating parecomponent and mire rope LL RULES AND LAWS DESCRIBING EQUILIBRIUM [A number of quantitative rules and Tans have ben devised to dsr and delineate ia tt of pyc equiv. Most thermodynamic fad pia chemistry ooks pve detaed development of the rls ced ere aod, herr, complete dusion wil nt be ind. ite Phase Rae 1. Wile Gide (16) eurbedequliviam mathematically in ters of ‘ne umber of components the number of phar coexisting. ad the cm ‘Bons cesar testi equlirim. Anite simplest form, presenting ‘Thysem a dine peesure und femperstue, the phase ule is expresed fai vacsa—P a where V= the depress of fredom or dees of variance ofthe system in ferme f the independent variables, concentration, temperate, ind presi, wbigh mast be fon onde to doie the lem tequila (C= the number a independent components appearing in all phases requis whete the amber of eomponent repeseat the Feqest alae coiiet from wish the composton each pias a be expresied Sirety or tr of am equation {he number of pes wherein 8 phase a plysclly stint tof the ssc vig the sue composition hraeghos and ies cpamte frm the ther parts he stem by meant tan ner ‘Thus for stems at eit, omposed of «vapor phawe and of a liu pase two vale defies inary system equim, the forsee a temury stem librium, apd n variables an meomponent ‘stem equilibrium. Por a item compored of tres pases, ng #1 ‘vines stiches egilriom fran womponent sae, eat Mixtures Iieal gases ae those whose tehiior dere by the Mel gas law she cam be stated mathematical 35 vit an Uuhovi te solume of one male af gas is related to the eondons of XGpostue and presse through the eae proportionality face IR dsl gues dom interact cheney by forming Rew mola pees (oF anacite philly because a eens Jo moka voles and onepecie mlaclar irate forces The same criteria tay be sid to pt dl gis “The concepts of “ideal” gas, ide” lg, “ie” pas mintres, and “dead mites hae formed the bass for many gut ean deserving equtriam. OF prin sere in the el of tition ae Dalton’ tw of paral prewures and Raoult’ Iw seing the prenere tered by 4 component inthe vapor phase of «uses mare to iS ncentiion i te gu phate ands por peste alton’ 1] law sates thatthe ol presse of a misture of gues equa othe sum of the paral presses oft med gases. Ths, Po Snon tpt tre ay [Aso Dalton postulated that he parialpresure of an del pas in a gseous ‘wate proportional to heel numberof molecules of that pn the mature (or fo He moe faction). "Thus pare, “ acu’ (965) lw, elting the parti presare inthe vapor pak othe guid pase composition, expressed as pas, «s Combining Dattors and Raoult’ ls ets in a exrsson describing stores of ea vapors and gus equim. Sonn Ear, 09 eet an ‘The eapor press P, of component i a unique property ofthe con ponent and a dra oncom of temperature. Thu i pets with 30 Treen in temperate, anda teri vig higher vapor peu ata [een temperature than anther component ssa to be mare tae ‘Vapor presire and iemperstore are commonly relied ty means of he AAntola BI equation ge =A a where and Cte constant for a parca compound over eaely| avow tenperstare range fasally not over 100%) Value of thee constants for various compounds and fails of compounds and the ferperture ranges for neh the sonstant apy pear in number of| Feito Drosha [12]-API Project Report No. at (3), Peey (4) and Tier presen either the Aone const, abulae vapor pes dat, of oth, Bsample 1 he oboing vp pete at ae ain i es “Tete pits of da pri te des shoe fo fA sna aiggran etn An aerate eto ered Deebach 1 em te wT ‘SEE Cd ora by eet oma cies ; c=m9-erKnaiy)— 20.2 ogiriny ass SEO ee” Tae Tea Ht Saag et fr 4, Seo matod [osaonm | setom ae eee | | [EE] Be a J = \+T= T=] soocemecr [re fae, [ine | ish Posies | ro | ek | or convening in inespoution, spor pes chas in the form of [nota Kate ta. 29, amone many