Energy and the FirstLaw = 3 3:1 Solution Given: 56710" m? 194.3.K ial gas volume initial gas temperature initial gus pressure = 10.13 bar 1208 doubles in volume to 1.133% 10% m* (667 10° m? Choose, as the system, the universe or surroundings exclusive of the gas inthe eylinder. Then, by the constraints given, including no friction in surroundings: change in volum ® : and W=P,(Y- ¥) +m, BAZ where P, = atmospheric pressure = 1,013 bar VY, = change in system volume = 5.667 x 107m? mt sass of piston = 226 ke st m/e ‘variation in vertical position of piston 0.3048 m if piston rises = Dif piston moves horizontally 40.3048 m if piston falls 0° N/m") acceleration due to gravity case 1: Piston rises (note bat We (1.013 x 105) (5.667 x 10°), OE pum = + W= 1.250 26) (9.81) (- 0.3048) =+1.250 kd ME yg =N, C, Ty ~T,) noes of gus = (1013105 (5.657 10°) uaa ae (8.314) (294.3) mee N, e ,= 5 Btuflb-mol °R = 20.93 Jhmol K22 Energy and the First Law Chaplet 3 And, setting -W = NCAT, ~ 7, =1.250° 10" = 2.346) 20.3) (Ty 2943) 68.8 K and from the ideal gas la (2346) (8314) (268.8) 4.627 10° N/m? C133 x10) Other cases: Case 2: Piston moves horizontally W=+0S741 kd 1,=282.6K 7124365 x 10 N/m? Case: Piston moves down W=-o10a1u 7,=2964K PES 5.108% 10 N/n? 82 Solution ‘The system chosen is the liquid methane and vapor methane inthe tank containing total moles. Superseripts Vand L represent the vapor and liguid phases; properties without a superscript indicate both liquid and vapor. Energy balance: dU = 8Q— Hig, Btyy Hoa Mase balance: 8%y=—dN =s0+H" an vu" +ut =H py Ht PE a=W dN + Hane ‘where, because both Tand P are constant, di = ditt and, since the total volume is constant, ("+ V4 =0. Thus, aN" + HE aN’ = 80 + HY CaN" +a) o Volume balance: V-= constant = V4 Ve= W/W 4 XE Wan’ + antalso, an = aN ae dN = aN/(V'- VV) = aN @ aw’=0-@)aN where = V'/AV, 8) With Bes. (1)-@), 80 [0- 0H" + 014 -1"]av=-—0anr,a oH where AMy enthalpy of vaporization For the case in question: P= 1.046 bs T=110K Vf =8.606 x 10° m'/mol VF =0.0380 10° m’/mol © =8.6036/(8.6036 ~ 0.0380) = 1.00444 ‘Ax, = 8193.0 mol ‘M-= 1601 gimol (Molecular weight) Thus from Eq. (4) 30/dt=—@alt, dN/at aN/dt =~ 4.287 x 10" move 8Q/dr= 1.00444 x 8193.0 x — 4.267 x 10'= 3.511% 10" Jr NNote that if had not been used, the heat leak would have been 3.496 x LO Wr Contractor pays the penalty fee! If the tank pressure changes, then we can no longer assume thatthe intensive properties of the Tiguid and vapor do not change. While it may be an incorrect assumption, let ws assume that the tank liquid temains in equilibrium with the vapor. The energy and mss balances then become: AU= 60+ BW-H1 B,,=50+H" dN U=HY +H PW + Vy oY 4 a Py = HY aN + He aN +N att" +N att’ VaPsey at Ft a Chapter a 3Q=H" an'— HY a+ HE dN WY dn + Natt’ Yap ith NTaN-M dN’ =an—aM, [yall yea 0 =, av vie ar To employ Eq, (6), just relate dN tod by a volume balance. av=0=V aN Vea ew av ena with an’ y= dN N x em” aN =ouv + Eq, (8) maybe writen as yr dV, ye di?) ap ae Gran where ap. at TRV, used. To evaluate the terms in Ea. (), @= 1.00444 from before T=112K Ady = 1.27982 10* ~ 4.6052 10? = 8193 Yimol dV" /dT = 65015 > 10% m/molK av'/at = 1.309% 1 yey! m'/mol K 65% 10 mol (0.01) (40,000)78.6036 > 