CHEMICAL ENGINEERING THERMODYNAMIC © 7 Thermodynar ~> Intvo duction. * Thermodynamics is ovighiated fiom Theyme C Heat) -Gveek word Dynamics Cforce) © All natural Processes occur with some wthm.Some ofthem ae spontaneous and Some we non- spontaneous ( we cause them te occur), Ex: water faving fom beight Tempaature Flow frm hot bedyto cold body. ® Mechanical and electical wovk is what drives our dally lives- cars, Ayains, Ships -alltransport reguive motors which are either based on the combustion of fuel ov on etechical users- * Our home and work environments ale unthinkable without many devices that are powered by electricity: miciowave,, tight, stove, re frigerator -TV & Yadio , smartphones, computers »washers, AC and the list goesan« © Clectidity is mainly obtained by Converting mechanical work into elechical workin a generator. our life stule requires an endless SUPPIY OF mechanical work. The starting point was the invention o¢ heat engines Particularly steam engine. far all engines bearis tyricatty created by buming a fuel like coal, natural gas cil ae. “Thermodynamics was developed out ofa desire to understand the limits Gp heat engine eF Fidency"! Te answers, tow much work can be obtained ak best fama heak Source aka given temperature ? Whak is the maximum work that could be obtained froma given amount of fuel?e Themodynarmic process flaw govern Heat to work conversion i heat engines & invelse; Work to heat conversion iN freezels, ve Figerators & NCS conditioning systems ; mixing and Seperation: transport through the membyanes ; chemical reactions and combustion etc: EXr weight on a coiled up thread canbe used to bring shart to vetation v Potential energy op weight is tansfomed to electrical Work UPON connecting shaft to generation. v Force of gvavity on weight generates mechani co) work v Mechanical work wotates short in a given divecion v Generator transforms methanica) to electical work Vv Forno Fictional & ohmic losses, amount o¢ mechanical work Spent = ammount dp eectical work generatoy v In reolty hee is loss, amount of electical Work < amount of smmechani cal work, wha has the remaining work gene ? © Mechanics explains frdion losses. « Rectodynamics clesctibes losses In ohmic vesistance Thermodynamics + due to Fiction and resistance, system becomes warmer than its environment, & then heak Rows into environment.e Mechanics > forte causes movement ofits point op application. @ Similaviy, temperature is a thermodynamic force thak causes heak to Flow. © Scientist asks — why does this happen? Engineer asks — ttowcah we use it? The basic \aWws fora scientist itis apart op anderstanding A describing the nature while for an engineer the basic laws are tools to model & itnprove engineering clevices - > Thermodynamic analysis Te entails the following. © Tytrodudory dis aission of system under considerakton - What is the purposear a system /hawis it acheived ? ¢ Genera discussion af wowing prindples ofthe system. # Clear identification of the system -Pecompasition into subsystems for eqsiey eudlwation, @ material consid erakions: fre there any limiting values for the system ‘paramekers, €-9- maximum tempeakure & Pressure Ahak cannot be exceeded? eo Dkermination of all yelevant Physial data at all relevant tocations inthe system & its subsystems. © computation of all heak and work exchanges fox the system and Subsy stems © Evaluation of system fetformances as expressed though meaning funy defined efficiendies measures, both Rr Subsystem and overall system. © finalysis oF system configuration and Petformance - Which contoliable Parameters thust be changed & how to improve or optimize system.e Second law analysis -Identi fication oF ireversible process In athe system Determination of ethoey generation & assodated wort less, oth within System and in exchange bjw system Bits sor andings . Which processes have laigest loses? can the system be modified to yeduce Loss? Is the systemas evaluated suitable for chosen purpose? whak ase the alkemakive systems