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Sandler

ejercicios

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Juliana Atehortua
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5348 Chapter 10: Vapor-Liquid Equilibrium in Mixtures PROBLEMS FOR SECTION 10.2 102-1 For a separations process itis necessary to deter ‘mine the vapor-liquid equilibrium compositions for mixture of ethyl bromide and m-hepiae at 30°C. At this temperature the vapor pressure of pure ethyl bromide is 0.7569 bar, snd the vapor pressure of pre mheptane is 0.0773 bar. 1. Calculate the composition of the vapor in equi- Tibcium with a Tiguid containing 47.23 mol % ethyl bromide at T = 30°C, assuming the So- Jatin i ideal. Recalculate the vapor composition in pat (a). a> suming the solution is regular. The regular solo- tion parameters are Brealeey™ Ethyl bromide 39 tlepane a «. Recalculate the vapor composition of part (a) us- @ _,, ingihe UNIFAC mode 4. Recalculate the vapor composition of part (a) ven that a vapor of composition 81.5 mol % ethyl bromide is in equilibrium with 2843 mol " liguid ethyl bromide soltion ata totl res sure of 0.3197 barat T = 30°C 10.2.2 A vapor-liquid misture of furfural (CsH4O3) and water is maintained at 1.013 bar and 109.5°C. Ii abserved that at equilibrium the water content ofthe Tigui is 10 mol S and that of the vapor is 81 mel 5. The temperature of the mixture is changed to 100.6°C, and some (ost not al) ofthe vapor con- nse. Assuming tha the vapor phase is ideal, nd the Tiguid-phase scivty coefficients are indepen- deot of temperature but dependent on concentration, compute the equilibrium vapor and quid composi tions atthe new temperature Data: 10.23 In this section it was shown thot if the equlb- lum pressure versus mole fraction curve fora bi- rary mixtare hasan imerige extreme value at some 1024 102-5 liquid-phase mote fraction (Ke. if (@P/@x)y = 0 for 0 -< x < 1), an azeowope has been formed a that composition. Show that if at constant pres- sure. the equilibrium temperature versus lguid- phase mole faction has an interior extreme value (oenif @T/2x)p = OforO . The mixture i regular, The mixture is described by the UNIFAC model 4. The activity coefficients for this system obey the van Lane equation and the datum point at "ea = 0.615 is used to obtain the van Laar pa- ‘Compare the results obiained in pans (a)-(@) with the experimental data in the following table es yea Prtban) ° 0 02939, Dox 0.1965 03613 doer 0.2885 0.3953 0218 © 03370 ase 03141 03625 o.atza oais0 0382 0.128 05199 0.4065 0.4100 0528 04101 0.4093 915s 043834028 07087 0475103891 08102 0.54556 03615 09193 © 07078 §~—03036, osssl 081 oT 1.00 1.00 o2s2i Sowre: 1 Brown and F Smith, Ast. ‘Chem, 7,264 0954), Also conipaie the computed van Laar coefcients wth hose given in Table 7.5-1. ‘The system tolvene-aceti aid forms an azeotope containing 62.7 mol % toluene and having a mini ‘mum boiling pont of 105.4"C at 1.013 bar The fol- lowing vapor pressure data are available: 1026 10.2. Low-Pressure Vapor-Liquid Equilibrium in Nonideal Mixtures 549 > (ban) TCC) Toluene Acetic Acid 70 02699-0813 300386302697 300539503916 too 0792903561 0 ag ores 071.0133, es is 10133 9 = 10386 ‘2 Calevlate the van Laar constants for this 35+ tem and plot Inj and Inyq versus sy. This is ‘most easily done using the MATHCAD work sheet ACTCOEFF on the CD-ROM accompany: ing this book and discussed in Appendix B.1T ’, Assuming thatthe activity coetMeiens (and van [Lear constans) are independent of temperature ‘over the limited range of temperatures involved, evelop an.ry diagram for this sytem at P= 1.013 bar. Compare this with the sy diagram ‘hat would be obtained ifthe system were ideal «Assuming the activity cseffcents are indepen= ent of temperature, develop an sy diagram for this system at = 1,013 bar using the UNI- FAC model, and compare the results with those ‘obtained in pat (b). - ‘The ilustraions of this section were meant to demonsirate how one can determine activity coef- ficients from measurements of temperature. pres- sure, and the mole fractions in both phases of 1 vapor-iquid equilibrium system. An aliernative procedure is: at constant temperature, xo measure the total equilibrium pressure above liquid mix- tures of Known (or measured) composition. This replaces time-consuming measurements of vapor- phase compositions with a more dessled analysis Of the experimental data and more complicated eal- a, Starting withthe Gibbs-Dubem equation, show that at constant temperature, at Dn diatar) and, For a binary mixture, year Sua) dy _ dinP nG= dda di since PVS/RT « 1. i. The equilibrium pressures above various mix- tures of earbon tetrachloride and e-heptane st 50°C ae given in the following table. Mole Perent of CCl. inthe Liquid Pressure (bar) 00 Duets 332 0.1956 533 o2i3t ina 0230 3024 0.269 35.14 0.2765 43.24 0.2963 5012 03007 57.00 03263 64.96 0305 7323 03616 81.26 03765, $9.92 03939, 96.49 0.4085 100.0 oai13 ‘Source C.F Sithand E,W. Engl J.Am. Chem ‘Soe, 2646 (1929), Develop the xy diagram for this system, and compute the liquid-phase activity coefcients of cstbon tetrachloride and mheptane. ce. Develop the -y diagram for this system using the UNIFAC model 10.2.7 For vaporlguid equilibrium at low pressure (so the vapor phase isan ideal gas) a. What i the bubble point pressure ofan equimo- lar ideal lgui binary mistre? 'b. What isthe bubble point vapor composition of ‘an equimolar ideal iqui binary mixture? ‘© Whats the bubble point pressure ofan equime- Tar Tiquid binary mixture if the liquid mixture is nonideal and described by G* = Aza? 44, What is the bubble point vapor composition of fn equimolar liquid binary mixtore if the uid mintuc is nonideal and described by @* Anu? 102-8 The following vapor-tigud equilfium data forthe rpentane-ecetone system at 1.013 bar were ob- tained by Lo, Beiker, and Karr [J Chem. Eng. Data, 7,327 (1962). 1029 10.2410 10.211 102.12 102.13, 10244 550. Chapter 10: Vapor-Liquid Equilibrium in Mixtures (an) » ee doxr 0108 49151560 O80 ost 0307 45.76 13970703 GI 047s 3958 L146 OSI 0210 0550 3667 10360493 0292 0614 343501960 0as3 040s 0664 ©3285 0913, 0425 0503 0678 3235 0903 04al 061 071 3197 O88? 