Phase Equilibria 15 15.1 Solution */g= 1.091 > 10° m'/g vii ve 1 0em'/g = 1.0% 10° m/e Fe = AH = 335 1/8 Starting, with equilibrium between ie and liquid water, dy {SAT, Pita give a Clpeyron equation: dP/dt = A/T V) inf can be expanded as a 1.35> 10" Pa/k “Tins a pressure of 135 bar would be required to depres the freezing point of water 1°C. Ifthe © ‘ambient temperature were ~10°C, a pressure of over 1300 bar would be required! “The "apparent melting” is most probably caused by friction in the sliding plane. See International J. Heat and Mass Transfer 18, 1057 (1972) for further discussion. 153 Solution Let represent napithalene and C chlorobenzene. At! bar, when a solution is saturated with N, te liquid mole fraction, xy =0.256. Therefore at 20°C, Gynt a) = Of (1b) ® IF te igus compresed at constant composition and temperate to 50 ar, Gy (500 bar) — Gy, (1 bar) =f VEAP and Yo=V+4OV/AKy)y, p= (102 + 26x,) + (1 — 49126) Fplaty 500 bat) ~ Gp (I at = VE AP = (1.28 x 1071500 ~ 11 105 ® = 6.387% 10" mol @ 256) = 128 em /mol 28 10° m'/mol152 Phase Eauiloria_ Chapter 15 sina forthe std pss e G5 (500 bar) ~ G5 (1 ar) = VEAP = (1.15% 1079500 — 1)(1 108) = 5.739 x 10° J/mol @) ‘Adding Es. (1) and (2) and subtracting Eq. 3) G (500 bar) ~ 6 (500 ba = (6.387 — = 648 J/mol Bur, ifthe chemical potential of a component in solution exceeds the pure component value at the same T and P, the system is unstable and precipitation occurs. Let x be the solubility of raphthalene at 500 bar and rq the solubility at 1 bar, both expressed as moe fractions tone bar, wth ieal solutions, 7739) 10 G.c.x GLO + RT In 2/ ry G1) =6) (500) -["" vE ap 6800) =G(500,3) G,(500,.1) =G C1 of ViaP De RT in) VAP + WE aP (8.314)(293) In (270.256) ~ 5.739 x 10” + [1024 264) + (1 —2)(26) Px 10° ‘Thus, with AP = 499% 10° Pa solving for x: 0.196 185 Solution Atte freezing point of the soltion, wo dings tnft Ateonstant pressure, only temperature and composition variations need be considered, thus: Pale PaAl orf @Praso Equitria_Chaptor 15 153 * &l- “(el fee &] Vy (0 Nene _ RE o ax, (AH,,/RP)+(GH/RP) ~ 3,AF, Integrating Eq. (3) (assuming y= 1 and Af/,_ >> BFE), we get AT/N,=-RP/N,AH,,,= 1.85 K/mol solute Oy From the igor equton (3) derived hove TLL +5, 00/20) pw 2 (20/002) o Since x, decreases with solute addition, and we are interested in depressing the freezing point, ths @r/inx,) <0 Since the numerator i alinostalwayspositve, thisean only occur when AHI, is negative and smaller e 15.6 Solution We have divided this problem into several sub-problems, In each we assimea model and examine the consequences, (2) In this ease only gas enters the tank and is well mixed. We will agsume the entering vapor is saturated as any higher temperature will reduce the implosion probability. Select the tank contents asthe system. The energy balance for this rigid, adiabatic system is A= H, 5%, @ with, bn, =aN enthalpy of saturated vapor = constant Integrating, Eq. (1) UN UN, @ Simplifying, with AH = GAT H,- UV, = 0 (Tu T)ARTVIG Tg DRT)154 Phaso Equilbria_Chapler 15 sir wed fof alot e Y= ((K7,/T)- 0 = (1/2 + Y) @ wr Yer) 2en-WVN moe Fer ne hang kt X == PPh toenyTe Clearly, from the equations given above, as N increases, P must increas. (Also since forthe cases of interest xT, < then T decreases