others, are commonly asd foi fe widely ed relton i silat caleulton sce wt msn of sear: the arer the value af yy the easier he ‘sparation tis dened by a o ak 7 [NoneaLGas Mistures| Acs ge and thr mintares generally do no follow the ies ecnse of the formation of dlleent molecular specs and because of imermekeulratacine fos,” Deviation rom te dels law cn Be {xpos in numberof mys an profably the most fl irom dt ton stipe ane thon F compres factor an fact cof. er cay here 2 is the compres factor preseatng the ratio ofthe actual as me to tha of ah desl ga under tie sae condos of temperature 2nd prssre.Ttapprnches alu of iy at ro presore and eel Tig’ for mos gar at ond around atmosphere. presure. However, ‘tome deviant an be encountered higher pres sample 12 rn te seme ype te ate ay Hi Rinne ai)s0e, boc ° cmpones = “Giprcemse | come | ata ae Epiganman | Gaon | tao | Solution Tempe [[ ee [aero] mer rami ORs | | Sade | Saba se | eo @Detytostbeune 50 | nese | samme | esas | seus Most thermodynamic hooks give methods of determining compres factors wing enc constants and corto based on the theorem of forterpondig sates. For example, Hougen eal 2] present a compres Si char relating compres actor reduced eperature, and rede rest or mates having crcl compres 2 0.27. By means lft dat anda coeltng equation, te compresbity for compounds ‘avng rites compres fastrs other than 0.27 can Be determine. "Ths method rene from the work by Lydon et al "Fogcy oot relates the prt prsure svete by an aca gs {o that which it would eet fit Bevel. 1 defined as follows a 2) where isthe escaping tendon oF sc defined hy Lewis an Randal (26) (2) = eramy (13) ah AM lower presures, around atmospheric and below, the foci is sel equal tothe pvt peesore ofthe gs nd te Tact eect ‘seventy unity, wheres at higher prewaest devises wey fom un, ‘Houger ea. (2) prevented a fugacity cofiient char aed othe work a Lyderion ct al [3] relating the eoecent with reduc temperatre and resure for compounds having aerial compressibility DET, Taber {ate and a orecon euaton enable evaluation of the gay cafe for other materi having dere crit compres faces “Thre are many compress and fupacy cetient charts in the leratare.”“These range in type fom gerald relonships to spe ‘sompound chart correated oa the hati of tte reduced conditions, peas ‘ever conitions,andin some elses on tet teperatres and pene For spc compound the sie charts are me acre or gee ‘se the author prefers to we the Hougen ca, [23 generale cht sd = enc al [2 pe Foca nondeagns mitre the Fpacity cof nts into Dalton vlaw gation ae Feefigs el ‘I ata tiga and igi mistres the mean distances betmeen moles ‘are much les than thos in the gaseous tate andthe forces of ataction tween them are much preater,"Nonieat Sehr is evalenced by nom adaitvty of volumes when compounds ete inslstton, tad By ats ‘of mixing when the pure component are mid at costa tetaperatare sad presure, The extent of deviation from monieality ofeompanents a iid Iatres is measured by the atid coin y= Agnn the renders refered to standard thermodynamic texts for deivations and dtntons oF this tector interme of sity ad fea “Applying this correction Tato to Rao’ lw ess io Aare as, Incorporating bh he fgacycoefient And acti cect into OCTET bas on eu in 16) hh en ewe os rohi= 1 (19 4 bass for caletton of aporliguid equi fhe itereationships of the natin ste known or can be preted. (Some thermodynamics ete to deine the oe ove fctors to correct for aondea behav. Fee the io dei ar consdeetsuicen) Relate volaity om nonsdelsystens is shown by wl Pm ay ‘nay increase, ders, ofemsin conan wth nes intemperate cpending spon the nature of esse. Because relive volt vans Jen with emporature than doe vapor pressure i used quite extensively in Galen ox Integration fro wap al zero pressure to he