0413 078 0739 3193 0880 0410 0869 0810 3227 0896 419 09530905 3389 O94 Oats” a, Are these data thermodynamically consistent? bh Determine which of the activity coefficient models discussed in Chapter 9 best fs these data Tiss most easily done using the MATH. ‘CAD worksheet ACTCOEFF on the CD-ROM accompanying this book and discussed in Ap- pendix B.IL Use the UNIFAC model to prediet the vapor iid behavior ofthe system in the previous problem, ‘nd compare the results with the experimental aa. Estimate as best you can, the vapor-liqud equilib- rium coexistence pressure and the composition of the vapor in equilibrium with a quid containing 20 mol % ethanol, 40 mol % benzene, and 40 mol Se ethyl acetate at 78°C. ‘The experimental data fr the hexaluorobenzene- benzene mixture in Table 10.28 and Fis. 10.210, Show a double azeotrope. Test the ability of com ‘mon thermedyramic models, such asthe equations ‘of Wilson and van Las, and the Reclich-Kisterex- pansion to fit these data. Also, est whether the UNIFAC model prediis a double azeouope for this system, (Note thar hexafluorobenzene is also known as peruorobenzene, and is refered 1038 such in the Propery program refered tain Chap ve6) Determine whether the data in Table 102-1 saisty ‘the Gibbs-Duhem integral consistency est Derive Eq, 10.2-26 forthe constant-pressure ebul- liomere. Using the following data, estimate the total pres- sure and composition of the vazr in equim ‘with & 20 mol % ethanol (1) solution in water (2) 38 78.15°C. Data (at 78.15°C): ‘Vapor pressure of ethanl (1) = 1.006 bar 439 bar ‘Vapor pressure of water (2) wo245 lim, 7) = 77% = 1.6931 lim, 7a = 73" = 1.9523, In vapor-tiquid equilibrium the relative volatility efined 1 be the ratio ofthe separation or K ‘tor for species ito tha for species j that i, Ki _yls ar In approximate distillation column calculations, the relative volatiliy is sometimes assumed 10 be 4 constant (independent of composition, temper- ature, and pressure). Tes this assumption forthe ethanol-ethyl acetate system using the following ata AT Inj; = 8.1634} KI/mol a PS = WP 10.2416 1247 4728.98 13.4643 Phe] bar 357058 4 10.4575 Based on vapocliquid equilibrium ta, some authors have claimed that the benzene (I) cyclohexane @2) mixture is described by ra ‘where A (mol) = 3780 — BF for Tin degrees K. a. Derive expressions forthe activity coefiiens of benzene and eyelohexane. », Determine the enthalpy and entropy changes on ‘mixing when | mole of benzene anid 2 moles of cyclohexane are mixed at T= 300 K and con- stant pressure. «. Given the following vapor pressure data at 320K, Ps = 0.3203 bar and P2™* = 0.3218 ‘ar, determine the bubble point pressure of the liquid in part (6) at 7 = 320 K, and the-com- position ofthe vapor in equilibrium with that Tigui ‘The relative volatility of component 2 10 compo- rene 1s defined 1 be Ans ce . nis, : 1. Develop an expression forthe relative volt. ity fora mixture described by the one-constant, ‘Margules equation. Discuss how the relative ‘olatlity depends upon temperate, pressure, and composion, b, Whar would be the relative volality at low pressures ifthe two components form an ideal 10.2 Low-Pressure Vapor-Liguid Equilibrium in Nonidest Mixtures 551 mixture, and how would the clave volatility in this case depend on wemperature, composi- tion. and pressure? 10.218 a. Develop an expression for the vapor-phase sole fraction of species | in an ideal equimo- Tarbinary mistoe at low peessres in terms of| only the pure component vapor pressures, 1, Repeat the derivation of part (2) for nonieal mixture described by the one-constant Mar- sles equation. 10.2-19 a, Develop an expression for how the bubble point pressure ofa binary mixture changes with tem perture at constant composition. b, How does the result for part (a) change iTone of the componens in the mixtures has such alow ‘vapor pressure a tobe considered imvlatile? -Enimate the vapor liquid equilibrium of m-hexene and toluene asa function of composition at 7 = "75°C using regular Solution theory and the UNI- FAC made, 10.2-21 After an extesfction reaction, iti necessary «© ‘separate the produet methyl acetate from the un- reacted methanol to obiain both components at ‘high level of purty. eis kngun tha at 20°C, {his system forms an azotrope with the fallow ing properties! yy, = Souq = 0.754 scan = dyon = 0.266, and P= 193.58 mm Hg. "A process engineer has suggesed thatthe Way to get two relatively pure components is 19 use ‘so distillation columns operating at differen con- tions. The fst columa would be operated to get one ofthe relatively pure components and the axotope, This azeotrope would be fed into the second column operating ata higher temperature, SOC. By this argument. the higher ermperature ‘would shift the azeotrope, so that the products {fom the second columa would be the other pure component and the new azeotope (which would then be fed back to the first column), To deter mine whether this proposed process is possible, compute the azeetopic composition of a methyl acette-methanol mixture at $0°C. For simplicity, sssume that te parameters in the activity coe cient you use are independent of temperature. “The pure component vapor pressures ae af lows: o 157.630 Josie AEX (rum Ha) = 7.08824 — . 152.271 Jogi Pg (He) = 8.0809 — =a 102-22 102.24 ‘The octane (I)-itaethy! methane (2) mixture has been studied at 50°C. From vapor pressure and calorimetric messorements the folowing in- formation is availble o 302 1/mat HS = 335,23 nol ee Ia aee where AL Bi 1 9am3 310029 G6 292508 3H —3757 with Pin bar and Pin K. 8, Caleulate the composition ofthe vapor that iin esilibriom with woetane-tersetyl methane mixtures at 380 K. In this calculation assume thatthe activity coefcients are independent of pressure b, Repeat the calculation above at fixed i pressure of 380 mm Ha, ‘Repeat parts (2) and (B) using the predicive UNIFAC model Eichingee and Flory (Tans. Fora. Soc. 64,2053 2060 (1968) report te following dara forthe ae- tivity of benzene (ap = 572) in poyisobuty Tene (MW = 40 000) and 10°C as a function fof the mass ratio of benzene to polysobutylene, mah ncfrime #2 = 1876 ass! 03811 oss43 0.9585 + 0291 0.8388 Using the data in Mustration 10.27, compare the predictions ofthe Firy-Huggins theory using x 110 with the data above, ad compute the equi- librium partial pressute of beazene over benzene polyisobutylene mixture Eichinger and Flory [Tran. Farad. So. 64 2061— 2065 (1868) reported the following data Tor the souvity of ejelohenane (ae = xc7c) in poly isobutylene (MW = 40 000) and 25°C asa fane- tion of the mass ratio of eycloexane to poly- isobutylene, me/mnw. 0958 | 0307 04937 oan | 022 — osi0s 0736 | 0198 05537 o7e3 | o17 062s Determine the value of the Flay x parameter in the Plor-Huggins model that gives the best fit Of the data above, and compute the equilibrium anal pressure of eyelahexane over eyelshexene- plyisoburylene mistoes 5 Eichinger and Flory (Tran. Forad. Soc. 64, 2066~ 2072 (1968) reponed the fellowing data tor the aetvity of npentane (op = seye) i posisobuty- lene (MAY = 40 000) and IOC 28 a function DF the mass ratio of n-pentane to polyisobutylene, nonin. Impfoina 9 = 207% [mem ras oso” | 02 a4 09263 | 0.153 0363 osaos | 00786 269-0803 | onze Determine the value of the Flory parameter in the Flory-Huggins model that gives the best Bt of the data above, and compute the equlld- rium panial pressure of pentane over pentane- palyisobutylene mixtures. 102.26 ‘The paral pressure of water above aqueous hy- * deochloi aca solutions ean be represented by 2 logy P= A= 7 7 where P isthe pressure in bar and Tis the temper ture in K. The values of A and B are given inthe ‘able MHC a 2 0 62357 2295; 20 6.103 70. 