with N.) Examples: (1) O,,#= 14, 7,=278 K, T= 100K Zz peer 1 0.25 2 033 3 037 4 @) Hy «= 12,7, Zz t 043 ou32 2, 08 4 0.69 os 9 078 18 n 080 146 0.868 (b) Next, we assume that the tank initially contains vapor at TP, with N, moles. Saturated liguid ‘enters and vaporization only occurs by contacting the warm gas, No heat transfer is allowed to the walls ‘The final state ofthe material inthe tank is all gas. An energy balance then yields, dU =H,30,= HAN H,=enthalpy of saturated liqui constantPhase Equitoia Chapter 15 155. We integrate as before and obtain (Hl, UV Bg = 0) = (N/N) = [C fT qT) + RT, ~ HVAC AT. 1) + RT ~ AH, ‘Then when simplifying ye(r/T)— 11-724 D) where Yand Z were defined eater and T=xI,-aH/C, xem Lets try and apply these relations to oxygen. With the properties given ealier and Aff, = 200, tar, C,= 0.656 Ki K, and 7” = (14% 100) ~ (200/0.656) =-166 K Then, Zz y Pa LK Par os 053 030 131 070 06 0.60 036 un 064 07 0.66 042 95 058 os “071 “048, 81 032 09 0, 054 oa 046 10 ~080 060 56 40 ‘These values assume only gas atthe end. Is this reasonable? Consider the case when the mass has just doubled (Z = 1.0), T= 56 K, P = 0.40 bar. But, at 56 K, the vapor pressure of oxygen is “0.022 bar so some liquid must be present. To find the exact conditions (again with no wall heat transfer), we use the following 1. Volume balance lume vapor + volume liquid AT) 2. Vapor liquid equilibrium, P, 3, Bnergy balance By tial and error solution, when P.=0,55 bat. An implosion ean oceur! A similar calculation can be made for hydrogen, Here no condensation occurs until Z is Large But, for example, when Z= 1.0, Y=-0.54, X=-0.0T6and T= 128 K, P = 0.94 bar. An implosion could stil occur, 85K, 0, of the oxygen in the tank, 22% is liquid, 7 (©) In thi case we have e mixture of saturated vapor and iid entering the tank. Let ¢= the catering ual, i, vapor vapor +iguid) =. An energy balance 3s before, yes ¥=(@"7T)- Mt) reste U-a HC,For the case where P remains constant, X= Ofor any Z. Thus 7" be found as and the critical quality may KIC /OH, (4) This ease was covered inthe earlier development, (6) Using the expression derived in (), Oy g=054 Hy: q=036 18.12 Solution Let =KCI, B=LiCl, i= either Assume fs present as pe the melt at P,7 old in equilibrium wi af ‘ay Take total derivative of Inf foreach phase and expand as af (7x) with P = constant (H/F aT = U0, — TEV RELA + @ nse ds 9 win, ® Combine Eas (2) and @) @ins/aN), = (GH /RPVA + s(n 4/21), 3 Assuming ideal solution, fi) and F'= Hf, and let Hh HP aa, Then integrate fom pure (T= toa mixture wih <1 in, = (CAH /AUD)— 177) ® Atthe eutectic point with /= A or B, the temperature and liquid phase composition are the same: AH, =26,540 Jhmol and AH, = 19,930./mol 1, =1043K and 7, =883.K Solving, xy=%¢q)=0.338; T=768 K () The ideal solution assumption in () is obviously poor. If we assume a regular solution, Se" =0, and BGP = arn y= an 7a5*Phase Eauitoia Chaoter 1 187 =H? =H o ‘With te Bos. (1) and (3), equate, take logarithms and expand ding,+ din y= (4 - H/RP) aT © Integrate from x)= I to x; (Note y,= 1.0 at x;= 1.0) tn y= Ins, (Ht Y/R) TDL o where In 6 given by Eg (3). (HE Hyer) =— ns, (cr Hy/RT+ HE - H/T} @ ‘To find 7, we need an estimate of (Hf ~ Hf). We know from the problem statement that AH = srf-17,580~377 x5) Thus in extensive Form JNy/N?