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ES TH ERMODYNAMICPROPERTI INVOLVINGDERIVATIVES
Using the Peng-Robinson Equation of State
R.M. Pnerr
The National Uniuersity of Malaysia ' Bangi, Selangor, 43600, Malaysia quationsof stateare amongthe marvelsof chemical engineering.Though simple and convenient,they may be usedto modelboth liquid and vaporbehavior r'2i such tbr non-polarand low-polarmixtures.l Consequently, tools of the hydrocarbonprocessmethodsare the pret'erred in ing industry.It is not often, especially thermodynamics, that you can do so much with so little. ln this article,we properties that containderivatives, thermodynamic calculate a topic not normally found in textbooks. There are two motivations fbr presentingthis material. First, the calculationsare simple, requiring no iteration or They are,however,useful items to solutions. trial-and-error add to the engineer'stoolkit, and they require only critical it data.Second, enables propertyand ideal-gas heat-capacity the studentto use some seemingly abstractequationsof cal t her m ody nam i cto d i re c tl ym a k en u m e ri c a l cul ati ons. s It is rewarding to see these relationshipsused to make of re a ac t ualc alc ulat i o n s n d to o b s e rv e l a ti v emagni tudes v ar iousquant i ti e s . equawe To illustratethe methods, usethe Peng-Robinson mixture. tion of stateappliedto a binary vapor hydrocarbon that can be numberof derivatives Thereis an almostendless calculated-we will consideronly a few of the more comones.It is trivial to simplify the ensuing monly encountered equationstor the special case of a pure componentor to apply the equationsto any number of components.The are equations valid for both liquid and vapor phases. 1t2

PROBLEMSTATEMENT
Using the Peng-Robinson equation of state,calculate the

I ) Joule-Thompson coefflcient,

',:_ d,P J " I | ar)

2) Fl ui d soni cvel oci ty, c: for a binary vapor mixture clf n-butane and n-pentaneat of 390K and I I bar that consists 35.630mole % n-butane. Take k,,tor this binary pair to be zero.

SOLUTION
We will solve this problem in three steps.First, we will the usethe Peng-Robinson equationof stateto evaluate three i nvol vi ngP , v, andT, i .e., (de/dv) r , ( aT/ aP) v, deri vati ves
Ronald M. Pratt is a lecturer in the engineering department at the National University of Malaysia. He obtained h,'s 8S in mathematics and in chemical engineering at the Colorado Schoolof Mines, his MS in mathematics at the Fuxin Mining lnstitute in Liaoning Province, China, and his PhD in chemical engineeringat the Colorado School of Mines. Research interests involve molecular dynamics and fractal modeling.

@ Copyright ChE Division of ASEE2001
Chemit'ul Enginee ring, Education

. and subscripted values for pure componentquantities. (4) to checkour work.We know that thesethree derivatives "cyclical rule.(bar) orrl 125.Y i T l Tl ll l " r L f r -ll We now solve Eq.+) Dr /p --. b 0.. Consequentl y. is closeto zero tor hydrocarbons./P.*.t=O. we find that cm cm6-bar/tnol 2b = 83.k. (4) is a bit trickiersinceEq. ( 1l lt is not readilyexplicit in volume or temperature... we now calculatethe three PVT derivatives. (1).252 fP'lt. and will evaluateeach derivative independently.0434866bar/K.we find that in Substituting the valuesdetermined ( aP) [.From Eq. k'. from Eq.the third may be calculatedfrom Eq. {w'}. the mol ar vol ume. Cu and Co.45723553 0. Z' iterais This equation easilysolvedusingNewton-Raphson or ti ont5l by usi ng the cubi c formul a.R T ' v-b v(v+ b)+ b(v.003545e / (cm3/ mol) bar The secondderivativein Eq.1794 for the vapor.017796074 T critical temperature TABLE 1 P critical pressure Critical Property Data for pitzer acentricfactor 0) n-butane and n-Pentane c c for The critical properties the of two components our sYstem aretakenfrom Smith and Va n Nes s( T ablel ):l rl n-butane n-Pentane T.and (dv/ aT)p.. indicated derivatives the calculate two thermodynamic quantitiesappliedto the mixture as a whole.f1". Then we will find the real fluid heat capacities.96 0.which follow directly from the equation of state. (l). exactly zero tor i=j.) and 6= !w1bi i=l is The binary interactioncoefflcient. alin the literature.54226a .(t-t'. with knowledgeof the molar volume and compressibility. derivatives. Valuesof (' for for i*j. Iap) \ar/" v-b (6) v(v+b)+b(v-b) and is found to be 0. Knowledge of these to quantitiesis prerequisite finding most any derivativethermodynamicproperty.83621 6 r / m ol a= 20631852 The Peng-Robinson equatton ts written as a o -. we using R=83'14 calculatethe pure componentparameters cm3-bar/mol-K: cm6-bar/molr ar= l59l ll l5 cmo-bar/mol2 az=2352259-5 b: = 90'14811cmr/mol crnr/mol br =72.31464+ 1./1\ aP i u\ (4) the For convenience.0.54cm3/mol. ( I ). pairsit is safe thoughfbr most hydrocarbon will henceforth use values without subscriptsto refer to 2 Spring 001 in The third derivative Eq. (3). ( ) is also found by direct ditferentiationof Eq.. (2) for the compressibility factor.l rlIn ei ther casewe calculatethe vapor phasecompressibility factor (largest of the three real roots) to be 0.. Therefore. (2) ()) above.ee558K/bar (3) \. = -0. we calculate the mixture parameters.1 0.] (7) I tJ . is therefore found implicitly.u o=II*. from the empirical relations: N N N oncewe have valuesfor any two of the threePVT Therefore.200 469. f'+) =22. PengRobinson equation is often form for the compressibilitY written in a cubic polYnomial f a c t o rZ = P v / R T 'i(z\--23 az?+$z+y =11 + where a=B-l F=A-28-3B2 T=Br+Bl-AB and A=aP/(RT)l B=bP/RT For an N-component fluid with composition." which may be written as must satisfythe RrT.43235 and then.1 3 3.b) (r) where i :I gas R universal constant temPerature T absolute v molar volume a ac ITI ac lLl + m l l .tJ-. 0. ft) I Ev .1 37.[#). (#). useEq.r/P. v' of the vapor m ixt ur e is ZRTIP = 2297. a and b.o. (4) is found by direct differentiationof Eq. (4)' We however.lal pairs are available many component we to takek.?6992 a2 RT. usingEq.(K) P. (2).=t[. and flnally we will apply theseresultsto above. The first derivativein Eq.