2334 30 612610, 2422 0 6.468 16 2681 Sours: RH. Per D. W. Gree, and J. 0. Mat ‘ney, ed, The Chemica! Engineers" Handbook, th (2 MeGeaw Hil, New York (1985). pp. 3-68. “The vapor pressure of pure waters given in Prob lem 7.12, Compute the activity coefficient of wa- Chapter 10: Vapor-Liquid Equilibrium in Mixtures ‘erin each ofthe hydrochovie seid solution in the table at 25°C. (Hint: hydrogen chloride canbe as- sumed 1 completely ionize in aqueous solstion) ‘The Following dats forthe paral pressure of water vapor over aqueous solutions of sodium carber- se st 30°C are given in The Chemical Engineers” Handbook Si ed. (R. H. Pery and C. H. Chilton, I, Now York. 1973) pp. 3-88. 0s oo 428 416 405 395 384 371 352 ‘Compute the setivty coefcient of water in each of these solutions. (Hint: Does sodium earbonate Jonize in aqueous solution?) 10.2-28 In this ection it was shown thatthe excess entropy and excess enthalpy can be derermined from var fous temperature derivatives of the excess Gibbs fenergy. These and other excess thermodynamic functions can also be computed dicetly from Gerivatives ofthe activity coefficients. Show that ina binary minture the following equations can be used for such caleutations: e) ainn , , tay = Rx Iny, +42 Inys) " OP seamen) ar? (2th, Bn) [Note that inthe activity coeficien derivatives ll ‘variables from the set T, Px, other than the one 102.29 10.230 102.31 102-32 10.2 Low-Pressure Vapor-Liguid Equilibrium in Nonideal Mixtures $53, being varied, are fixe, “The following vapor-liqud equilibrium data have been repored® forthe sytem I,2-, Calculate the excess Gibbs energy at each com- position © Obtain values of the van Lasr parameters that best these dats. ‘A binary liquid solution, having mote traction x of ‘component 1. is in equilibrium with a vapor that thas mole fraction v ofthat componeat. Show that for thie enixture the effect of a change in temper- lure on the equilibrium pressure at fixed liquid ‘composition is approximately (28) =e ‘Where (gaa 6 the heat of vaporization of y ‘moles of component and (I = y) moles of com ponent 2 from a lrge volume of flution, Extmate the equilibrium pressure and isobutane vapor phase mole fraction a8 a function of liquid composition forthe iscbutane-furfural system at [378°C At ths temperature the vapor pressure of {urfural is 0.493 KPa and that of isobutane i 490.9 Pa. (Hine: See lstration 1-2-2.) Polyethylene of molecular weight 2800 is to be isslved in compressed ethylene at 10°C. Astum- Ing that a6 a result of the similarity of exhylene to polyethylene, thee is no enthalpic interaction between these species, estimate the excess Oibds energy and activity coeficients of ethylene and polyethylene asa fonction of composition. ‘A mixtire of 8 mol 9 acetone and 20 mol % war teris tobe ttnspored in pipeline within a chem: ical plant. This mixture canbe ransported as ether A liguid or gas. A reciprocating pump would be used with lig bid mixture, Because of vapor lok, this pump wll cease functioning if any vapor is resent Compute the minimum pressure that must be rmainiined at the pump inlet shat no vapor is formes when the liquid temperate is 100°C. >, A centilugal pump would be used witha gas mixture. To prevent erosion ofthe pump bades, ‘only vapor should be presen. If the pump ef Fuent is 100°C, compute the maximum pump eluent pressure s that no liquid is formes. Data ‘Temperature CC) 3667861130 Vapor pressure of acetone bar) 1.013 2.026 5.065 10.2-34 The figure that follows fr the ethanol + water sy tem isan unusual one ia tha it shows both vapor- Tiguid equilibrium and the enthalpy concentration iagrams ona single pot. Tis is done as follows ‘The lower collection of heavy lines give the en thalpy concentration data forte Tigi a various temperatures andthe upper collection of lines is ‘the enthalgy-concenation data far the vapor, each attwo pressures, 0.1013 and 1013 bar. (Theze are also enthalpy-concentration lines for several other {emperatures) The middle colletion of Hines con- set the equilibrium compositions of liquid and vapor. For example, ata pressure of L.O13 bar, a saturated vapor coniaiing 71 wt 6 ethanol with tn enthalpy of 1535 KK isin equlbriam with 2 Tiguid containing 29 wt % ethanol with an en- thalpy of 315 k/kg at a temperature of 85°C. Nowe also that the azzotopes that form in the ethanol + ‘water system are ingested a each pressure. Consider the vapor liquid equiibvium discussed above, in which 90 porcent of the mixture by ‘weight Is liquid and 10 percent is vapor. If the pressure on this mixure is now redvce to 0.1013 bar by passing though a Joule-Thomson expan sion Valve, what are the compositions of the va- ‘or and liguid phases in equiur, what i the R.Eng an 1 Santer, Cham rg. Dt. 29, 156(1980). ‘354 Chapter 10: Vapor-Liquid Equilibrium in Mixtures ass Sepnte pa 01 seeker ate 10 / von ona 4651 ms Fewaing 0a ee we Wei erent tana equilibrium temperature, ad what are the weight fractions of vapor and liquid? 10.235 A binary mixture of components 1 and 2 is in ‘veportiquid equilib. At 90°C and 1.8505 bar pressure, a vapor of ‘composition yy = 0.3767 coexists with alge uid of composition 1 = 04, Use these data to determine the van Laar parameters for this hb, Determine whether the mixture hasan zeotrope at 90°C, and ifs, determin its com- postion and whether ii a maximm-pressure for minimum-pressure ezsctrope. Obtain the Pox-y and x-y diagrams for this sys tem at 90°C. 4. An equimolar mixture of species 1 and 2 at inialy very Yow pressure is compressed st ‘constant temperature of 90°C, At what pres GQ) sure does the fst drop of igi form, and what “The enthalpy concenuation diagram for ethanol + water sytem, The reference states are the pure liquids a O°C. Based ‘on detain Chemical Process Principles, Port I: Material and Energs Balances, 2nd ed. by O.A. Hougen, KM, Watson, and R.A. Raget, Joha Wiley & Sons, [New York, 1954, p. 327. This igure ap- pears as an Adobe PDF file on the CD- ROM accompanying this bok, and may 10) beenlarged and printed for easier reading and for use in solving problems. Rasps is its composition? At what pressure does the last bubble of vapor dissppesr, and what was its composition? Data: The vapor pressures of the componenis axe given by toate R™ for pressure in bar and T in K, where Ay = 4.125, 8; = 1500, Az = 5.000, and Bip = 1750, : 102.36 The equilibrium ttl pressures above liquid mix- tures (that is, P-T-r data fr the system ethylene ‘bromide and I-nizopropane at 75°C are given in the following able. Develep an x-y diggram fortis system, and com- pute the Liguid-phase activity coefficients of ethy- lene bromide and I-aiopropane. Use the UNI- 10.2 Low-Pressure Vapor-Liquid Equilibrium in Nonideal Mixtures 585 Mole Percent ‘Mole Peccent of Ethylene cof Ethylene Bromide Pressure | Bromide Pressure Liquid (bee) cy 00) 01333 0.7 298 0.1556, uma 3520568 oma, 535 0.1397 0.1699 1550 0.1659 0.1652 26.98 ars 0.1596 39.95 0.1760 Sowee: 1 Lasher W.B, Bue, and W. H, Par, J Am. Char Soe. 66, 2622 (194, TPAC model to predict sctivity coefficients at other composions. How do the two ses of activity 2o- efficients compare? (Hinz: See Problem 102-6.) 