gui state ike oo asp, Using the assumptios that Vb and thatthe constants of the mixture ‘ould be obained by ne = Ga? toa bt on ad = the 33) be derived aay (as «a the cae van Lane utons reste Tin= oF aay 1 T= TT aaP ae rine gt (38) are Wobt Equations Feom base therodynamic equations it can be shows that the astity collet of ny component cn be late pari exc fee energy a ‘mponiton o Solution follows: act) Pe vanes 7 BTN us» Won! [6 47 lated excess re energy and compostion athe liquid phase by theexpansion of he exes e-anergy equation Foe soar — BeeA + Bees (040) ere ag” 22° (partiat molar ewes fee enersy) (41) nd fo at festive mol volues of components or etal, on Son nd de ae constants relating Fore iteration between combinn- ‘ios of uite mokeles ora binary, Becm~ (etkeveyolume faction of) (142) Fein — Bein ay Sine a= ea oy the preter the numberof terms in Ea. (1A) the more accurate the co ‘cul data, uations inolving fr example. yy ae hitarer equations nd those involving or example gy ate fourorder uations jplindreqton or hy sem were doped hy Wola erga Beet Betta Snstine (149) SSURT arg, et Bnet etn Since the su ofthe elestive volume factions i 94 1 1.0 terms can te mliplied by =) 5 sor soar Lesing A 4f2ay +S) oan ant Balan + Sa) oa) ace ® ; sonra (4+) ow Diteetatg 9 1.39), 0) asp om oe —_ nese . Tae mga) me mg C aim Ang + mt log 7 a Fmdgulga? Ve Inter fete vole rato =the Wo equations come toe = 3¢ [442 (8% —4)] ass) vosre= at [ns a(«ft— a] 056 Other Equations Correlating Binary Vepor-Liguid Equilibria ‘Carbon and Colnurn [9] mode the van Lar equations to eimiate the temperature vaibl.” Since van Lats atime ge ange mere he van ‘er Waals volume constants, andthe rato of tbe ePectve moll volumes comes equ tothe ato of the died constants. Thus qn — nd tog asp orn a) Rew Genealy the “normal” brary stems show postive values of lng y oer the whole compostion range” The miumum boing szeotropi stems he posse values throughout the compostion range, an the maximum boing azeotopc stems eahibt epuve valcs evr he enti range of Composition. The constants 4” and Bin the Care-Colbare modised ‘am Lar equation ae related tothe coresponding constant ia the origi ‘an Lar egutions 9 ols: 2 Dur os rout eo where A’, ate the Caloa-Colburn constants and A, 2 ate the orga The constants A and in the foregoing equations can be evaluate from experimental data, “For a binay system only one pit of data would be equa, theory, for simutancous solution of pas of equations. ‘Tis requires an ociratlyGetermiped point sich as fat represented by ‘an seotope composition and temperate. Other points may be wed i they are seurtlyevalated and thot determined Inthe middle ange of oacetration, ie © Ot 06, ae sally more eae "Acorn method 4] utig the Cutomelburn modified van Lane caiatios for evaluation of Hobare ary vaporiqud equlibrum data from one experimental pot without the we of walantertor eleuations is outlined as follows. Solving for the constants in Tem of composion and ett coetisiens and wtiing A atopy (1+ SREP sy torn (14 BEY ae) so wing oP the method ie flows: 1. From th experimental point Stein. 7 a and Py 2 Catala the values of 1 and from Ege (1.61) and (43). 2 Compute 7 ad afore whole contention range abd ‘Calette andy dat hy the Flowing steps (6) Assume tht Ey (148) "wil expan the vapor presse reltion of bod components wth cmperstare meres x eo8R as) (This atid for most biary ystems over thee range of bling temperate) Pata 69, ass) 6) as — (69) 1 isobtained rom the vapor presures ofthe to componets at wo dierent ‘temperatures thin he Bolles range betncen that of the vo component) ve rr} Fa Pa Ba a) and canbe comidered constant fora gen system, (6) Calculate a and for anu valves of and clelate a and 8 From Eq, (168) cialuste 7, coresponding to the diferent values