\17.580 377 Ny/N) Also, Vous =~ Nall Noblg = NEE HH) + NlHlp— Ha) Differentiate with respect to Ny at constant N,, T. and P to get AHfj and use the Gibbs-Duhem equation. ay © Simitary, Fi, ~ Hi; = 23 [-17,580-377655— 9] a) Using Eqs. (8) and (9) for B= Lic 1, (17,580 + 754 x9)/RT= ay and, with Eqs. (8) and (10) if A= KCL, i= A, 17,580 +377 (4g 5)V/RT=— nx, ~ AH,/RT-+ AH, /RT, 2) Solving Eqs. (11) and (12) together gives: x= 0413, P= 624K “These estimates are very close to experimental vas.158. Phase Equitas Chapter 15 15.13 Solution Let represent acetaldehyde and E ethyl aleohol. The liquid composition is constant at 80 moe percent alcohol. At equilibrium. fi=fe dnfi=ang Expanding at fixed ss i, ‘amit Wi, (ert eet oar loe i ee ‘implying, with ideal gases, assumed forthe vapor phase Soe inn @ Sth rae Thus Bq, (1) becomes: on 4 Asouming Vi>> VE and Vf~ RU/P, Ea. (3) reduces to jain, a He (BOL ain” From the data given, P may be determined as a funetion of T with P= ypP. Estimating the ‘erivative in Eg (4) with these data gives: Tie The=40 x 10" vo! 1.15 Solution Since there exists such a good correlation between anesthetic pressure (AP) and solubility in olive oil, it would appear reasonable to hypothesize that the anesthetic effect is independent of the chemical characteristics ofthe gas and depends only on the solubility. Iso, assuming deal solutions, P,=4P (3102 K) o In this crude analysis, et us relate P,, at 310.2 K to the boiling point (7,) and the critical point by +RT iwhere aT=T, Py=lbar arat, Py=P. then np, =(inP/- 7,17 where 1,=T/ Substituting Eg (2) nto Eq, (1), we can check the assumptions by using the given values of forthe gases with their T, Z.Pe, At310.2 K, the calculated values ofx which fit Eq (1) are shown below: Gas from Ea. (1) nat a Ne 8x10" : 32x 107 Ke 13% 10 @ Xe 13x10 * H, 12x10? nN, 3.8% 107 No 1x10? cH, Lox CH 13« 107 on, 13x107 Cyclopropane 1,1 10 cr, 95x10? Sk, 22% 10" CRC, 4.610 cul, 18x 102 Bihylether 2.9107 To calculate the x values in these cases, we used Newton's cule such tha: P. P.(exp) +8 bar15:10 ea Phase Equlioia Chapter 15 T.(exp) +8K @ where P.(exp) isthe experimental value of eritical pressure. Except fr fluorinated compounds and He, all gases give similar values of x. Choose x= 1.8 10 as an average value. They using this in Eqs. (1) and (2) for CCl, the anesthetic pressure i approximated as, AP = 4.9 x 10" bar, 15.17 Solution (a) Let solute gas be i, then By chain rule expansion D/P) abs (1/P) aP, o The last mon the RHS is zero because we are at constant partial pressure. Thus, using the librium criteria of equal Tugeites inf’ =dtof @ ‘Where B; is the Henry's Law constant for each gas, assumed here to be only a function of temperature, Substtating Eqs. (1) and (3) into the ferential equation (Eg, (2), we get with appropriate substitutions using Eqs, (9-111) and (9-113): [ewer a wer [lon eae] U erven (77R PPB, { fo| |Phase Equivia Chapter 16 15.11 Therefore, assuming Vjf>> Vand ¥* 1 (deal solution) and an ideal gas mixture fr the vapor phase, that iV" = RI P, Lg, (4) reduces to: BM, won| Re 6 But, forthe cissolved gas, at equilibrium Therefore, @ Substituting, into By.) A/D y wy © where {S(t ba ~ 341+ 6 SC bas) But PI bar; therefore we can