102.37 Use the UNIFAC model to predit the vapor. © 102. liquid equilibria for the benzene + 224 trimethylpentane system at 55°C, nd compare the resulis with the experimental data in Illustration 10248 and with VLE predietions using the Reg- bar Solution model 38 Use the UNIFAC model to predict the veporiquid equilibria for the acetone + water system at 25°C, and compare the results wit the experimental dat that ean be found inthe DECHEMA cata series. 10239 The following vapor-liquid equilibrium data have ‘been reported” for the system water (1) + 1 sioxane (2) at 323.15, P (ams) * * 120.49 ‘0.0000 0.0000, 140.85 0.0560 ~ 0.1920, Isis 0.0570 02680 1917 0.1700. 03450 16457 02160 03830 165.65, 022980 0.4030 16789 03660 04250, 16778 04400 asa 167.79 oe6o 0.8460 16795 04840 08510 166.84 0.5390 04550, 165.48 0.620 0.8660, eos 0.7490 04950, 155.16 aio 0.5430 126 0.3900 0.6040 11476 09670 0.7950 92.31 110000 1.0000 2. Compute the activity coeficints for this sys tema each ofthe reported compositions. ba, Are these data thermod+amicelly consistent’? © Plt the excess Gibbs energy for this system as ‘function of composition, Determining the activity coeficien! parameters ‘values in several ofthe following problems is most easily accomplished using the MATHCAD work. theet ACTCOEFF on the CD-ROM thet accom nies this book 102-40 Determine the parameter values in the «wor ‘constant Margules equation that best fit the dats (of Problem 10.239 10.241 Determine the parameter valves in the van Laar rode! that best ft the data of Problem 10.2-39 10.242 Decermine the parameter values in the Wilson ‘model that bet fit the data of Problem 10.239 Determine the parameter values in the NRTL mode that best fit the data of Problem 10.238 Determine the parameter values in the UNIQUAC. ‘model that best ithe data af Problem 10.23 § Compare the predictions of the UNIFAC model ‘vith the data of Problem 10.239. ‘Tue following equilibrium pressure data for the system water (1) + [dioxane 2) a 353.15 K have been reported! P (mmHg) s P team Ha) * 3828 ‘0.000 S58 0.600 4960 0.100 569.5 0.700 3265 0.200 5500 .g00 3565 0.300 5015 0.900 smo 0.400 351 1.000 5765 0.500 Fit the P versus xy data with a su ‘mia. Then use the syathethic method; that is wse the equation developed in Problem 10.26, (1=s) dy dine Oa Was de to estimate the vapor compositions a each of the reported liquid-phase mole factions Determine the parameter values in the two: constant Margules equation that best ithe P ver ss x data of Problem 10.2-46, and then use this activity cosfcient model to estimate the vapor phase compositions. Yo, Korn aa V. Vent, Ber Bunsenges Phys. Chem 81,752 (197, 55. Horna, RA. Setter nD, Drie, Are Chr So, Sk, 264 (1935). 556 Chapter 10: Vapor-Liquid Equilibrium in Mixtures 10.2-48 Determine the parameter values in the van Laar model that best ft he the P versus. dats af Prob- Tem 10.2-46, and then use this atvty coefficient ‘model to estimate the vapor phase compositions. 102-49 Determine the parameter values in the NETL model that best ithe the P versus x dta of Prob: Tem 102-46, and then use this activity coefficient model to estimate the vapor-phase compositions. 410.2:50 Determine the parameter values in the Wilson equation that best fit the the P versus xy data of Problem 10.2-46, and then use this activity coef lent model to estimate the vapor phase composi- 102.51 Determine the parameter values i the UNIQUAC model that best fitthe the P versus. data of Prob- lem 102-46, and then use ths activity coefficient ‘model to estimate the vapor-phase compositions 102-52 Compare the predictions for total pressure from Ge UNIEAC iodel wits the ita of Problem 102-46, 10.253 a. Joe Udel argues that iin a low-pressure binary rmixtre, Gee) have opposite signs, the sytem will have an azeowope: Can you simply prove or disprove his contention? (The simpler the proo. te be tex) b, Will the system for which, at 65°C, PE? = (0.260 bar and P= 0.899 bar described by = LIRT S82 have an szeotrope? 102-54 The following excess Gibbs energy model de- secs the l-propanal (1) + n-hexane (2) system Gh = RTE (Ac + Art) In the temperature range near 65°C the parume- ‘er values inthis equation are Ay = .867 and Az = 1.536. The vapor pressure of I-popanal at this Temperature is 0.260 bar and that of n-hexane i 0.399 bar ‘What isthe excess enthalpy of mixing of this system as function of temperature end com position? b, What isthe entropy of mixing ofthis system a5 2 funeton of temperature and composition? ‘. Obtain expressions forthe activity coefficients ofeach compound, 4. Obtain values for the infinite-diluion siviy coefficients for each compound inthis mixture Does this system have an szectrope? 102.88 Calevlate the boiling point of aqueous sodium chloride solutions at ambient pressure over the range from Oto 10M NaCI, tn this caleultion, use the following expression fr the vapor pressure of pare wate: oo in pr (7) = 13.149 — for temperature in K and vapor pressure in bar 10.3 HIGH-PRESSURE VAPOR-LIQUID EQUILIBRIA USING EQUATIONS OF STATE (¢-¢ METHOD) ‘The discussion ofthe previous section was concemed with low-pressure vaporliquid equilibria and involved the use of activity coefMicient models. Here we are interested in high-pressure phase equilibrium in fluids in which both phases are deseribable by equations of state that is, the g-# method. One example of the type of data we are interested in describing (or predicting) is shown in Fig. 103-1 forthe ethane-propylene system. There we see the liquid (bubble point) and vapor (dew point) curves for this system at three different isotherms. At each temperature the coexisting vapor and liquid phases have the same pressure and thus are joined by horizontal tie lines, only one of ‘hich has been drawn. The intersections of these tie lines with the bubble and dew curves give the compositions of the coexisting equilibrium liquid and vapor phases, respectively. Figure 10.3-1 shows some of the variety of phase behavior that occurs in hydro- carbon mixtures et high pressure. The lowest isotherm, 261 K, is below the critical temperatures of both ethane (7. = 305.4 K) and propylene (7. = 365.0 K). In this 11.2 Liguid-Liguid Equiitsium 621 TEC. Teva PROBLEMS FOR SECTION 11.2 11.22 8, Show tha if ewo liquids form a regular solution, the eres terperature for phase separation is arp 28 iy by Show thatthe composition atthe upper console temperature is Wis vin yyy ~y, and develop en expression forthe upper conso- luv temperature for toe seglar solution model. 