: . (g) yielcting of .{. 1 l 1 0 6 x t 0 0 . 4 0x2 1 0 ' 6 .may be evaluated directly fi'om Eq. 0 5 0 J / m o l .( l3) with respecr of to temperature yields (au1 = [Vii.r. The idealgasconrribuII+ o.--gil i=r=l l r L{ u . € ) .'.1 4 . l The pure component parameters found from Eq.-z a ) T [. 9 1x l 0 ' 4 5 . albeit tedious. l T r = a a i= . a'=dat/dT. ( t6 ) TABLE 2 n. we use the the standard equationfound in many textbooksta'6t the for residual internal energy derivecrfiorn the peng-Robinson equation state of (e) U R= T a ' : a .e.2 cm6-bar/mol2-K and da/dT tbr the mixrureis tound fiom Eq.t ( t . o { Jri )) (r-5) where d2a..*. t 2 ' 2 6 3 e 6 ]/ m o l -K cm If we multiplythethree numbers together will seethat we wehave satisfied (4).t +J..f.. C I D= F w l C v D I i=l I (r2) and [ a n 1 = p ( .butane A B c D 1.l ) (ll) which is not recommendedfbr temperatures below298K nor valid fbr temperatures over I 500K. -u *T)J " Lv: a a Evaluation thepartial of derivative Eq. .'=-25547.bar/mol 2 K 2 crn6 Clrenti<ul Ettgitteering Etlut'cttirnt 3 6 .-n.. r / ..+-".. calculate eachcomponent we fbr C I P = 1 1 3 .+ i) m 2 TT.ll . to which are available in many thermodynamics textbooks.K /m and for the mixture c f Dr : I . = . (10).261 9cm6 bar/mol2 .: 8 2 ) \ o I /r.2732 .1. where To calculate residualcontributionto Eq.=#=+ii.935 n-pentane 2. We flrst find Cr.-. (7).K2 a i : 8 0 .o= 141.1 1 . . 3 5x l 0 r 5 t . (3) as u. the calculation but is straightfbrward.464 Theseequations appearcornplicated. 7 4 9 6 c n r_ b a/tm o l 2. ( l5) to be tr"= 70. 4 -----.. " [ t . . cmn-bar/molr-K.*. we flnd that in br/s (l3) Iz+n(r_Jt)] The valueof C$ is calculated tiom its definition n R. For n-butane and n-pentane.0cm6-bar/mol2-K a:' =-38460.K C l .z s . 2 8 3 / m o t . Eq.D+C$ iii*.."i _Jl)) br/s Iz+e(r with the temperarure derivative Eq.- ( t .-*.. N [?f ro 3 2 2+ 2 ( B -t ) z + ( n .. i. 8 Substituting known values to Eq. . \ m l tion tbr the mixture is a mole fraction weighted average of the pure component values.37 6J ol.K J The derivative term.rro **. we will use the sim ple or r elat i o i n S m i tha n d Va n N e s s l rl c n C { P= n ( n + B T + C T 2+ p r .*.i. z+s\t ^tltl + c$=f+ .We will consider this real fluridproperty tcl be a sum of an idearlgas contributionand a residual comection non-ideal fbr behavior: Cu=Cl.(.q) tdzl l . the coefficientsare giv enin T able2.u ) \ f gq'l = -bP dr /p R T2 Inserting the known temperatureof 3g0K into the above equations. *ff'. (g) to be a' =-33543...f.pure componenrparameters fbr a" are found from Eq.K 2 6 and a" for the mixtureis fbund f}om Eq. N N t | - -\l (r0) The ideal-gas contribution found usingheat-capacity is data applicable gasesat very low pressures..F*.r \ (14) d2 Ll - dT. ( 16) to be ai'= 53.where (a. (9) as are a. +i{ " i +.)lu .(. d r a..