of From the vapor prestur data determine the temperatues comeponding tothe diferent les of Pe From th init equations ogy. an B= timlor rs any 4 an 8 can be determine also by extrapolation a he og vers cures fo vyorO and 0. This method i subjet to posible eror because the esperinental points at ow concentration ate dificul to cralate sample 14 styl gfe Conca ied Tae ago The Solution ‘ago emery hon ag ae ye Aine gun ig Polite at Several Presa, “C rer, He omen vaca ethene aig {etc cohan main fen a gan romano Rips oom[s« Bren) # (¢ ge BE EL Se evens 14 mDodosine buy itil sem at 160 men Hg Eguiue Eg pl dg ons Fn Wit Ba 8 Many eqtions izing basi thermodynamic reltons and based upon ‘vations pling sumptions have Geen developed to desert iner- ‘ellonhip betwen acy couficet snd competion of onde binary ‘stems for the parpone of extending partial ata or coreg at ‘Scatchard and Hamer (39) asumed the elective moll volume of the component was equal to is mola! volume, te, g¢— Va and ge = Ve “Marguies (2) asumed the eee mele vlunes ef the components to be eq ie. gun = 10, resuking in the following frequently used equations logy, = 82a +2008 a wy logye— sl} 29d — 8) ay Hala etal. 19 assumed ideaLvaporphase behavior and derived from the Redichand Kster [37 egatons wet of euation ivoing vapor pesoes ifthe pare components Wht [8). Ya and Coll 9) Li and Cl (27), Bonham (7 ME (5), luck et al. 6, and others have derived equations ‘ofthe nan Litr type. Ia aon there have been many other methods propood for prediction of vaporqud equitricm date-om total pret re mestrement [38 fom dita on othe tsar rystems [rom ‘ate volte (17, 8] and from purecomponent proper for cen Slases of stems (29). Binary aacurope emperture and composition can be predicted at iferent press rom dat atone peste [2 Esomple 15 Wah dw fe Maris gation and te long eprint pi doin gree citi oe com Dac Gaarei| nowse | iss | anes ea” | Ghat |e | eae Solution Ashe motos m= 9.4 cog 7 = PP 6809 1881 tgs 0S ya 7uN62 = 1589 lage ass ‘Tae Marple ei a: heey asta +2 degre 00 244) Seting alte of compo and ny alc ae nota ea ors = 0254 8 91 ose 02405 4) Sedtin or and Bi et he pis Repetto of te Mars gen gives loing wo aoa be ae leeaee anes 15. Aci cote —te Smeaton sate a he me th koe a slob pcm 2 irony, 1A. PREDICTION OF BINARY VAPOR-LIQUID EQUILIBRIUM DATA FROM PURE-COMPONENT PROPERTIES ‘The prediction of misture properties fom properties of the componsats omponing the mitre she mort desile method beeae exe age ‘antes of pure-component data ae avaiable compared fo mistre prope ny data Forvery gross approximations thalues of thea und onan ‘ofthe van Lar equation ca he eimated from Se urs oe 4139) Ctl data canbe estimated by the method of Lydon 90) When the ita are subsite nt the van Lat equations for and, the flowing, rene te obtained Tab ana 4 am am aasnen fi (t {Ax bes these approximations could be applicable only to binary mites sowing no chemical interaction ees oe hydrogen boning, Finch and Van Winkle (4), using Scatchard’ and Hamers (8 40) rmodifcation of the van Laar equation, Héeband’s [2] approximation for inerna pressure and posites by van Atel [2] and London (28), eveloped a method for prediction sf vapor gid ei Tor binary ‘Ssteme from purecompoenpropenis. For noapelar nonpolar stem Story apecment mith experimental data war blaned For pol oapole stems the apreien an les saisfactory, and for pola paar fps the method faled to predict data within ruled enpinering ‘wears. 