10° += ¥7¥- = 0.99) (40,000)/0.0380 x 10° = 1.042 x 10? mot apa Substituting 742 10° Pa/mol (0.001)/-4.277 x 10 24) ]x 108 = dN = (1.00444 + 1.414 x 10%) dN = 1.00458 dv [Note tat the terms multiplying dP/aN contribute litle ‘Substituting Eq, (10) into (6) and simplifying, o & © o ® o i)Energy ad tho First Law_Chapter 9 2). at ae. using the data given and the dP/dV calculated above, 52. +6652~3.9) 4569.42 By 7 (82307 + 665.2 -3.9) Sh 7569.4 2 with 28 4.267 10 movie fe 80. $2 -3.230% 108 Jar (On this bass, the contactor collet the fee! ‘Note that the small change of 10" bar (100 Nim? =0.4 inch of water) makes a great difference! ‘The assumption thatthe entire liquid mass remains in equilibria asthe pressure changes is not ‘warranted--but other "reasonable" assumptions ave also questionable, 3.3 Solution Area = 6.45% 107 m* Go a wlan sah USOT 6° stares The pressure initially in D- 1.013 x 10° Pa, uae (0.508/2(6.45 x 10? ~ 1.29% 109) = 1.31 x 1 es (0.508/2\(6.45 x 107) = 1.64 1m? Py= 1.013 x 10° Pa Pe= Ppt (9.07 +4.53 + 18.14)(9.807/6.45 x 10 O13 x 10° +4,83x 10° = 1.50 10° Pa No= (1.013 x 101.31 x 10°V/(8.314)311.0) = 5.13 x 10? mol Ne= (1-50 10°)(1.64 x 10)/(8.314\(311.0) = 9.51 x 10 mol(Case 1: Piston Diathermal @ ‘The walls are adiabatic. With the system asthe compartments D and E,. results from the piston rod compressing the atmosphere, the only work ‘The piston moves up. Define x= distance from bottom to piston when all motion has ceased. The temperatures in D and E are 7, in K by stipulation. is defined asthe mass ofthe piston A and rod B. Energy balance: aU: W=~(1.29 x 107)(x = 0,508/2)(1.013 x 10°) J aU=Y/-U, =No(Up,~ Uo) +NlUg~ Un)+My ete) +W = (6.13 x 10791267311) +(9.51 x 1012.6(7- 311) + (4.53 +9.07)4¢-0508/2).807) [Neglect any energy change dus toa temperature change in the piston. Therefore, 1.847— 311) + 1384(¢— 254) =~ 130.70 258) 1847-311) =-264.1c2~.254) 0 T= (0254 ~3)(143.5) +311 » @ Tn auton tothe energy balance fore balance a he end yields Ppl6.45 x 107 — 1.29 x10") + (9.07 +.4.53)(9.807) + (1.29 10°)(1.013 x 105) = P,(6.45 x 10) @Q) wit Py =Glax 10 \8.314)(7)/(0.508- x9(6.45 x 10° — 1.29.x 107) @) (9.51 x 10°)(8.314\T)/(x}(6.45 x 10°) @ ey han when singed beome Pp {5.16% 10) +264.05 = (6.45 x 10" )Pp @ i: Pp = $2.66 1/(0.508 ~2) i 8) ppemzers w ons sl + 2610502506 ®Energy and the First Law Chapter 8 ‘Solving Eqs. (5) and (1) simultaneously 28485 m 7=3053K y= 1.13% 10° Pa P, = 1.3110" Pa ‘case2: Piston Adlabatc Energy balance: The equation is developed as before except Tp, Tr, 0, (0.6464(7;, — 311) + 1.198(7, ~ 311) = 264.1 0254) 6 Force balance is given by Eq. (2') ‘Material balances given by Eqs. 3°) and (4) become P= 82.66 Tp/(0.508 ~ 5) o P,=126T,/e ® “There are 5 unkmovins (Tp, Poy Tz, Pe,*) and four equations. To abtsn a solution, some ‘assumption must be made conceming the ireversbilities inthe process. (@ Assume the helium in E expands reversibly and adiabatically, Then for compartment E, dUp=8Q+8W or NpC,dTy=0~PedVe Cag =-R aT + (RTp/Pp) dP Cpdfy=RT pln, (G/RydinT = dinP Pe/ 150% 1090" 15/3 R/Cp=8314/(12.6+ 8314) =0.3975 11(P 51.50% 1057" O} Solving Eqs. (6), 2), (6. and @) 394K Pp= 1.157 x 10° Pa 296.9 K28 Energy and the Fst Law Chapter 3 P= 1.335 X 10° Pa