cp =cF +cF (17) are unusual velocity units. c.31cmr-bar/mol-K.. S.\r 4g I .1 6 4 m3 -b a r/mo l )0 5 ncethese Spring I 200 .E. NY (1969) Kyle. -?e..Adding the idealgasand residual to tionsaccording Eq. Van Ness.Sth ed.:l '=+['(#)..Co is approximated evaluating by the enthalpyH=H|I)+UR+RT(Z. 8.586m/s=646. ( l9).M." Chem.. Wilkes.M.at two nearbytemperatures l) at I I bar (andsamecomposition) aboveand The two partialderivativesare alreadycalculated into canbe substituted Eq. ( l0). Prentice Hall...K ..597J/mol-K.-- (18) D IS C U S S ION Calculationof derivative propertiesis easy if there is an equationof stateavailableto model the PVT behaviorof the fluid.we can calculate Cu We derivatives. (c Si.l S Z int Z J/mol. and the speedof soundin a J. u5 . ( l4 ) (u s i n g r= 0 .^= J/ 67 )v 391-3U which is essentially sameas the resultobtainedabove. 2.O.. Ed. Introduction to Chemical Engineering Thermodynamics.. New York. J/mol-K. 1. 3. Chemical and Engineering Thermodynamics. i n toE q.A. NY (1999) Smith. Eng.For example. a g ei n c alc ulat ing the 70. the with any emordue to the finite-diff'erence approximation.590m /s I-v m- .85 or cmr-bar/mol-K therefore and C$=t 36. is calculated workingequationt6l 4./-tsf+l Lv\dv/r (20) 7. The residualcontribution may be calcubetwe. P.5krn/hr a n d s inc e Ct o= ClP + R . o.bar/ . Joule-Thompson fluid. NJ (1994) "Spreadsheets Savage. B. H. some units conversion is in order. we obtain / from the The tluid sonicvelocity (d P d p ). ( 20) y ieldsc = 1 4 7 . Chemical Engineering Thermodynamics. we now obtain Cu=132. Phase Equilibria in Chemical Engineering. for Thermodynamics Instruction.ltl Including theseand other thermodynamic derivatives would be very easy. J. coefficient. Wiley. New York. . averintroduced usingthe mole fractionweighted 2o/o)is by a" a" .22s1y !$ 16t or c=179. J.very little enor (usuallylessthan If doinghandcalculations. NY (1997) Sandler.=u. 152 g/mol and we find that the sonic velocity is ( p .o = . is worthwhile fbr the studentto develop it a spreadsheet set of computer subroutinesto calculate or thermodynamicpropertiesof hydrocarbonsand hydrocarbon mixtures.30012'++e 9 . Applied Numerical Methods.(aT/ It is simpleto calculate Joule-Thompson the usingthe working equationl6l aP)H.70s'e77 =I 53. Chemical and Process Thermodynamics. Abbott. In th i sc a s e w e w o u l dc a l c u l ate to . Winnick. It is interestingto estimatesome of thesederivativesby using their finite-differenceapproximations and to compare with resultsusing the equations theseestimates discurssed above.236mol K cP .9557 cm6-bar/molz-K2.637 J/mol-K. Boston. will only a largenumberof thermodynamic ones.the two of the more commonlyencountered evaluate coetficient. McGrawHill.n Cv and Cr.G. Two such propertieshave been evaluatedhere using the Peng-Robinson equationof state. H.n ' ') [^E-.5. w e re a d i l y c a l c u l a teC fD to be 139. and M. Wiley. The averagemolecular weight of the vapor mixture is 67. cr l(X _d ) 0 g l m o l Tmtr". Butterworth-Heinimann.. this ln age of computers.683(cm3 mol )" ' '= 226. contribu13.It is trivial to evaluate a large number of other derivative propertiesonce we know the threePVT derivativesand the two heatcapacities.C. Substituting into Eq. and Cp.os cF=c$. Luther./i fi -R T = I 85.. New York.436 We will usean equation to analogous Eq.29(4) (1995) .. Substituting abovemixture be g q u a n t it ies oE q. (18):we find that CF =C$ +124.-"] I=1. ( l7) yields Cp=153.235Jlmol-K Now that we have valuesfor the three PvT derivativesas well as the two heatcapacities.M. and J.__ m 1tLtr1cm3-h. 1 Substituting All the requiredvalueshave been calculated. New York. 3rd ed.. MA ( 1985) Carnahan.indeed. . REFERENCES 1. latedfrom the generalrelationship (idealgas) We can compare this resultwith the low pressure limiting value . ffi= 3. NY (1996) Walas. UsingEq.'[#)"[#). ( l0) to calculate cP. Wiley.1 1 9 4 3 8 )i v e s C $= l .: i ^ l =21657:rl_:j:1100000=.62195K/bar (' e) sinceall the required values have been calculated.

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