rewrite the above expression as 5} $= (6 baw) — 5) +57 +50) ~ C1 ba} ” With, S(P) = S(t) = Rn, and “Rin, (ideal gs solution) ®) Therefore using Egs. 7) and (8), Ea, (6) bacon: 5D py. =U /BY/RTPUSE — 51 ba] = 9/)/NG or, with Bg. B/N, yy G-S/RT Thus, if¢—S> 0, the solubility increases with temperature 15:19 Soon (6 Fal ear ibe bene Tio AG" = Dv 30" = DN a, A =n ain D0, and LN AF =D Nn,15:12 Phase Eauitoria Chapter 15 Finds pcr e ‘Thus, ally values are equal, Next, and BE = BG =n yn @ AHO ye =@ny/2N,, e) since 3H, = BFE [Now combining Eqs, (2) and (3), @lmy/an, “ Untingy)] =n) tn T+ 3) 7 In4=fP. o © I Tiny, = 1.7 ny, e if y= 1.291300 K, then st 400 K, = 1.17 (© FromEgs. (1) and @) a Rmy "| Since RIn-j>0 n=! , BP=0 @ asi >0 co) n>1 <0 © In @) AS = 0, ie, the solution is regular (©) AS™> 0, i. theres les ord (©) As" < 0, unusual, perhaps could be due to strong interactions between unlike molecules in the solution than in the pare liquids; andPhase Equilibria. Chapter 15 15:13 15.21 Solution (@) and (b) In the early phases, the fugacity of the incoming steam is 1 bar; this exceeds the fugacity of the water inthe solution so condensation occurs. Choosing an open system consisting of the caustic soda solution, n,.=0, 3Q=0, and P Law gives ‘constant, then the Is aU = +3W + H,bn,,=PAV+ HBr, But Bn, = dN, thus dU = UdN + NaU = (H ~ PV) dN+ NUH —d(P¥)] =—PaV + Hyd (HH, aN= NaH Integrating, and 4-H, ‘Hy ~eathapy of saturated steam atone bat = 267 kg. Hse soon enthalpy’ at 3682 K and 45 wt fe NaOH = 451 Kkgsooton, Ths, we havea relation between #7 and. Alc, fom Figure 15.21 when the saaton reaches its oiling point toe bac te can obtain the temperature and wight fraction eau By atrial nd err method. the caustic solution attains the atrspherie boing point st 4089 K with x = 0427 (1 =5675x 10 Mg solution) “Thus W/N,=0.45/0427 = 1053 and 0.053 g of steam ae condense foreach 1.0 ¢ of original sclton ‘Any further addition of steam lead to futher dilution and cooling~-but, also, some steam leaves superheated at I bar. An energy balance in this case yields ll = HAN + Na =H, —H,, Bhs dN=5n,,~ 8,NdH + (H~H1,) N+ (Bigg H,) Bg Choose basis of 1g of original solution, then a NaOH balance yiclds N=O4S/r, dN= Thus, combining and simplifying (l= x0H/a) Hid) C_&, & ) ig der in he square bracket is found with the slopeimercept rule ftom Figure P15.21(6) on a curve which represents 7, asa function of Graphical integration then y elds ra a8 a funetion of x rams vented per grams condensed gram of original per gram of original % RES solution (©) You can discuss this situation from the equations derived, but us Stem is passed through the exchanger, since the area i inf ‘common sense. I the ite and the flow rte in in, the outlet temperature must be 100°C. Now draw a black-box Steam in a 100°C; les steam out at 100°C! Thus, we must be both dilating and heating simultaneously while keeping the solution at its boiling point ‘Conclusion: steam flow rates in and out must be equal; system has no change, around the syste1528 Solution “The criterion for stability fr binary constant and Pis (hte »> 0 with the imi of stability a hy/2ry » But, with y= RT Infy+ 20) and fy Yong fC Py =H) WARD Og/Dxpz,r= On fy/ Dep» =(8n(495/ hp tn to/Diph + Wy = (I/xp)bey(2 In g/t), p+ Thus, if (9 In p/p) p+ L equals zero, immiscibility occurs at some point in the range acl 18.30 Solution @ x, RMny, o AG" = RT hy + RTsyiny = C8 -+ 1,083 AG = Clay) by +) = Ce, @ and AG? = RTx;Inx, + REIN, @) Fortwo stable liquid phases to exist, the chemical potentials of both components must, bbe equal ineach phase. Given this model for AG", we can examine the stability envelope and decide what values of C will lead to phase splitting and a point of double tangency ‘on the G versus 4, surface at constant T and Pas illustrated in Figure 15.36 and discussed in Section 15.7. For phase spiting to occur, an unstable region must exist where (Gia 2 (Pa) <0. (ae <0 av \ jew with Gy, =4G = 46" +46” o© © Phase Eavionia Saing Eas. (2) and (3). the derivatives canbe obtained analytically, to give afer some simplification 6 2C> Ry, o Therefore inorder to ensure phase separation for all compositions C must be > 2RT. ‘he boundary between unstable and metastable tates isthe spinodal which sa limit of scabilty where (asa) con ® |e ae Ung 2a (60 defn the temperate long the sind 2 Rr, i Ate rita point he id derivative Gy =O as we (aac... 2c; sewn, aRTN, (aM OE a cagF aa row 2% (35-)-RT=0 0) At the critical point, 7=7, and x, =x, ‘composition, therefore solving for 7. 0.5 (symmetric mixture of uniforra phase e ay18.31 Solution @ © Ac equilibrium along the Solid-vapor coexistence curve fae) = Mae TB WV) o Assume Dv >v 2) Vapors ideal, W = R1/P 3) Alig = constant Then, Eq (1) reduces to dP, _~Allay aD), ® From the information given inthe problem, AFlay= GHIS)(R) = (3115)8.314) = 25,898 Jmol @ [Now to estimate the vapor pressure of liquid CO,, assume 4) Alyy =H! ~ Ht and Atl, = HP are constant Then Mag = Atay AH, ‘and we can write the Clausius-Clapeyson equation for L-V equilibria 25,898 8330 17,568 Jmol ® similar to Ea, (3) (a Alay a aT) |, “Matching the vapor pressute atthe tiple point and integrating 0 find Pt we get Bel P= -S6.2°C) =P (P=862°C)= end Sigg + 16| = 5.137 be Keo,Phase Equliona Chapter 15 ifthe solute has low volatility fh =i, oe C0 » Using a afte i appotch expanding dain cach phase asa futon of T;P, and eo liquid only) we get with C= CO, a subset ~i- Ht) ee 5 9) In general fm yaeft ay buasa fist approximation we can assume an ideal solution with = 1.0 and Fé = Hf sume tha the vapor phase isan ideal gus with V">> VE. Now Bs (10) simplifies Mla gpa? a ep 2 ay, ) me pram integrating, over appropriate Tins from x, = 1 eS ea sLT ke | +n x, (13) R(T _ » With s.=1 =a, T, we can estimate the decrease in vapor pecs ine Wn Te)= Py eT.) (1-3) Paya T,)~ Py AT.) =P, =x, 40 the decrease i linear in mole fraction for an idea solution. For values of x, hat are small < 0.01 this is avery reasonable approximation. The integral approsch using Eq, (15.97) asa starting point will give the same result 15,32 Solution ‘The Same approach that was used for Problem 15.31 canbe followed here. Basically we are ring to estimate te biting pont elevation resulting rom adding sa to wa ba. For this constant pressure case, for liguid-vapor coexistence at equilibrium, ffs! (pare water) “Chapter 5 15-19 ing as dn asa function of Tan , imi only) Hat ae Tl aa | don ® Assume with ft = pat 1) idea! liquid solution, y, = 1 and Fy = Hy 2) HY — HE = Ally =constant 4D) [4 eo a .? Laz (5) y However, x, =1—2xe if we assume thatthe salt i fully dissociated into Na" and CI ions. If TT and x, is small e saan [Now lets substitute values Rr er? o BL) Pd (8.314)373.15 >= BADD 1/—) 18_/mol AT, =268 (2x) =53.6., chieve 1°C increase in oiling point, x, =0.019 or if NaCl is used then the wt.