x=02727m (b) Assume that the helium in D expands adiabatically and reversibly. Eqs. (6), 2), (7), and (8) ae sill applicable. Bq, (9) is replaced by 311(P9/1 013 1079" 277K and Pp 1158 x10" Pa Tq, 2975K and Pp,=1.333x 10" Pa x=0.2735m [tis interesting to note that eases (a) and (b) yield quite similar results and as these cases bracket the true solution, one can make a reasonable guess as othe Final conditions even though the exact details ofthe process are unknown, 35 Solution Given: A B Gas helium hydrogen ‘Temperaure,K 31 311 Pressure,bar 10.13, L013 Length, m 03088 0.1524 Area, m? A 4 Moles, 1794 5.8944 CollmolK 12.56 2093Energy and tho Fst Law Chaptor 39 © © Pron a te Gb feta ai slo Th=Ta ad Py=Pp AU, +AU Ny Cy, (Ty311) +N C,, p= 31) Ty=Ty-31K ‘A mole balance yields (PX.3088-+0.15204 (@31H(11) 00 bar 11794458944 = P=7.00% 108 Nim Since length (L) is proportional to volume, y/lg= Y/N Mg= 1794/8 844200034 arial yy =02018 01524-04572 1.=04854m ty-01t8m © © Prone at sn pron: Stew banka eye or i) sme (©) Piston adiabatic, no heet sink ‘When the piston comes to rest, there are five unknown quantities, Ty, Tp, P(P4=Py), Va, Vp. There are four equations relating these variables: (We use, however, Ly, Ly instead of V. Vp) Conservation of energy AU, + AUs=0 Na G,,Ta~ 311) +Ny CG, (Ty—311) = (1194 A}(12.56)(F, — 311} + (5.969 A}(20.934Ts - 311) Mote balances in A and B: 194A=(PYL,AY/B314NT)) 5.969. =(P)Ly A)/(8.314)T;) Length balance: [y+ g= 04572 m@ ‘There is no tre solution. We can, however, find limits, ie. we can assume that either the gas in A or B expands (contracts) adiabatically the hydrogen is compressed in this manner, from Eq, (3-48), GAIN =@/013x yen ‘Then, P= 6.925 x 10° N/m = 6.925 bar T=223K Ty S373 04187 m Ly 10385 m (Om the other hand, if A expands adiabatically, (AB) =(PA0.13x 195942568316 and, P= 6.680 x 10° N/m? = 6.680 bar [2 263.6 K Ty=8813K 1,=03917m Iq = 0.0655 m ‘The real case must be between these extremes. (Discuss implications that arise between the two cases) Piston adiabatic, heat eink in operation: ‘The mass and length balances of (c) are still valid, The energy balance, however is AU, +AU, =0 and the temperature of A remains at 311.1 K. As in (e), no solution exists. The Limiting cases, however, result when B is assumed to be compressed adiabatically (and in a reversible manner) or when A expands isothermally (in a reversible mannes), fis compressed adiabatically, using the equations derived in (€) except for the energy balance, 35% 10° N/m? =7.35 bar ©Energy and the First Law Char ot = 04202 Ly = 0.0369 m {A expands isothermally and there is negligible pressure drop across the piston, for ideal gases, Wy=—f PAV = -RT, MN, I(,/V,) = +R, Ny IP/P,) W)=-W, “RT,N W(P/P,) = Np C, (Ty ~To) AU,= 0, + Wy=0+ Wy ‘With this relation and the mass and length balances, 795 x 10" N/m? =7.795 bat 3K T,= 994K 14 =03962 m Ly = 00611 m 37 Solution ‘This problemhas many variations and only afew are noted below. Weselect the gas inthe cylinder asthe system and assume that the expansion i adiabatic and the gas ideal, then for this closed system ‘on a per mole basis: dU =C, dP =80 + 8W=0+ 8W=-PdV=—PAdh with A the area ofthe piston and the eight In this ase, we are using