oy system congigurations? which system | configurakion shoud be. fo\lowed? —> Applications of Thermodynamics — Hydrostatic and barometic pressure laws. - EFfidency mits for heat engines, refrigerators & heck Pumps. — compressor, pump, tuvbine, throttle, nozzte, diffuser —Heak exchang ets —fhefrigetaion cydes ~psychomeinic s -ostnosis & hearse osmosis — Mixing & sep erakia ns > Fuai celts ~Gecholyzers Combustion 3 ~Reatting mixtures “themodynamics also tells things which we cannot do it”—> System — portion oF aur study with a boundary. contol tass system control volume system system of study has tuo main chatactenstics 32 <2 Sompunding — Certaid quantity of matter system | — Boundary. (sotid or may not, imaginary) Lew ve —77"Spoundary of Boundary seperates system fom Sorpundings. aii the system except system comes unde sarmounding. @ conto] mass system mass + identi£y are fixed. mass interaction ic vesticked- Mass can neither go out poy comeiny but thee may be exchange OF energy. Tis also cated closed system. closed system : No exchange of mass Exchange op eneigy in any direction © Como! Volume system— volume is fixed Cexcept for deforming). the boundary of conto volume is contol surface. Boundayy a\tows trans fey OF Tass Y energy. Mass coming in = Mass going ovk sf coming an steady state Ereray consuming oy Coming In = EADY going OWS contol Roumnet e Asolated system- closed system with no energy intaadton, Tsolated system: No mass intetaction INo eneigy interaction[oc fees so) Psy opeh system, dosed system Tsolaked system EX- Boiling water EX: Refrigerant ExX> Practically not Human body water in botte possible Frutomobite engine piston eylindel delice Nudeaw reactor > TWermodynamic groperties Tdentifyable & obsewable characteristics ef a themodynamic system used to specify. a) Extensive Intensive © Extensive properties- Properties that are directly depend on mass & sige of system. TE system covlapses to a point the value of thic extensive property is zero. EX Mass, Volume jintemal energy, enthalpy Intensive Properties ~ Not dependent on mass.wheh system collapses toa point it attains a finite volue- Stvess -defined at point « EX> Pressure, temperatwe . Reman urchanged eth system is doubled.e Specific properties- A class of intensive properties which are defined ® as vatio of extensive Property toits cones ponding mass o= fry D= Specific grperty EX-spedfic volume, specific intemal energy, specific entropy a —— | | m Vy | Mam, Totensive progetties P77 [avs | yemain unchan ged, while | | 2 Va rT | estate ofa system~ Condition of a system whichis described imerms of certain measurable Properties inthe system.To do so | P,T | extensive properties | mass ¥ volume addup. Le we hove “N no-of Properties: So, ue have to identify those in depend ent taxameters to specify aq system: This is done by Gibbs phase wle. F= C-1+2 F=no-of independent jntensive properties C= No0-oe components TT=no-af phases 4 | x * EX> single gasin @ yom c=V Te=\ Pee : x Te means two independent intensive Ty two dimesiona) system if Properties are needed to des cibe a Xiy are thennod ynamic properties system. PINK A is state oF syste.presswre of steam-waker ak ee is iotm. Feat T= 100°C Ex Col @=3 Triple point No variable orno variation op Feo stake property B one phase exists. > Equilibrium. when can we specify a system with single valued property oy uniform Pogerty ? — No intemal processes should occur. — Nottomake it interack with sorsundings, so thak properties ih System donot change with time. How equitibrium is attained ? - Make boundary rigid sothak it doesnt altow system to interack ~ Mokke system attain same propetties as sormunding (dead system) Thermodynamic Equilibrium. Eauilibium Ye I I Thermal eouitibyium mechanical eauitipum — chemical eouivibnun eThermal equilibrium -Zeoth tawor ‘thermo dynamics ~concept oe temperakue “twa bodies are said to be in thennad equilibyium ¢@ both haye Same temperature throughout" How was this onginated?consider two systems A and ® dwactereed