% would be __(0.019)(58.5 g/mo x 100% (W19)S8.5 g/mol) + (0981)(18 g7mo}) allon pot of water weighing about 8 lbs., you would have to add 0: the hypothesis is wrong. o a Bs) 0% NaCl 92or about 6% ib, of salt! Clearly1833 Solution e BEAN nO) +N In + 4 870% W, + rv o where, with G,= G? for pure component i @ ® and, asa nf ana -09-[1 a =nr| a a3 7Phase Equliia Chapter 1824 (©) Given the general stability extra Yim o ‘where m= +2. Thus for binary system, m=2+2=4, yy>d o If yx = 04S, VM, ND), then ® Since the tial point is onthe spinodal curve (&c) Aso, athe crcl point With rer simpson: (@a) i vinta rt \ (10)1522 Phase Equi Chapor 16 For polymer systems, takes the pace of ss the appropriate variable to consider, ‘equations satisfied atthe eritcal point ars so the 190. ay «wy or with (13) as (16) (6) From Ea. (16) ay Inserting as)Phase Equitila Chapter 15 1523 Qe Solving this quadratic equation for y yon? +y—n1-y)=0 a) (20) en Now using Eg. (17) Note as r=, 1/r—+ 0and 7,9 1/2 wi @ ol yo i in aac 1000 slope 500R_1 intercept == «+ (spe) From Figure PIS.3() he dt ae consistent wth Eg, (23) but the parame values v0 wipe = SOK 21s 2519 sre not consistent 4834 Solution (@) General equilibsium criteria applies forall components in all phases. e Bef i=Borw oing that there are atleast 2 phases present the phase rule says Font2-m24-2=2 a ‘There are wo (or less) degrees of Ireedom, so its going to he necessary wo fix Tand P to specify the componition ofall phases. As T and P are increased from 10°C to 350°. and 0.1 MPa to 25 MPa. The types of phases prsent may vary from a normal VLE type system to SCW-L or SCW-V type system. There are many approaches to this problem’ Case I~ nonsideatties in all phases (high P region) Assumptions and approach: 1, Solubility of Bin asy Thus, =m consisting of liquid water (w) and a vapor rich in benzene eo f=fe 2. Cue EOS describes the vapor phase mixture prope 3. Liquid solution model NRTL or Wilson) describes the liguid aqueous phase 4. Vapor pressure data available for water and benzene as af(7) and Vf (or liquid density) known f(T, P) erative solution required for each T and P specified 1, Estimate fy’ and / using EOS to evaluate 9” Y= 1%) 9 HEAT Py vp (fae RT) 6 w= (8) Bee 2. Bsiimate ff and ft using AG*™ (solution model to evaluate) : eee 6 B= noanrn ry snl ar ’ LeutirD een, a (i) Depending on P, the Poynting correction may be negligible, {ii $, oF can be estimated dreetly from EOS but will most likely be 1.0 unless high pressures and temperatures are involvedPhase Equiloria Chapter 15 1525 e@ 3. erate onthe yd. goesses uti \fa fe se o lef ovhee eis some level of tolerance, Moe elaborate algorithms could be used to get new guesses of yy ad. based on old vals. Tn this particular ease, tore wil be exons ‘whore significant no-idealites are present in vapor and gui phses Case 2~ Vapor ideat-liguid non-ideal (low P region) yP=p,=4s,Pi Cevised Raoul’s law) 6 390°C liquid and vapor streams starting with a25°C, 25.5 