14, CONSISTENCY TESTS FOR BINARY VAPOR-LIQUID EQUILIBRIUM DATA, ‘isilation proces design genrlyinveves the seo some experiment ssporgud qullriom dat. Thee data nay be repre he erature {nay teva, or multicomponent data and maybe complet. pataly ample, oF comist of ony Tew points. Beause the sues of Such ‘itn vary widely with rpand to methods aed, lehnigne involve, and ‘en in sil f the indi termining them may be nessa for {he eines, who propose 0 se the dats, to apply some kind of tel fo ermine approximately a least, tsi quail” Alouph ths teing proware may inate only whether ent te data aeieteraly consistent, feck an indication i of consderabe value ia establishing the probe ‘curacy of calculations fa which the data are involied, In addon there ‘may be more than one st of dita reported on ope stern which die in ‘omeicl values of temperture of composton, Consents ll {enerlly enable the selection ofthe data which ae peasy more core Moxt of the conneney ts ave heen dese Irom thermodyramie relation for Binary data, aad most of he Css ae based upon the Gibb Duhem [15,13] elation ‘Reavrangemeat ofthe Gibbs Daher expression writen fra binary stem penis) (ata ye, om “This states thatthe rato of the slopes of the ati coefficient cures vernisliuld composition i equal othe negative ation of the mole factions any poine This it called a sermadymamc cmtstensy fet ee he ibs Duhem equation war developed from has thernodyamic dei tions To check the consistency af ty sto dle curve are plod as Indlesed andthe slopes a ete composition ae evusted Sd ome aed with te ratios the gid compostions Redich and Kiser [34] resommended pling the rao of logy ‘rau the igi composition sy and dtermiing he areas above ans below ‘eine whet log (7/7) 0, and extending tthe curve. Ihe areas ae uth, the data re coded be comtet. The extent of deviation fiom equality meamure of the inconsistency. Figure [irate the Inethod Broughton and Brearley [8 developed a consiteney test based Upon the assurption that the tet log independent of temperature, “Thay recommended ploting Tog) versus mand measuring the areas above and Below te line Flog(j7,)~ O and the pled line. Ths test Bihown in Fip 15, 1 dfret type of consistency fest se om the van Lar equations was propos by Back [4] nhersin the vals of (log) are pote spans the wales of log a shown in Fip 1.8. Ia stag Tne esl the ti ae said tobe coment with Ge van Laat relations. The Now tnd Twig 5] comstency txt wed the following relations 30) ‘her kis the rtio of the tll latent est of vaporization ofthe lower Toling component to at ofthe higher bong component They cai thatthe da ae consistent when a sspht ine rss trom pling > ‘past the lig compontion my a8 ented in Fp 17. Thus somete asp hee and Care constant fo partie binary tem, "Adler eta I] proposed thermodynamic comistency test for Neary systems when the ore ola componet above Weil temperature “The following equatlons are presente: sdlnaPonp) + sdinetionn) = Zndinh, (18) were a ~Ne asa) whee ¥,~ vole of gui, es ole AMIN Prnn) + dK Pre r) —Zedin (180) where eet (sy) sdln yb adin ky =Z dla Pe (1.86) Bsample 18 “epee © pr pea mig Temp ior esi hh of tsi renal cost by (te Resi ad Kie ‘ere repens ea Sotuton Atty codes recat by (tana component eaMMLE 6.) Rsvh aod Ks temadynaconsiteney tet) Bough {oad Beaty thermodymane conten ee “erat re ted 6 teaming gure. Thee fae ae the sts oe into) ow Neth oda ep sient to ten atm sweater oie. Toa ye tare om emer te Psample 12 “Theft son he ny em moc Cal eet er here symm) 5 the Ba te) he Nera nd Tug es "hcg eatin daa forth meine Cele sn Hg sre : apes [A] A)» |» [est we oo ‘Avr esd singin cn be dean ough ep oss x ining eo syne Sse Equations (182) to (186) are graphicly integrate withthe me of| vibe data ov peered corelatone the dala are not at hand Figues 18 and 19 eoematiealy state the integration. rene LE Inggation of egpaton, nOURE 1 tegatin of eqn Hesingtn [20] devised an empl test which ais to be a consistency tsstforbinary data He recommends the ollonng procedure. 