11.22 Following is @ ponian ofa phase diagram for Wo liquids that are only patially miseible. Note chat ‘he phase diagram contin both the coexistence curve (Solid Tine) and a curve indicating the st tality limit for each phase lashed line) (it the ashed line represents the greatest concentration of the dilute species, extent of supersaturation, that can occur in a meiastabe phase) This linc is called the spinodal curve, Fora binary mixture foc whieh G* = Axyrz, develop the equations tobe used 10 ‘2 Compute the liquid-iqui coexistence line. 1b Compute the spinodal curve, Spins 11.23 The two figures below have been obtained from measurements ofthe excess Gibbs enerzy and ex- cess emhalpy for the benzene-CS> and benzene- CCl, systems, respectively at 25°C. 002 a4 a6 a8 o ‘8, Comment on the applicability of the regular so- lation model to these wo systems. b, Assuming thatthe excess Gibbs energy forthe CHa C5> system is temperature independent, cetimate the Upper consolute temperature ofthe system. Since the meting point of benzene is 5.5°C and that of C52 is ~108.6°C, wil iquic liquid phase separation be observed? . ALH6.3°C, the vapor pressure of CS is 1.013 bar fd that of CH is 0.320 bar. Willan szeatope ‘ecurin this system at this temperature? ‘The liquids perluoro-heptane and benzene are only pany miscible a eraperatues below their [ppet console temperature of 113.4°C. At 100°C one liquid phase is approximazely 0.48 mole frac ‘Son benzene and the ether 0.9¢ mole faction ben- zene (ee Fig, 112-3). The liquid molar volume of perluorosnheplane a 25°C is 0.225 mol. 622. Chapter 11: Other Types of Phase Equilibria in Fluid Mixtures 1, Use hese dita to compute the interaction pa- amer A ina one-constant Margules equation for the excess Gibbs enerey. Is the one-constant “Margles equation consistent with the exper mental ata? », Use the experimental data o compute the value ofthe regular solution theory solubility param ter Tor perfuero-mheptane [the value given ia ‘Table 9.61 is 5 = 6. (eaice)""), Is regular solution theary consistent withthe experimental aa? ‘The Gibbs energy for highly nonideal solutions can behave a shown here, Prove that liquid-liquid phase Separation will cccur in this system, and thatthe composition of the coexisting laud phases are d= termined by the’ two intersections of the common tangent line with the Gag curve, Points B and Care inflection pois on the Gibbs energy curve. What isthe relation of these points tothe stability ofthe cvexiting liquid phases? 127 ‘Show thatthe Wilson activity coefficient model of Ege. 9.511 and 95-12 cannot predict he exsionce ‘of wo ligud phases for any values of its parame: Polymer-polymer and polymersolvent systems sre important in the chemical industry, and typically the Flory-Huggins model is used to deseribe the activ- ity coeffiiens in such systems. Assuming the va ‘or phase is ieal, and thatthe vapor pressure of the polymer i negligible, 5. Develop the equations that should be solved for ‘he bubble-point pressure as a function of tem perature for polymer-solvent mixtures using the Flory-Huggins model. », Develop the equations shat should be solved fo the molten polymer-molten polymer liquid= Jiqui immiseibiiy region as a function oft perarure using the Flory-Hugeins model. ‘What data would you need to do numerical ealeuls- tions forthe phace behavior withthe equations you have developed above? 1128 129 11.240 2a 242 Eglin why the activity Ge 7) based on the pe component standard ss of asperiesin 0+ lion eannot be rete than ony Compute the cage of emperaies and compo- sions over whieh the copolymer polssyrene: aenloniile (GAN) and plymedyimeiscyate (PiNta) are mise i these polymers have be following properies. SAN has & molar volume, Yesgu OF LE 10" em? fmel. and PMMA has molar volume, Vyas 15% 108 em mo. The Flory parameter forthe SANCPMINA mince is sven by 1895 i where Tis K “The excess Gis energy fora mintre ie sven by G sna +or telnT) For this system 2. Find the expressions for ff, Sand CP 1b. Determine the range of valves ofthe parame- ters a,b and e that result i liquid-liquid que {ibum with only an upper consolute pint ‘Determine the range of values ofthe parame- ters a5, and e that result in iguidlquid eguie {ibrium with only a lower console point. a. Estimate the heat and work flows nesded to reversibly and isothermally separate an ‘equimolar mixture of two species into ts pore components ifthe excess Gibbs enersy forthe snistoreis given by Ga Aun where A Is independent of temperstre, 'b, Flow does the temperature at which W = 0 compare with the upper consolute temperature ofthe mixture? How would the answers to parts (a) and (6) change if A were funeton of temperature? The binary liquid mixture of nivometane and ‘nenonane exhibit liguid-ligid equilibrium. At TO°C one phase has nitromethane mole fraction ‘of 0.131 and the other phase hasan n-nonane role faction of 0247, At90°C the mole fractions are 0.214 and 0.0468, respectively a. Estimate the excess Gibbs energy of mixing at teach of the temperatures over ihe whole con- centration range (that is, extrapolate into the Yiguid-guid equilibrium region). a3 112 Liguig-Liguid Equilibrium 623 3, Extmate the exessenthapy’of mixing at 80 ‘over the whole concenvation range. Esiate the excess entropy of mixing at 80°C cover the whole concentration range, “The difsive ux is usually writen as j= -eD@, where D isthe difsincoefclent and i he oneeavation in ol so, cy she concen fon of species I in mol. Howeves when srt tem tis way is found thst D cepees on eon. cenicaton, Also, this relation incorety predits {hati «concentration giference exit besze8 to phises of eiferent compostion in eq tom, thre wl be a difasive fsx. To comet for these problems, ons can instead write an expres Sn fore five Ru in tems of grade in herves potent: Dees j= Oy hav Where Dp is assumed to be independent of compo ‘Show that D and Dp are related via p=o,(14 222) 'b, Find th relation between D and Dp i the sys- tem is deserbed by the one-consiamt Margules equation. ‘Consider the difusvity as described by the re sults in gar (3) and (b) in answering the ft losving questions: ie ithe difsing component 1 is at infite Aiton, what isthe relationship between D and Dot fi, How does D vary with composition 2 he Upper LL ertcal point of & binary mixe ‘ure? ~ fi, Describe the effect onthe value of D ifthe mixture exhibits negative deviations from Rout’ law ‘The bobble point ofa liguid mixture ofan alcohol and water containing 2.0 mol 6 aleobal is 90°C 1.013 bar The vapor pressure of pure water is (0.7733 bar and that ofthe alcohol is 0.4 bar this temperature. a Assuming thatthe activity coefficient of water is unity (Since its concentration is 98 mol %), what iste composition of the vapor in equilit- ‘om withthe 20 mol 5 solution? What isthe 624 Chapter 11: Other Types of Phase Equilibria in Fluid Mixtures 245 aT inn ean} +02) 1246 247 tivity egeticient af the alcohol in his solu b, At 90°C, the maximum amount of alcool that tan be dissolved in water is 2.0 mal &. When larger amounts are present,-2 second liquid phase forms that contins 65.0 mol alcohol ‘What are the scivitycoefciets ofthe alcohol and the water inthis Second liquid phase? "The activity coefficients fora paricular binary ig- id mixture are given by fori= 1,2 Determine whether a mixture containing 30 mol of component 1 forms 2 single, stable liquid