system A bytwo independent propetties X and Y. They axe combinedusing anadiabatic watt. An adiabatic wall is a wall which "cup peiently / resist (strong enough) ary shess developed System B | adiabatic AVE toimbajance oF properties blw A and B, % Ye | wail Tk was made of wood, asbestos etc. IF Lo the total system was isolated X and Yin both system attain random values. system A TE the Same system is seperated by high Xa Ya conductivity watl (diathenmie wall) then under Ee Sapte Ams condition X & Y poy both will attain closer = within some veshicked vatge sothak further gjore™ system @ B [aaa change wil not occuy. iol Xe Ye |* i “The equilibrium states acheived by two Cov more) systems chataderized by ceshicked values op thermodynamic properties SE systems, after they have been in communication with each other through o diathermic watt” “when two bodies oy systems are in thermal equitibyium with a Hs giatvern AhNdone then ‘ey ase in thermal wal equlibvium with each other" ( | —Zeth Law op Thetmo dynanig Temperakwue is Athennodynamic property thak determines whether oy Not a system is Ty thermal eonitibyum mith eatrh athorse Mechanical equili bium =Nek fore onthe system is zero oy there are no unbalanced forces. e chemical equilibyum - No nek change in chemica) potential oF veacants & products: Cdynamic e9™) ce Rake of Forward reaction = Rate o¢ backward reaction. > Thermodynamic process. RN, A\natuyol kocess can never i - oxe55 be specified bya favticuiar pal. - consider o ylinder and a piston, Va Pistonis loaded with different a weights as shown-There is a gas A _ present in Ylinder & thak is our system. vey mz w Initiay, after eaui librium is aktained, tek | Pre pressuke op gas & V\= volume of gas. TP WereMoVve considerable amounts Of weights Piston Vises due to imbalance in pressure. Instead ‘E We VeMoVve only Small amount of wk sg thak piston Moves very very Small Cintinitesima) 7 Zp = Brae WNz | vi=\y-de sirnilany (pwe continue this cazaiedy 4 tls f-de vils Vi-dP Qi, an This says all other intermediate states willbe in equilibrium,TE we Plot all those interme diake stokes we will attain above © otaph. such process is called quasi|statve e¢™ process: this means a process happens slowly enough fy the system to vemajn in intemal equilibrium. > Thermo dynamic concept oF energy. Energy canbe expressed as two ways - enaigy as Point fundion Cenagy storage), energyas rath functfone transfer of energy), Ene¥gy nna trees tL Tt Enetgy storage Eneigy trons fey (Internal energy) (Path function) faint Fundion -stake variable — Wark tan ster Heak energy The different types op mechanical work transfer ave © Displacement oY PdV work- Tis associated with closed system. No yeshictionin boundary ‘The work clone dueto the ee ocenee of system bound aryin quasi equilibrium Stake, ie, System can collapse through timiting em States infin itesiinany slowly, when extemal N PESSUKR is cued to intemal pressure thenit win 77 4 . Pexp=P aktain equilibrium. then ig system attains second eg state , state is PN. Hence workis done on Sonpundings 2 w= f pay (ss vipference of PAV from state \ 2401) Vis extensive soit changes but not P.wore PX A = force exerted Workdone = forte exerted X displacement TE displacement = dz Womwdone= PXAXKdAZ We tdv whue dV=A-dz 2 Uo done fon staterto2 wy, = f PAY CNON dissipaive work) \ Misis often called reversible work . @ Paddle wheel work. (stirrer wort) WOMKis transferred from paddle to te \fquid system. Fridiion makes it do- TF flutd doesnt have Friction then no need to stivy Treyersible work transfor = dissipative work © Flow work - pettains to contol volume. Womis done On neighbouring tayeloe fluid & itis stored-This Stored energy ts cated flow worior pressure eneigy ( veauived to Row) [ cont, = F 7 & — am=smat element op wok vowwme CV) PL 7 Py + - FERPA Ian We P, <2 m = Pade WorKdone Perunitmass = PA-dx —— dm= adm m= PAAX = PAAX eh _ pp V-SPROIFIC Pha Fo volume a. Mow Work= PY@ shart wort @ work ueated dueto wtatton of shape p= ak F cont) —_ Wowk & Heak are path functions. C2 volume {heshare NA rm yt \ ku Wye gen % Wi-We Si-a-2 61-9. Wye g-2F Wi-av- fone 1+ Be2. -A-2 2 sy Sip # 8 -g-2 ; ig adiabatic TT TTT L. cased) Heat (8) cold bath cased) caseltily Cased) - Adiabatic system . work Is done by stining the liguid which vses temperature oflantd. casei) - Heakis Supplied to the same system & he observed that temp-vise is same as work done temp. rise fingy caseGi) ~ Inserted hot bath into cotd bath & ebsewed that amount of heak lost by hot tiguid = heak gained thwgh o¥ by cod \quid, Aur temp: is measwed by a thermometer.gor” is W-. “wemis givento system 2 §2_\ -Neat is veleased ov Go-5 given out y = Joule found that Wyr=Qy-, Bit 'S cyclic in nature- ° ns 4 sign conventions of wovk & hectt plow. V. Work =+Ve Ceoming ak fem system to sompunding) o-work =—Ve (given to S$S8nFrom system) 3+ Heak = +Ve Caddedto system) q- teak =-Ve C removed fiom system) ¥& Rrst lawoe thermodynamics The algebriac sum of nek heat and Wo ihteradions between a system and its Sompunding in a thetmodynamical cyde is zeio" OR on Energy can be neither created nor destroyed , it canbe only trans Fened ov converted from one form to another” OR Energy is consewed » Makhemakicaiy, eS Q= Ew cde. ade 2-Swe=o PiFFerence op heak & work interactions ina adie £ (9-w) =o process is zetn. v Integral over cyaiic PECESS§ (§Q-Sw) =O — Coydc integra of anu Point Aunchian @ ; First la oF is 220) Thermodyt Now, the difference §Q and SW canbe exPlescu us pune fundiondhange: §6-Sw= dx X= property|] point function Q-W= bX OX = Intemal energy, fovan infinitesimal process = §Q- sux dE — $= §w+de {> point fonction => g-W= oe > 82-Wy2= &2-& Now internal energy is composed op several components of energy E= U+ Ey + Ep +any other kinds of eneigy (= Intemmoleaay energy CiFit is ak rest) Gy= Ainet\c energy Point funcons Ep= Potential energy AES d+dek+d Ey d(----) “Tnte mal energy is o progetty of a system whose change is @ process execsked by system cgnals the difperence between heak & woyk interachons bythe system with its Sormundings'! For a dosed system at eonitibium, de= du +d&p buk dp is very sman due to its change deé=du8.78 440, amic - SQ= dus Sw Te we consider thar system performs dnly displacement work , 2 Gia Us-tit f PAV 1 sQ= du+pdv {closed system Lek M= mass oF system (fixed) §g du ae Ne oe am om We Speafic volume > Gia = Us-t f Pay W= Specific intemal m mepy Ls spedific beak @ Enthal py H= W+pv — [arpticable for both open & dosed sy stem ) H= extensive property he ut PY h= enthalpy perunit mass V= spedific volume consider a closed system yedeves heat from ~ outside, ferfoming a prcess fiom state | to 2. dosed - Pdv work ak constant pressure Cdispiacement sox )\ system 2 NS 7 Qi2= werue f pdv F Gi-a Gyn = Werte P(V2-W) take P= heh Sir = Ur-Ur & PVF Pa Ve Syn = (U2 Fava) ~ Cult Pav) eastfom definition of enthalpy, H= U+ PV @ Gi2e Hath fora dosed system, change of enthalpy is egua) to heak added to system] released. oy = §G =du+rdv SQ= d(utPv)= dh §i-2= Hat How to perform displacement wok? When wort is done on a system the system bound ay expands , So pressure decreases, heak has to be added sothak pre ssile remains constant Nv {NS T increases, to Keep P constant, V vatig should be changed 7 T e specific Heats Co= Specific heat ok constant presswe = igi constant valu cy Specific heal ak volume. System consida a small amount op system Sm recieves &m . g @ small amount (infinitesimal) ap heat &@ for which T there is a vise in temperate § 7. &Q jouw, Cy= lim (Fen) o¥70 & Vecenstant fom Aistiaw, SQ= dU+ pdv sy = du +Pduv¥ &m Veconstant ak constant volume, (38) = (da) y= constant Cy = tw (du) Veconstant 800 ESCy= (& w=a(T Ww) atly Now, Cp= im (888m) p- constant Csame work done OE eT bak ot-onstant P}) fiom frst law, SG= d+ pdv 88 = dus pdy sm 8&6 Or = py) = ol pceonstone = dur Pl) = dh 89. = (dh [ Sm ) p=constant =(4 ) p=constante Cp = lim (dh) p St90 BT A\iabove approaches are for Cpe (22) corel mass system. ST /p © Fast law applied to an