1. Cleat the val of fg (ri) Fr Series of ompostios and plat thot vale aie the ales of “F Evatat th integral 3 allows: 1 f (oren~ te) a an Fron Fe Lt _ aso ae, Beate (ss) 4 aie oss din Peel (19) “The valu fF taken wih postive sgn. fun 10 Art in Hengon 4. Determine the lowest bling pat inthe binary system ty whic i citer the boing point f te lowest bling componeat or hat Fe si ‘mum Boing zctrope andthe maximus boing ange ‘From Fg (131) determi J, 150 0) us “The data are considered comsitent when bos as) Pre lems “Tp | Spal . i CatPmmHg ore ee 1 ri conn tens oe ae es Be os eat eprom gta. (i; Pt pes par enprn ir anten dnekon theta, Dacre pseu gay St fr x39 46, 9a 7 he Satna sat Ne sta ous ‘Glew be aan ant: Mugen 0 Cons Cadre sont mts he ca Set go Deva esa fo he yy meta aes 700 men eel ap e) Amming cn scone syen to besos (no me stra hse ny Sagan aye Kae Jr {Ug owing spit a pte a tos ‘Aecoee-Ciorform Syste a 1H ‘Thesis esr ae Commons Ke een | Appr th isk tthe wing itso he 1 band rope pen, 9. Apply he Nor and Tog ony a te 10. App ett ndcned ah flowing cts nthe joo Oden sem. 2 venue mun ‘Cetera (o) Arty he Rion and Ker (0 Arte Henan Nomenclaure 42 constant, van der Waals equation of sts, oF moleuir fore = Antoine constant, o¢ constant defined in activity coosent que “van Laar constant {= Garson and Caturn mood van Lase constant constant van der Wale equation [Antoine constant or conan ined in ati coeticentequtions = van Lat comtant (Carson and Colburn modified van Lar constant ‘Antoine castnt or number of phaser conponeits = dierent ‘ened quansiy. Eg (1.9) (sapere) denotes exes peopesty Capt {Gib mot re energy iby prt mola fe energy exes Gibb re eneey tnthapy ot entre = molar enthalpy of component, ened quantity, Ege (87) and (188) = subscript any component ~ defined guamy, Eg (291) bcp any component ratio of mola ets of vaporization lover to that of higher oling component Stern oth component = nhsolte pesure umber of pases piace egactessoReeeAs & ip = eta presre 4, sapr presse of component 2, Laat pressure [7 Spal presse of component = Het mola volume of component = iets proportional factor ‘mol enon {38 moll E07 Sit — r= sia temperature Shot temperate Srenpersre = honmal bing pint tlle eerey en ey ao poe = foal ame = digs of fesdom 1 = ol volume of pore component Xt racton of compet gui 4 nde actin npn pr compress ator Grete vue action; dened quantity, Eq, (140) 2, ~ sia compressibility factor, 2. = rec teers eae voay > hetvycotient 1 Laittrene 2 itera operator > fugacity softcien = consane = Smmation o dines by H. (1.39) Sudeep ees 1H = higher biting componcat Lower baling component 1 Shui REFERENCES. 1 A, S 20 Fn idan Mah CAE 2 Keine, Cop ea Aca Sy Pr Ma 1 e4a9n, Se it at i ee mec tn occa eee (a ha ab The chem ogee. ATT 14 BERTIE tn ah tt : Soe cee er och, Rand M. Van Winkle: LCE J. WSS 40 (190 ‘Gitmowt, RD. Zuhevieh and DF. chr: nd Eng. Chen, $3223 (1961) hee eer Saekt a : peacnai cece Fe eer Sunk naan nth pete he Seen strata Et tm ic poses metas a ees ere ds eae ‘oper of Pres, Uae Es. Ep Sta pte 199 eee ecco eee reg MWe M, AP Cho, BB 0 (96 ei Onan A Ri ay. Cho 40:4 (98 ‘Sena, an. Hamer: J. Am. Chm Se. S05 (1939, ‘Sitar Chem Re WI ‘Scie By an Man Whe: Po Rf 3 Spent, 195. Sm AL AE Tm Foray S28 (ed, Vander Waals. D-oOr Secon vn en gre sift" Letn, We CR. Ton Area asi). ‘Wo Kure hg Pr 218095, ‘Won, Es Chen 0 (98. YL Tyan). Col Ch Eg Par Sp Ser AS (1D, chapter Multicomponent vapor- liquid equilibria A nsskicomponent system is dened here as 9 syst composed of more than two scentible steal compounds or peewloompounde of mater to wbich phyal properties can be restoably signed. Asn the ete of batty sem, ulomporent sats are encountered which enenally tee ely Under comitons of lw press and normal ding tem peratutes. Those composed af minus of Kydrostbons, mintres of 0. Ivic compounds, or mixtures of homologous compounds my approximate Hal behavior in