phase ‘orwo ligid phases at 245K if the infinite-iltion activity coefficients ofthe so components at this temperature are Inv =20 and Ing =30 ‘The binary liquid mintre of nitromethane and 22.Srimetnylhexane exhibits lguiclquid equi Tibsium. At 100°C one phase has a mole fraction (f0.361ofrtromethane, and the other phase has 3 ‘mole faction of 2.2 5-timethylhexane of 0.0969, AL IIOPC the mole Fractions are 0.580 an 0.198, respectively. ‘a, Estimate the excess Gibbs energy of mixing. cach of the temperatures over the whole con entation range (tbat is, extrapolate ato the Iigui-tiquid equiicium region). by, Estimate the excess enthalpy of mising at 105°C over the whole concenation range «Estimate the excess entropy of mixing at 105°C ‘over the whole concentration range “The greater the difference in the pure component vapor pressures in a binary mixture, the greater the solution nonidelity most be in order for an szeatrope io form in vapor-liquid equilibrium. As- ‘sume that fora mixture Tiguid solution nonideali= ‘ies canbe represented bythe simple one-constant “Margules equation G* = Axia. a. Determine the values of the parameter A thet will produce an azeotrope in terms of the 1 tio of vapor pressures and the mole fraction of species 1. by. Compare the values of the parameter a ro: quired to form an azeotrope determined above ‘with those necessary to peedce a liquid-liquid @ 24s 249 112.20 221 aaa phase splitas a function ofthe mole fection of species 1. ‘The aerviryconfcient model parameters in Prob lems 11.2-18 0 11.2-25 ae easily detennined us Ing the MATHCAD worksheet ACTCOEFF on the (CD-ROM accompanying this book and described in Appendix BA. The following smoothed iui equibram data have been teponed"* for the system ni- teomethane (1) + eyelohexane (2) 35 function of temperature. ‘Mole percent, Mole percent. Teo, Hin Lind 5 276 290 20 320 333 25 3n 381 30 433 435, ry 581 332 30 in 338 a 06 952 a. At each temperature find the value ofthe 0 parameters in the van Laar model that will these daa Develop a comelation forthe parameters found in part (a) as function of temperature. For the dts in Problem 11.2-18 at each ter perature find the valve ofthe two parameters in the NRTL model (keeping « = 0.3) tht will these data, Develop a comelation forthe parameters found in part (a) as function of temperature 1, For the dats in Problem 11.218 at each tem perature fn the valve ofthe two parameters in the twe-constant Margules equation that wil ft these data Develop a corelation forthe parameters found in part as function of tempersture. Forthe datain Problem 11,2-18steach temper ature find the value ofthe two parameters inthe TUNIQUAC model that wil fie these data. Develop a corelstion forthe parameters found in part a ata funtion of temperature. ‘The following smoothed liquid-liquid equilibrium {ata have bean reported! forthe system ethyl es ter propanoic acid (1) + water (2) as afoneton of semperature. b 13) Seenson and WA Liguld-gu Equi Data Cllecton: Binary Sens, DECHEMA Che guy Du Seis, VOL V 1979, Felon p38 "Sorenson and WA, LiquiLigud qari Dare Collection: 1. inary Steme DECHENA Chem ny Dns Sens, Vo. Y1879, Fane. 297 11.223 1224 1.235 11.226 ‘Mole percent, Mole percent, req lin? Lin? 20 OMT a7 2 0351 867 30 0358 9.30 0 0379 109 30 ‘08 127 6 04s 148 7 319 170 0 0.659 192 |. At each temperature find the value of the wo parameters in the van Laar model that will ft these data bs, Develop a corelaton forthe parameters found in par 8a a function of temperature. 1, For the data in Problem 112-22 at eoch tem perature find the valve ofthe to parameters in the NRTL model (keeping a= 0.3) that wil fi these dt 1b, Develop a correlation forthe parameters found in par asa Function of temperate. ‘a For the data in Problem 11.2-22 at each tem- perature find the vale ofthe two parameters in the ewo-constant Margules equation tat wil it these data by, Develop a carelaton forthe parameters found in par (2) 38a Fonction of temperatire 2, Forthe datain Probiem 11,222 at each temper- ure find he valu of the two parameter nthe LUNIQUAC that will these ata, b. Develop & eomelation forthe parameters found in pat (a) as function of temperature. Iehas been observed tha an equimolar mistore of liquid oxygen and ligid propane has an upper crit eal solution temperature at 112 K, Assuming the one-sonstant Margules parameter for this system 227 n228 112.29 11.3 VAPOR-LIQUID-LIQUID EQUIEIBRIUM Although the discussion of the previous section concerned only liquid-liquid equilib- um, the extension to vapor-liquid-lquid equilibrium is straightforward, As mentioned in Sec. 8.7 the condition for vapor-liguid-liquid equilibrium is, or equivalently & hi 11.3 Vepor-Liquid-Liquid Equilibrium 625 is independent of empeature, compare the liquid Tiguid equlisium phase boundary for his system $2 function of temperature a Ihe Flory-Hozsins 7 parameter is equal <0 er, wil that model exhib lgui-lguid eae {ibium ina binary misnue? Ifo. what will be (i) the mote fraction and fi he volume frac tion of the liquid-liquid rial poi Note that if a iguidtiguid phase spi oceurs. it wil be completely entropic in nature thats. are suk of only the size difeence berween the molecules.) bb, Assuming the 7 parameer is equal to A/T, Find the liquid-liquid erica! temperature as & Function ofthe parameters 4 snd the volume ratio m. Also, fad the mole fraction and vol- ‘ume fraction tthe liuid-liuid iia! point {a5 function of these parameters. In Problem 10.24 i was mentioned that he foe lowing excess Gibbs enecey model describes the [propanol (1) + 1-hevane 2) system: BT p39 (A184 + Aas) In the temperature range near 65°C the parame tee values inthis equation are Ay = 1.867 and Ay 536, The vapor pressure of I-propanol at this Temperature is 0.260 bar and thal of hexane is (0.899 bar. Does this system have an azeotrope or exhibit ligndigud phase spitting” In determining the consolte temperature (rites temperature for Higuid-tiguid equilibrium we used 8 shoneut method described by Eqs, 11.211 11.214, A more rigorous method to Wenify art eal pint iso set bah the second and thir deriva lives ofthe Gibbs energy with respect othe mole number of one ofthe species equal © 20, Prove ‘that doing this gives the same result 38 Ea 1.214 Gl =e! 3.) =f (113.2) for each species distributed smong the three phases (liquid I, liquid II, and vapor V). Consequently, one method of computing the three phases that are in equilibrium isto 15.3: Vapor-Ligui iquid Equitibrium 633 involstile paint pigments and her impurities, Seam is injected into the bottom of kettle that contains the used turpentine. and the temperature inthe Ketle i kept at 100°C by removing the ‘vapar that forms, Assuming that equilibrium is achieved in the kee, how many kilograms of| turpentine are obtained foreach kilogram of steam that is condensed? ‘The molecular weight of turpentine is 140, and its vapor pressure at 100*C i 0.177 bar. SoLuTion ‘Since water and turpentine are essentially insoluble, the