an intensive formulation for SW. From the ideal-gas la, RT = PA + hAdP combining and integrating fom P10 Py PHP, h/WhCO/ = PWT With R = 8.314 simol K, C,= C, +R, C,=20.98 Itmol K, f= 0.61 mand P,=4.05 % 10° Nin P=(405x 100.6178)" [Another relation results from a force balance on the piston of mass m. PA=PAtmg+masiz Energy and the Fst Law Chapter 3 whet isthe ano press, gh celeron du gv end the aceeraton af he Piston. Note that a = dic/dt=d°h/de = w du/dh where w is the velocity. Elimining the pressure betwen thes eution els elation between and h Wit te devie nsconsucte, when heigl are jten thee = LS aces ee X 10° Nien’), The flare is now in “free-fall” and the maximum height attained is 4.36 m above the round, Le, the tbe height pus height Inthe epi ater eto rom thu, th tine about 0.67 Todatemine he tine the inl late sends ins thee, we ca asthe relaonship dived caterbewean the vloty wand he hagich ta frau since u=ahvar and img betweonh=0161 an 2.13 Theme is bout 02 . The tl ime forthe are to tcheve maximum height she bout 09 ‘Toincrase th maxinu eigh a numter of changes re posible, Te mast obvious on i to cons the device otha gat pressure amenpherie hen enc fat cae one he accomplish isthe tbe length ay be edcedo6¢ main he op Ost maneinan ips 78m othe gal abe nth may be use bate sap nivel fom Det gene (raxinum helghe= €20 Many oer schemes wll work ot 89 Solution (2) The pressurization of the gas volume in the storage tank from 1 stm (1.013 bar) to 150 pia (10.34 bar) with air may be modeled in several ways. (One model assumes thatthe operation is dane rapidly with negligible heat transfer from the gasto the RP-4 or walls. Also, when pressurizing, the gas entering is well-mixed with the gas already present. In this case, Eg. (3-74) is applicable. C,=20.93 mol K. R= 8.314 Jmol K, x= 1,397, P= 1.013 bar, P= 10.34 bar, Ty = 294 K (@10°F), T,=T, = Tr Then, T, =395.3 K, Ths inal gos temperatures too low to lead to ignition al the air RP-4 interface ‘Another model might involve the assumption that the entering air does not mix with the air initially present but compresses it as though a piston divided the two air masses ‘Choosing he original ai asthe system, if this were compressed adiabatically from P, to aU=C,aT=-Pav ‘with the ideal gas law to eliminate the specific volume V, (fT) =P peo T,=5689K 6Energy and the Fist Law Chapter 3 as ) © In this model, the air atthe interface is heated sufficiently high that ignition may be possible. Clearly, this model leads to an unsafe condition. Other models may be selected and evaluated. The important point is that thermodynamics can only tell you what may happen after one specifies the fluid mechanics and heat transfer applicable to the problem, (It is also interesting to calculate the final air temperature ofthe pressurizing air in the second model.) The method of solution is identical wth P, = 1000 psia 1, (well-mixed) = 408.3 K T, (lower layer is pressurized adiabatically) = 975.7 K Clearly, in tis ease ignition is probable. Daring liquid transfer from the tank, the gas pressure remains constant st 10.34 bars as auditional gas flows into the tank. The enthalpy ofthis gas i constant and equal 0 Hy Choosing the gas in the tank asthe system, dU = 60+ 8W+ H, Bn, =NaU + VAN Where represents the moles of gas into the tank and Ni the moles in the tank at any time, Ths, bn =dN and 8Q =0 (adiabatic): - 8W=PdV-=PNAV+ PVEN ‘combining, with the definition of enthalpy, H'= U+ PV: aH__ aN i,-H ON 69 bar and integrating Hy _M,_PV/RT)_Vi Ty_G(ty~T) HH, Ny PYRE) Vs 7% ~C,T,=7) i +1 1 ‘where 7; isthe gas temperature initially when the volume is Vj Tis the temperature of the pressurizing gas, and T; is the temperature when the volume is V3. V, and Vo are related to timer (minutes) by Yy + (1809 V,—0.1 ¥,) bot, with Vi =0.1 Vp wy vu+@ona4 Energy and the First Law Chapter ‘Substituting in the expression for 7, one obtains a relation between 7; t, Ty and T,, is @ 204.3 K and T, is obtained from (a), e.g. fo the well-mixed case, T; = 395.8 K. Note that is in minutes. 8.12 Solution (@) Analysis of the gas inside the "bulge." Write the open-system energy ba dU =60+8W+H,3n, —H, Divide by at, note 3 (dU/d) = MaU/d) = NCfaTIAe) (Hy ~ Hoy )(By/88) (Tig THB 4/81) since Ty = 7. With N= constant it may be determined by the initial conditions, N= PY/RT =(1,013 x 10°(0.0283)/(8.314(311.0) = 1.1087 moles 2256 2 With C,=20.98 tino K and C, =29.30 mol K, 29,30)365.5~ THA. 54) 1 =3665 ~ (66.5 ~ 311.0) expl-0.1972) t= 6s, T= 3495 K, and P= 1.139 x 108 Nin’ (0) Forthe tank, V=0.2832 m* dd =60+ 8+ 1,6, 80-8 Divide by dt and note thet ay =NaU+ UaN 54 gis = 0.1566 mos (Hi, ~ UAN/d) = NaU/d) =N Caras And, N = (AN/die T,,=3665 ~ $5.50 exp (-0.19721) {from ()] “Ty C, THAN) Integrating,Energy and th First Law Chap T=(G/C)13665 + (281.3/0) ("= 19) (54.6 K, N= (0.1564)(3) = 0.4692 moles (0.4692K8:314)(454.6) (02832 when £=3 5, 26% 10° N/a? 3.14 Solution First, consider how the properties of gas in the left (L) and right (R) ends of the tank behave as gas is removed from either or both. For the left end dU =8Q+ BW Hi wo but, 30=0 BW =-Pav =-PNaV ~ PVN d= UdN + NdU & tw = Hyg =H_ (well-mixed) ‘Thus, Eq, (1) becomes, AN(U+ PV-H) =0=-NalU + Pavy=—M(C, d+ P dV) @ (R/PYAT ~ (RT/P?\AP Suibstitati 1/7, =(P/Py ‘where 7 and P; at inital conditions. For the right end, a similar equation is derived. ‘Since P (left) = P eight) and 7, P, (left) = TP, (ight) T (let) = P (righ) and this results valid regardless how the gas is removed. Letezbe the fraction ofthe total tank volume in the left end, Then Nef a o Wight "T-a “There are many ways to instrument and operate the tank, One possible method is to start initially at some standard pressure P,, Ty, c¢=0-5. Measure the total gas used. Obtain N (let) +N (right) by difference. Measure ckand caledate V(le/ft).N (right) Calculate N (let) and N right) and, therefore, the amount of gas used by Company A and Company B.346 Enorgy and tho Fist Chapter 8 3.18 Solution @ Refer fo parts (a) and (b) of Problem 3.9 for a method of approach, 820 Solution 10x 10° Pa 10° Pa jatm O=AT,—D, Arp) ( e d te R CRG ) gz. (g)a-» CA \\(p—p,) ® with T=T,,P=P,@1=0 © ‘You can obtain functions for P and T'via numerical integration (predictr-corector, Gear algorithm, Runge-Kutta, etc) or by simply using a forward-finite-difference approximation, Here's that algorithm: Algorithm to Integrate ABC Equation Set mt Bo rosin: Stieat }# — oe Pavan ney sar(if) nesag-roves (F) we) = 9the Fist Law Chapter a9 ©) (Quasi-adiabatic (7 Mission Heat tranfer becomes important |p Quasi-exponential decay ——} 0.1 MPa > Pressure will all in a quasi-exponential manner (similar to an adiabatic reversible ase) until large f, when heat transfer effects will have some moderate infivence on system pressure (giving a longer “tail” atthe end) ‘Temperature wil fall exponentially at shor times also, but as the Flow rate decreases (as AP decreases) heat iransfer will gradually become important. (0) will then pass through ‘a minimum before re-equilibrating wit 7, (©) Look at Eq. (A) where the rate of Tchange is given by asum of two terms: heat transfer term and an "enthalpic" tem, The former tends to raise 7, while the later tends to lower T.A dimensionless group canbe formulated as a ratio of these terms. For heat transfer to be negligible ‘At small this criterion is met because T,~ T= Oand. substitute instantaneous values for Tand P and chee — P20, Atother times, we can If we assume the blowdown is adiabatic asa first guess, then TT, will be maximized. For the adiabatic ease (part (@)) Eby and then the eriterion becomes220 CAR RP, ‘This is stistied if = >>0,00507 or P>> 0.114 MPa ‘Thus, only during tis last part ofthe blowdown a eat transfer effects important. (@) For negligible heat transfer (BQ ~0), Ba. (6) reduces to (Ge \P ar _ ae RIT ar” at rey" TR which gives us the familiar Again, Eq, (B) reduc ap POP eR(G } ?, FHP, ep ls porn] -SAaPt (Cp) Porth, Poene| SAPO le Pressure follows an exponential des With atime constant of 21.5 s (©) This part was solved using MAPLE (see attached input file) and corresponding plots of TE) and PCEnorgy and the Fst Law Chapters > # MAPLE V Code for solving part e, problem 3.20 > Setup the differential equations. No symbolic constants allowed! > Teqn := ditf(r(time) time) = 0.80389 * (T(timeyP(time)) * (300-T(time)) -(0-08326°0.40 (timeyP (time) * (P(time)-te+5); ‘Tisime) (300 - Time) ‘Tiime) (P(uime) - 100000.) 2D (900- TAD) oysa67194 (Pisin) = 100000.) Purine) Purine) ‘aifiP{time) ime) = 0.60883 * (300-T(time)) -(0.08325°1.402) * Pima Ter); a Fae Time) = 90383, Pea raps ne) BOLAND ine - in Sit Walia] condilfons for Tand Pr > Consti z= T(0)=300.0; Constt = T(0)=3000 > Const? == P(O)=20.06+5; Const = P(0) = 200 108 $i Perform a numeric R-K solution > Soin := deoive{Teqn,Peqn,Constt,Conei2),{T(time) P(time)}.ypesnumeric), Soln_:= proc(rkf45_x) ... ond >ekunWa tape a ee > Seln(0}; [0=0, Pime)(0) = 20000000 10%, (time X0) = 300.) > Soingaay, [0 22, Prime (22) = 7234343523275264 107, Tse X22) = 224.1529382251792} ¥ Soin($600); [0 = 3600, P(xime '3600) = 100053.8694883280, (sme 3600) = 296,9873235409763) 5 You can use odeplotij to plot the numeric output of daoivel], butt you just ># want to see the graphs, use DEtools{DEplat] to plot a system of DE's > with(DEtools); [DEplot, DEplot!, DEploi2, Dchangevar, PDEplor,dfitdplor, phaseportrat) > DEplot{fTeqn, Pea} {T(time) P(time)] time=0. 250,{(0,300,206+6) atepelae=T,ecene=[ time,Py.tile='Pitime) vs. time’): 5 DEplotifTeqn,Peqn}{Titime),P(time)] time=0. 9600,{(0,300,20e8)),stopslze=T,acene time, TyAitle=T(time) vs, time’ Tn 4 These commands produced the graphs Included In the solution