Equilibrium Criteria = 6 6.1 Solution Given aconstant volume, wel-insulted vessel containing both vapor and liquid. There sinitilly only compound A. In the vapor phase A reacts to form B and C by: A=2B+C Cis soluble inthe liquid, but B is not, The reaction does not take plac inthe Tiqud. ‘The vessel asa system s isolated at constant S, V, mass and the eriteria of equilibrium is azo duh du" = Pas’ Pav’ + wlan" + wlan + wlan’ Has! Pave + pha + un + ub with these restraints as-+as'=0 dv +av’=0 dN! +aNi = dN, =Vyd6 aN +dNth= Ny ANE + aN: avo Thus a w= — thas! —(°— Pha + ua Hy FUE HD Hl Hy 20 Thus the constraints of equilibrium become: rerdayet aia toe= 62 Solution Since the oa volume, temperstre and mas are te, te criterion for equilibrium is az0 aaa da +a! = Pay! Pat +utan! «plan with a +de=0 ANY + dnt ths, an =P" Pav +n” —phyant 20 and the equilibrium tera ae 63 Solution Let us begin with N,, moles of A in a constant volume vessel and sllow reaction to proceed at constant pressure, Then if A=2B (Rs) define asthe fraction of A that reacts. Let the volume = V= constant and the pressure P= constant. ‘Then, assuming an ideal-gas mixture, if the inital emperature were 7, when e& has reacted, the temperature will be zi 1, @-a +a "Tra 0 aplot of Tvs. «for constant V and P should look like: o T=Ta)pulbiien Gitar “Geplidh | ES ee is Now, if Reaction (Ry) applies st equilibeium then Zygt,=0 and (see Chapter 16) a=fAD ifthe reaction is exothermic, a | a8 TT ifendothermic, Tas 77 Bat, in any case, the ovs.T plot for Eq (1) covers the entire temperature range so itn the 7 plot for PV constant, At the point of intersection we have an equilibrium stare, as indicated below is ¢ | Fado 7 64 Sobtion (@) The subsystems II, and I may be considered as being at constant S,V,N. Then aut=au'sau"+au">0 w With he constraints ast=0=as'+ay+ast" ® ave-0= ay+av'+ ay" % AN,= AN + AN + AM =v AE oyAnd, in adltion, av=0 AN! =0=Mir AN =0= aM, ang ‘Then vite rMag!_pitgylt = TMcas'~ as')~ PM-av") aut=13s'~ Plas «an FAS! + ph AN + Wh AN, + ay AN Substitute Eqs (9), (10), (11), into (1) Fas! + ras! ras! — 1s" —play« play! FAN, + HAN + Hy AM + Hyg AM, >O but AN = Vy, d5— AM, ANG, = VeAE + Nay = Vou asl cr" — "has! aN, + Wb + aw +, thus the equilibrium criteria are per au! AUP = AU — TAS py AN, >0 o © ” @ ) (10) ayEqultvium Crtoria Chapt 6 es x onside suey 1857 ny Nay Mn) With y= T8— tn 28 the function to be minimized 65 Solution (2) initially T,=1,=2732K e ¥,= 9.086% 107m? ¥,=2271 x 107m? pure A) 0 moles N{pare B) = 1.0 moles [Now let the piston be permeable to A, but not to B.Itis rigid and diathermal with Section | is connected to a2 bar reservoir Section 2 is connected to a3 bar reservoir At equilibrium: P,=2bae 3 bar », My 4, oF for ideal gases P, (©) Now, at equilibrium: 0,Ny,=1,Ny +N, =4 moles P,=2bae=P, Bbar= Py +P, thus Pp bar66 Egultrium Criteria Chapter 6 ‘hus also thus 4RT tus To try and obtain some idea ofthe final temperature, we will have to assume that the movement of the pistons represents a reversible process~but this is probably only an approximation, ic, slow, near-quasistatic compression and expansion instead of a epi, transient jump. Then, pee W=W,+W_=— 2x 1071, ~ 9.086% 10% - Gx 10)(¥, 2271x10%) and from the First Law W20+AU=+W,+NJCAT With Q = 0, we can substitute for W to solve for T: ea ee ae 0x 10522 ~9.086% 10) x 1025-2271 x 10 x10 )-¢ fs =+5x209x(T-2732)e 2RT-+ 3RT'~ 1.817 x 10" 6813 x 10° =—104,5T +2855 x 10 115%8.314 + 104.5] = 5.353 x 10" 723665 K and with V= RI/10" ¥=0.03047 m" (©) the piston is permeable 1 both gases, one cannot satisfy the P, criterion and the Py criterion, Piston M moves all the way tothe lef P,=2bar N, SRI/O If W is determined as before, T= 367 K, and V, = 0.0752 m* 66 Solution Initial Conditions P= 2 bar Py= | bar 7 =300K T,=400K 1, =6 moles 1N,=5 moles 204 4,208 “The dlviding piston is now made permeable to A and is moveable and dithermal at equilibrium: 1\=% Pi=P, Ha =e, thus: since we specify n +1 intensive variables, then AU,=AU,=0 wo e av, +a¥,=0 @6 Equltrium Criteria Chapter 6 Athy #220 » @ Ny = AN =O 4 Assume idea! mixture of ideal gases. Choose a reference state of 7” and let Tbe final temperature. With a constant C, for A and B. AU,=N, Uy +N, Us, +My {C,(T-TH14N, likewise for AU, Adé and cancel C, = C Thus NAIC @-T) ,-T MIC 7, -T1 snd also all terms with 7° cancel due to mass balance, TIN, +N, + 1, (My, +My] + My, + Ny IT, 300x6+400%5 a 11 SSK A volume balance, with Eg, (2) gives y WaMu t Vy VV Va NRT/P thas 6 e #95 511 = 300/264 400/1 x5, ri ince the dividing piston is not permeable to, then Ny, =Np, =0.6x6=3.6 moles 31 bar 0 Ny, +Ny,=04X6408X5=2444-64 thas:Ny = 14 moles So atthe end, N= My=3.6 inside 1 mals inside 2 [As the amount of B in 2 decreases, then more A is transferred o 1 In the limit, all A moves from, 2001 67 Solution 248K v=001 m M,=005 ¢ Let €= fraction evaporated. Thus, initially €=0. Atany time © eM,= vapor (1-2)M,= g solid P=P, AU =[eMU'C) +0 OM) = Mie UP, N-eUP,T) For an ideal gas there is no change of P on US, then AU=MjetUp, - Up) =Myetef, -#, - RT-+0) = MCA gy RT) = MpTAS yo ~ BD Ths AUslneain witha slope of MITOS y= R)=5% 105244 K (1.62 8.314718) AU= 1360 AS=eMS"(T, P.)+(1 QM SUT, P) - MS! AS=MIetSs SE] —_with sf Morn)610 Equilibrium Criteria Chapter 6 but with 17, = molecular weight: P,=MgRT/M,Y MgRT AS,)—R In MVP y eS 8314, [5x 107xex 8314x244] ] Seeesni0"y ania Ate se | Mg ase[oss1 -0460%3 10° 640) A4=AU- Tas px Mtg pT, le e l AA=-MERT [1 ~ In 4.40¢] =-5.635e{1 ~ In 4.40¢] aba Since at equilibrium —— AA = -Ke{1 —In 4.406] K [(1 ~ In 4.408) ~ e(1/e)] =Kin4.40e if =0, then e=1/4.4= 0.227 eaquirium Criteria Chapter 6 eat @ iw du=80+¥W thus