equilibrium pressure in che kettle is 190 bar POP(T) + PMT) = 1.013 + 0.177 “Therefore. the mole fraction of turpentine in the steam leaving the kettle is our os HT 20.9 0 thatthe vapor leaving the ketle contains 0.149 moles of turpentine foreach 0.851 moles of ‘water. Since the molecular weight of turpentine is 140 and chat of water is 18.015, inthe vapor 20,86 kg of turpentine ate recovered for each 15.33 kg of steam used, or 1.36 kg of turpentine foreach kilogram of steam. Comment [Note that any inert and insoluble uid could be used instead of steam for this sort of distila- ton process, However, here are several avanages to sing Steam, eo vaporization and its general availability ina chemical pant. PROBLEMS FOR SECTION 113” usd 132 its high heat of “Toe bobble point ofa figuid iste of n-butanol Dara: and water containing 0 mol butsnol is 92.7°C 301.013 bar At 92°C the vapor pressure of pure ve . ‘woter is 0.784 bar and that of pure butanol is 0.477 PET = 318°C) = 4.909 bar bur. PIE(T = 318°C) = 4.93 x 10" bar a Assuming the activity coeficient of water inthe 40 mol % buranol soluion is about 1, what is the composition ofthe vapor in equilibrium with the 40 mol # butanol b. AtoZ 7% Isobutane and furfural are only partially miscible in the Tiguid phase. At 37.8°C the two coexisting mixture, and What Tiguid phases contain 11.8 and 92.5 mal isobur is the activity coefficient of n-butanol? ane, Yao up, = 0.925) = 1.019, and Yradltort = ‘the maximum amount of n-butanol 0.882) = 1.033, that cen be dissolved in water is 4.0 mol 4, 113-3 Ethyl alcohol and n-hexane are put into atrevacu- When larger amounts of n-butanol are present, 2 second lguid phase, containing 40.0 mol % ‘rebutanol, appears. What are the activity coef- Gients for mbutanol and water inthis second lige uid phase? Ifthe two coenisting guid in part () are kept at 92.7°C, what wil be the pressure when the frst bubble of vapor is formed?” Estimate the pressure and vaporphase composition in equiv wit liga whose overall compos tions 30 mol % furfural and 50 mol isobutane at T=37.8C, sted, isothermal container. After equilibrium is es- tablished at TS°C, itis observed that two Tiguid phases and a vapor phase are in equilibrium. One Of the liquid phases contains 9,02 mal % n-hexane. Activity coeficients for n-hexane-ethyl alcohol lig- uid mixtures ean be represented by the equation aT In ‘a. Compute the equilibrium composition ofthe co- existing liquid phase. '. Compute the equilibrium pressure end vapor 634 Chapter 11: Other Types of Phase Equilibria in Fluid Mixtures phase male frictions : ‘Daxa: Vapor pressure equations (Tin K, Pin bar) ln Pr = POSE pasts sup _ 4728.98 in rag, = SE + 13.4683 11.34 Giyeerl and aectophenone are parlly miscible at 140°C, one liquid phase containing 9.7 mel 86 ace- topherone and he other containing 90.3 mol %ace- tophenone. The vapor presse of pure glycerol a 1HO'Cis 313 x 10”? bar and tht of acetophenone i: 0.167 ba. Assuming that he activity oeffilens forthe slycerob-aetophenone system obey the one- constant Margules equation, compute the pressure ‘eras liquid phase mole fraction (P-s) diagram for thissjstom, 1135 Foro separation proces. itis necessary to ascer tain whether water and methyl ety ketone form san azeotrope at 734°C. The engineer needing this Jnformacon eould not ind any vaporsliguid equilib ‘iu data for this system, but the following liquid liquid equilbiom date are avaiable: 20°C Liquid phase | 00850 0.9150 Liguid phase 2 0.6363 0.3637 In addition, 8 73.4°C Pi = 0.3603 bar PB = 0.8337 bar Calculate, as best you can, the Pry diagram for MEK and water at 734°C and determine whether this system has an azeotrope, and if 0, at what com= position the ezeotrope occuts. 11.3.6 Ethanol and n-hexane form two liguid phases at many temperatures. Assuming that the activity co- ficients for n-hexane-ethy! aleohol mixtures ean be represented by the equation RT Inyy = 8.1633 1 /mol and chat the vapor pressures ofthe pure components are given by (P in bar and T in K) 3570.58 T + 10.4575, and sp _ 4728.98 In Poy = EE 15 68 a. Compute the upper consolute temperature or upper ertical solution temperature (UCST) for the ethanol~n-hexane mixture b, Develop a plot similar 19 Figure 11.3-3 for this system vsing pressures of 0.1013 bar, 1.013 bar, and 10.13 bar «, Develop a plot similar vo Figure 11 system at 1.013 bar 7 Develop an algorithm for solving vapor-lguid= liquid phase equilibrium caleuations using. an equation of sate. 11.38 The infinite dilution setiviy coefficient of [propanol in n-heptane is 16.0 a 6OFC, and that of mheptane in I-propandl is 6.34. AC this temper- ature the vapor pressure of I-propanol is 20.277 Pa, and the vapor pressure of n-heptane is 28.022 kPa Prepare a P-r-y diagram for his system. Does the system exhibit szeotropy (ether homogeneous ‘oF heterogeneous) or liquid-liquid phase splining? 3-9 AU298 K itis found that component A has a vapor pressure of 0.8 bar, and component B has a vapor pressure of I bar. Also. by diluting component A, ‘vith 0.01 mole Fraction of B. the equilibrium pres= sure decreases to 0.7975 bas. while adding 0.01 ‘mole fraction of A to B reduces the equilibrium ssure 100.9945 bar. Determine the phase behav for of this mixture at 298 K over the whole com- positon range. (Is there an azeotrope, liquid-liquid ‘equilibrium, vapor-liquid-lquid equilibrium?) 11.3-10 At 110°C, a saturated ligud solution of aniline in ‘water contains 0.0162 mole fraction aniline, and saturated liguid solution of water in aniline con- tains 0.587 mole fraction aniline, At tis temper- ature the vapor pressure of pure aniline is 0.0923 bar, and that of pure water is 1431 bar. Construct 1 P-x-y diagram for this mixture at 110°C. VL3-11 The excess Gibbs energy ofa certain liquid mix ture containing components and B is found 1o be given by the expression forthis aL wr, where Tis in: The vapor pressures ofthe com ponents at 320 K are (4500-37 a= J/mol Nd |Sbar and PY? = LO bar ‘a, Whats the expression for the excess entelpy of this mixture? 'b, What isthe expression forthe excess entropy ofthis mixture? ‘e Whats the expression forthe excess constant- pressure hest capacity ofthis mixture? ‘One mole per second of A is isothermally mined with two moles per second of B ina continuous mixing process at 1 bar and 275 K. 4, What isthe rie of heat adition or removal for the mixing tobe done isochermally? What isthe rate of entropy generation ofthis process? £. eis thought possible that his mixture is suf- ciently nonideal fora liquid-liquid phase split to oceur at some temperatures. What isthe up- per consolute temperature for this mixture? ‘Compute the vapor-liquid equilibrium Dehav- ior of this mixture at 320 K, Does the system hhave an azeotrope at this temperature? If so. ‘what i its composition? bh. A mixture of one mole of A and two moles of B undergoes an isothermal fash vaporiza- tion at 320 K and 1.5 bar. What are the com- Positions of the coexisting vapor and liquid phases, and what i the vapor-liqui split? 