both vapor and gid ste. Ware mistutesofmaterials ‘of highly dime nature ae eaouotered o the conditions of presire tnd temperature are Severe, exteme nonel behavior Is evident 211, IDEAL MULTICOMPONENT SYSTEMS Mulicomponeatvaportigh equim data for thse stems which appointees shave may be alelated by Raoul’ and Dalon’s wt in he sme manne those For bay ystems PnP, en ra Sra en, 0) For 3 fve-somponent stom with s40 pase in eguiriom according to Gins pave tle, there are fre depress of feed, four independent Composition varies, and tempertare or premare I the gut com postion sLaown aod the temperstre sete, te vapor conpoton can be eleusted from Fq. (24). {If four liguidcompontons are Knows, the Ath is ako known neease $x, = 1.0) SRM Pah wR ee Ad the otal peir i eau by mea Pee nP oni shah es Ie the temperature an spor composition & haw, the equim com: Peston of thelial fact mat be determined by tab oderor culation. Thi may be accomplished by asuming atoll pes and ‘leliting a total presse by Snr eo Thi may ss be done by xen pit pressure elelton, By defiition the dew-point pressive hat pcsue at Which the Hist drop of qui fone a the presure onthe vapor mate isfeased at constant te perature. Mathematiall. wo $0 en for an idcl mixture. In ether caksation, plotting the calelted toa ecrre ere the ass’ foal presures fr thee oF four tal aly Snlerabe the ort prewar to be evaluated fromthe plo ith alent teuruey. Then the liquid comportons cam be salted ying the ‘Sotety deternined pressure ey Considering a fvecomponent sytem of a faed constant presre wth coctiting vapor and liguid phates, there ace four ering degree) of freedom, four independent compontons, and te temperature se. If the liguid compositions are known «Pableyin temperature caksation ‘sul made to determine the termpertare By definition, the babble at tempeatre that temperate st which the ft bubble of vapor i $8 argu equim formed on esting gu at constant pressure. Thus, quantitatively, Sn-8 29) [A isimun of three tomperatere i assumed, the cowresponding vapor fsstres ae obtained, and Eq. (29) is wd t clelte the summon Seye The sum ss potes vero temperatore std, the pot whee the Shim squeunty, ue correct bubblepoint temperature i alse By Inova ofthis temperature the addon values of) ae clued, wing the covespondinaly correct vapor preres, "When the vapor compesions and tol pesure are known, the tmp ture andthe compention ofthe gu in equiv may be eulated By 2 dew-poetronpraure eaeaition. The dewepont temperate dfned [the temperature at which the Bist drop of gui sfrmed spon eng 2 apor mare st consant pressure. Mathai st expresed by {eq 27) At east thee valtes of temperature ate selected, the caret ‘spor presares are obtained, andthe summation i clevlted by Eq (27) The ested sum ar plotted versa the aesmed temperature, and where Ex, 1.0 occur the comet equim (dew-point) trperte Is eb lished. "The ligid compostions may then he ealelated by means of 2, Relative volatiles may be used whese the temperature range (ie ifr: ace in boiling points of he Hghest and betes components) o he mul Eompanent eum data isnot great Usually the restive vlan retuned onthe eavet component in the mie, Arithnetc sveage ‘elative volte (athe highest and lowes temper) ay be ted er, {fhe variation in relative volatiiy ith temperature eshte may be cvalted at one lempertare and sumed fo he sonst ver the te atie range "Tas, forthe dal ve-commponen mitre. Divide umeritor and dsnominstor oF Eg.