MPa feed stream may be too larg tobe practical (4) "et down” system to eo! off he approximate ~£0% NaC liquid solution may be lficalto design since solids are present 15:6 Solution ‘Assi (1) ideal gas phase, since vapor pressures are low, Y = 1.0 (2) ea solution in iguidphase, f= L0 and F= Ht, i= p oro 6 Poynting comets for solid an Tau phases ae negligible (@ pare sti pases ff =f and ff Therefore a -L equilrium condiions for paracresot Sotasiewsiah . where p = pars-cresol and o = ontho-cresol. Furthermore along the vapor pressure curve for S-V coexisence for pare pars-orontho-cresol where Py,» =/(7) and Py, «= (7) af ad =f ® so at some specific Tand P =O TP, prado He ge] @) ‘The fugacity coefficient 9,8 seto LO by assumption (1) and te exp tem it th Pyating cometon which we sett LO by astumplln 3). Staring with Eg, (1) we can now use Ea. 3) testa f orf Tiaddion, we can follow an analogous aprosch to estimate the pure component gud phase Ngacity ftom the L-Vecensence data proviced in the vapor pressure equation with these simpleton: 5 Pnpm Pin and =P om Pe © “aking the In ofboth equations and using the integrated forms ofthe Clageyron equations provided inthe problem statement for expressing P,,, (7) and P,,() for both L-V and S-V coexistence We can solve forthe eutectic condition where both emperatires are the same, T= 7, therefore we have 2 equations and? unknowns: ing=in PE —inPct and nat = tn Pht InP, o Tas Ing = 22.42 ~ 4690/(7,~ 112) ~ 1620+ 3479/(7,~ 111) ane ing’ in(h ~¢) = 22.32 —4536/(7,— 108) ~ 15.91 +3308/(7, ~ 108)1838 Solution @ © Avequiibrium the are equal Using the fugacity coefficient and Poynting correction to express either fugacity at a specifie T and P and assuming that slid caffeine is pure. (x= 1), then = OT Pied Phat aff el ) H=WsfP=Ur Pye a quating Eas (2) and 3) we ean solve directly forthe solubility (y) in the supercritical CO, pase Given tat the vapor pressure of slid caffeine stow, 4 (, PS) = 1.0 11 Problem 134, we estimated critical constants and for pure calfeine using molecular group contributions, This, we can use the PR EOS writen forthe binary CO,cafeine rine to estimate (7, P, ). Te other information provided in he problem statement allows us estimate vy, Vp!) 194.2= 6.334% 10? mmol login PE? =-S781/7+ 15.031 The PR EOS form for fis given Chapter 9 by Ea. (9-144) using the standard mixing rules that apply to the PR BOS given by Eqs. (3-27) - (9-30). FORTRAN cose was ‘waite to selve for (Eq 4) asin the PR EOS to estimate 8 for assumed vals of yf at specific values of T and P. This involved an iterative approach with the sum of Squared errors (SSE) between experimental and predicted y, used as an objective function to find an optimal binary iteration parameter 8, where SSE = ®ycve= [Onesfor pressures ranging from 150 C0 330 bar, was minimized by selecting 8, Results follow for the following specific set of critical constants and 1 for caffeine derived using the group contribution methods of Chapter 13,¢. see Problem 13.4 T.=872K P= 41S bar @=0898 ‘The optimal 6,=4, was found 10 be 0.059 where excellent agreement between experimental and predicted solubilities was observed, Asan alternative tothe FORTRAN code, MATHEMATICA or MAPLE could be used to iterate on in Ea (4) and 0 locate an optimal 8,