113-12 Using the liquitliquid equilibrium data for the nitromethane + n-nonane system given in Prob- Jem 11.2-12, compute the vapor liquid-liquid equilibrium for this system at 90°C, 11.3-13 1383.15 K, Wo, Locke, and Sandlee'® measured the vapor pressute of pure pyroliine and cyelo~ hexane o be 39.920 kPa and 51.886 kPa, respec- tively. After the isothermal addition of = small amount of pyrrolidine to pure cyclohexane, the total pressure was found to be 52.270 kPa when the pyrolidine mole fraction was 0.0109. Sim- ilerly, after the isothermal addition of a smell amouat of cyclohexane to pure pyrtlidine, the total pressure was 40.280 kPa when the eyelohex- ane mole fraction was 0.0064. ‘Compute the infinite-clution activity coeffi- cients of pyrrolidine in eyclohexane, and of cyclohexane in pyrrolidine. Compute the complete P versus x, and y ver- sus x diagrams for this system at 333.15 K. © AC 393.15 K, does this system have an azeoitope? Does it liquid-liquid phase spit? 113-14 At 353.15 K the infnite-itution activity coef- ficients of benzene in ethanol and of ethanol in benzene are both approximately 5.0 10 within ex- perimental accuracy. AV this temperature the va- por pressure of benzene ie 1.008 bar and that of ‘ethanol is 1,086 bar. Compute the phase behavior a 11.3 Vapor-Liquid-Liguid Equilibrium 635 ofthis system at 383.15 K sceounting forthe fact. that vapor-iqui, liquid-liquid, and vapor-iquid- liquid equilibrium and azeotropie behavior may be possible. TBS The change in vapor pressure of a pure liguid with temperature can be compute ftom the Clapeyron equation, a at ~Tav where AH and AY are the enthalpy and volume changes on going from the liquid tothe vapor. The ‘vapor pressure and temperature must, ofcourse, be related, since the Gibbs phase rule indicates that the systems univariant. Now consider (wo par rmistible liquids andthe vapor in equilibrium with these two liquid phases. The system is also univariant (eo components and thee phases). a. Derive a “generalized” Clapeyron equation re- lating the equilibrium pressure and temperature for this system. '. Qualitatively discuss the variation of the equi> Tibrium pressure with the overall two-phase Tiquid composition for this system at xed temperature. How does.the pressure variation , with composition differ in the one- and two Tiquid phase regions? Also, discuss the varia~ tion of the equilibrium temperature with over- all liquid-phase composition at fixed pressure. inthe singe-liguid phase and swo-liquid phase regions. 1.3.16 An equimolar mixture of ethanol and ethyl acetate is maintzined at 75°C and 10 bar. The pressure fn the system is isthermally reduced to 1.12 bar. How many phases are present when equilibrium is achieved under these new conditions, and what are ‘heir compositions? Data: For the etbanol-ethyl acetate system, 0.896(1 ~ x) PE = 0.9460 bar and PSB, = 0.8905 bar 113-17 Estimate the equilibrium pressure and isobutane vaporsphase mole fraction as a funetion of liquid composition forthe isobutane-Furfural system at 37.8°C. At this temperature the vapor pressure of furfural is 0.493 kPa and that of isobutane is 490.9 Pa, (int: Ses Ilusration 11.3-L.) 113-18 At 20°C and 101.3 XPa dichloromethane (also re fered 10 as the refiigerant R30) is found to be soluble in water to the extent of 2 wt %, while the 154.5, Wa, W.E Locke I and, Sande, Chere Bag. Dat, 35,169 (1990) solobilgy limit for water in dichloromethane is 0.3 ‘wt. The vapor pressures ofthese compounds are 636 Chapter 11: Other Types of Phase Equitibria in Fluid Mixtures per critic solution temperature of 112 K. Assum= jing that this system can be described by a one- ‘constant Margules expression with @temperature- independent parameter, determine the liquid ene = liquid and liquid-liquid- hase di fo gud and iauidsliquid-vaor phase diogram for 20 00234 this system ata pressure of. bar. 30 0.1235 11.3-20 Using the liquid-liquid equilibrium data forthe ni= 80 0.4739 ‘tromethane + 2,2,5-trimethythexane system given 100 1.0138 in Problem 11.2-30. compute the vapor-liquid- liquid equilibrium for this system at 100°C. a. Assuming that the van Laar parameters for this _11.3-21 The following data are available for the acetone + mixture ar independent of temperature, obtain the ethanol system at 49.3-C: ‘hace diagram for this system at 50°C. ‘a, Assuming that the van Laer parameters for this _ 198 ‘mixture are independent of temperature, obtain the Whe 17 and Sea pase diagram fortis system at 80°C. . Assumi thatthe van Lar parameters for this mixture are independent of temperature, obtain the phase diagram fortis system at 100°C. 113-19 An equimolar mixture of iguid oxygen and Tig- uid propane has a liquid-liquid equilibrium up- At this temperature the vapor pressure of ethanol is 0.2854 bar and the vapor pressure of acetone is 0.7710 bar. Compute the phase behavior ofthis system at 49.3°C. Does his mixure have a homo- geneous or heterogeneous azeotrope? 114 THE PARTITIONING OF A SOLUTE AMONG TWO COEXISTING LIQUID PHASES; THE DISTRIBUTION COEFFICIENT Distribution coefficient When a gas, liquid, or solid is added to two partially miscible or completely immis- cible solvents, it will, depending on the amount of solute present, either partially or completely dissolve and be distributed unequally between the two liquid phases. Most chemists and chemical engineers first encounter this phenomenon in the organic chem= istry laboratory, where diethyl ether, which is virally immiscible with water, is used to extract organic chemical reaction products from aqueous solutions. The distribution of a solute among coexisting liquid phases is of industrial importance in purification procedures such as liquid extraction and partition chromatography, of pharmacological interest in the distribution of drugs between lipids and body luids, and of environmental interest in determining how a poltutant is distributed between the air, water, and soil, Experimental data on the partitioning ofa solute between two liquid phases are usu- ally reported in terms of a distribution coefficient K, defined to be the ratio of the solute concentration in the two phases: [+= Serene The porpose of this sections to study some aipects ofthe partitioning phenomenon and to relate the distribution coefficient to more fundamental thermodynamic quant- ties, so that we ean (1) pret the distribution coefficient fora solute among two given solvents if experimental data are not available, or (2) use experimental distribution coefficient data to obtain information on liquid-phase activity coefficients, However, in this section we are considering only the case in which the addition of the solute does not affect the miscibility ofthe solvents. The more general case of ‘multicomponent liquid-liquid phase behavior in which the solute addition affects the ‘mutual solubilities of the solvents was considered in Sec. 11.2. The siiion consid aL)

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