(24) by Fy The compontion of compogent inthe por tay tama nh in term f etive ot e a en Sau ee ten eS Silay, en en ew 22, IDEAL TERNARY SYSTEMS “Ternary seme represent somewhat speci esac many dilaton problems can be reduced to sonidration sf exeatly terry sytem {nd the calalstion are somewhat spied asthe result.” From the pe fale thee are thre degree of feed Tor trary system in two cor ting pase Raoul and Dalton’ ls ae followed Eg. (21) 0 (23) appy and bubbepoin and dew-poin aelation are made to ter. ‘mine te phase eomposton temperature and prestressed esse nebntm 1D ais) od pobych= to a6 5, 2mh whe, (m= SoBe M SRE ean os ao IP, 4 Cena WF _ 19 (18) In many cases, particuaty in graphical Madi it is uel to determine ‘thermal vapor and liu composition lines, This involves fing Fan ‘F,and enables ditt cleulton of the somnpostions sing one ad eae lating the others) fom the allowing lations: — em honanth—nvinth-n) ah 5 when am “Ths, with temperature and presse ted, the vapor presses Fed, andthe aviation of oy 8 freon of yam Ye alelted. Fo isi ternary saems tis sa stp line onan yer plo Example 21 Catster vapor and eds or te Herts so on sdbee pte 3s Wal sur af tm Hp se ston SRESHIZE,“adegteminy seasoned ote aly for an, copnens | _—__Anommenmms I Le Sarees Tame wean | pase | aia 1 Feowe —| Spe | Hanah |B DipRiow | some | Te | Ht Solution ‘ The ii npn eo rom = cerremmnig | tn pt Orkin | @ Ebb | OTe |e ee ee Withee fa ga of (ed) et, eal y= eta Fran £9,020, a ee Silay, he sthermal spor compost ie san be eaeulatd by MPa By RRR "RRP (is epesnts the equation ofthe sl ine in Fig. 2.1) n 229 Yount 2.1 tema vapor and oun or Ear 2 Wen one cmposton eshte he emg vapor and lig com poston can etal bd um he hte pre ‘Sali eompoton peste fd foul peso. Teter a ‘eave volatilities, the following equations for Wel ternary mixtures cat tine negations Tor el ternary st 2 OTT eT a °° TER D Gate ee ce eneaeee Filia wlan OFT ) ae lam Filia wile DFT am (Qeattative Graphical Study Visusising the variance of compostion, temperature, and pressure in a inary sam is reatively easy stce the nue of variables such that the naraton eta be shown on 3 two-dimensional plot the ease of teeny syste heredity in vraliing the variation of composition tnt empenture st constant peste, nls oh gues oe type show InFign 22, 23, and 24 are comsrated or plate sect mods such Showa in Figs 25 {0 27 are availble. Thee are extremely well and Informatie although my not be faible o spend the necsay ie ad ‘Horo ths Kind of tree dmensions plo. ‘On many scans the engineer x terested in etiating quately the temperntre-compositionrelasonsiptefore the actual try data a ‘dermined or eat. Te such aber a fail good presentation ofthe ‘rand 1 surfaces can be ented Irom the characte of the Bint ‘ystems alone. To do his diagrams of he type showa in Figs 28 0 211 une 22. Sod model of «teary — moins 23. Solid mode of a wemry peatrecomgostion pine "Gi lnprturecmponton Pose S- Erte Soar" Gauy ene, certo kanfempee URE 24, Said model ofa ternary oenE 25. Pllc St moe of fam mong Spor andiguu sur game aoa Say en fic tee Waar scope Boch vests the err ws stunt nd oe a plghee eamnatpac te ante tng ROADS Wim ean oy pC Witt tp ronal ahem ahaa Satay Spee eg ees Sire Se das" ao sean tp ohn eps openssh 34 rmsquo squuim reas between the ies re the approximate aterm, enary, wo-phise "Thc Us ies ines connecting vapor equilibrium compositions) for then inthe sides the eouy ot and in the ternary diagram ll A lnc general endo pont to corer ofthe gram. I nay isotopes ae present the ees ed 0 coners a the inary azctrope "Such grams ae sf in caring the vapor and lig sree fs teary stem. Sie the ti nes shtehed for eich other {orice region represent (tthe intentions wih the Iquépate ad ‘apor-pbme oundare)the gtd and vapor composons a quit that tempeatre,contnsoa nes cin be daw from one eompostion in one prt the dagrm to another composition in another pat ofthe Slag This ne repress he eso he agency pos of he ere ‘ihe egitim eines treuphou the whole compotion temperature ‘age Such icy we sal eee, epee pone dso pats

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