contol volume Copeh system) conside the fortowing open system where fluidis 2 dm, . : poo eS SE comming in and going ouk & depine a section | my, He = 2 L ak iniek Bouklek as \-1 and 2-2. | conto | y Vol i. Take that contol volume is taxing lume | 8 dm | | heak. since itis a continuous process a4 Ew Te whether steady oy unsteady processwe Gt = st define quantities per unit time- Heat added = 88 Work given out cuety _ SW ge a Shape wok &Mey= Mass of contol By consewakhion of mass, dm Ldm. = d(my) dt volume. “ae at CInpuk— eutput)= Rate of change of mass By consetvahon oF energy, e( stored energy ina sheam of fuid) has ty be Anow because it \San open system . Intemal energy in Auid = Kinalic eneigy + Potential energy + intennotewar adit (p0ss energy + (Pressure energy flow work) . C= utpl+ WV 492 Catt quantities are pet unit mass) Kinetic energy = ame per unik mass = Ve 2 potential energy= mg z Hressure energy= P_ Se Pey unit mass > gz Perunit mass > PY Ss speciic vowme We velodty of guid Z = elevation. Eetgy cutpukr = dm. e dt? Energy input = dm 6 dt! prpetties are invanant with ime Kunifom At Section t-1 K2-2 Any ey + §§ _ dina e, - BW dE “ae ste dt bt “dt Egy = Intemal energy op c@nhol valuine d Se (art eh tu +9%1) + ss - 4m Ct Av ta = 4.922) -8W = dtw & qeak steady state, Mey W Cay are invariant with time dmey, =o dE “ae ae ~° = dm ~ dm consewationop mass) dt at dm at Sean ui fh +e z, | + SQ _dm fus+pvit ve oat +971) * 58 am (ur nthe 492) oo be divide by AM | weget at wae avragz, + $2 x dt —Curh Va Vee +922 a ere 9 be dm ) - sw ydt . se am” ure WG aw sB\ _ x > wrhh os +92 + (§8) Cathe + Mo 4 ges) ~ @e\ <0 &m 88 = Weak added par unit mass uP C= 4b, SW Wor perunit mass (velesed) athe Vy =b om NS ete = (ha *¥ ggza )~ (hit gga) i... Steady How enegy equationWhen we consider changes in Kinetic energy & potential energy @ are negligivle then 88 _ SW L ba-h, Sim Sm change in enthalpy = pigperence of heak & work interactions a) for wavs Thterading devices, g &G — si Swe hh i z b> &m ig i fora compressoYy, PT, 7 VL g ‘JeRew i = sw + Sm Temeans it takes vor to do this: fora turbine woyis coming ouk So by-h.= -Ve so-h7h, & Sw =4ve () Omy beak ‘interacting devices. SW Lg om = Dy-h, a8 some Umer th contol yolume thee ismo uiow A heak iMelaction but thareis convelsion , e.g, Nozzle | . | Here, V2 2V, (velocity) by ba wi Va hoch re Vary . J! gpHtt S odiabatic wary s-8 Su =[ bere )- (made )since Were are no work Sheak interactions, £@ oles im Sm 9 Exe A Piston [cylinder contains 0-9 Kg of Iiguid water and o-1 Kg of water vapor ak Soo KPa Whe 2000 KT of head are odded at constant pressure, what is the final temperature and whak phase ov phases are present? 2000KT | Vapor | heak C4) To? 0-9 Kg Waid our system, is dosed system ak constant Pressure dU= G+W = Q- POV = Q- (ory) BU+O6PV= G o(U+ Pv) = g oH= @ Cuse steam taltes) H.-H, = 2000KT yoroy Hy=McuBL+my Hy (mix tue) go W= (0-%x 640-2) + (O-1K 2149) = SSI KT Yo= Hit 2000KT= 2E5(-1KT ak Soo KPa, H=28SV-1KT - Te = 198% & 200°C sak Te = 151-9° Coy vapor is pressureEx A gas of mass \-SKQ undergoes @ guasi stave expansion which@ folowsa relationship p=a+bV where aand b ate constants. The initiad and final pressures are 1ooosKfa and 200 KPa restecivay and cowesponding volumes are o-2m} and 1-2m3 - The specific internal energy ofthe gas is given by u= LS P= 8S KT/Kg ohare Ris in KRa and Vin m?/Kg-calauate the det heat transfer andthe maximum intesnal eneigy of gas during expansion. sl GU t fedv 1 Luo rdv @iven 0\= 1000 KPa V\= 0-2m> “CoP Wy, = 2 P2= 200KPa Ve = bam? > \oo0= 200 = we 0-2b QAti-2b Q= I160 KPa 800=-b b= -800 KPa 93 b= 800 2 2 Wia= f Catovpiv = f av+bu™ay 1 \ Ware aC) + &(V,2 v7) z Wia= N60 Cr a-o9) + (800) (4.2% 0.2%) a Wi. = 600 KT Si-2= Us-Uy + 600 KT ULs tspV- ssxm M=Mass op gas =15Kg We Uopv- 8S xsUUs SC Pa PV) = BSKES +H BSxLS Un-Uy = FS ( @00xt8 -1000%0.2) ~ 8 fs U,-U,= 60 KT Q\.= 600+60= S6OKT Given Us= VS PV- BSxXES = LS(QtbVM BSS Us bs (avtby2)- 8SxVS du = 1S (QtabV)=0 Cfoy maximum) av du zs ap) [vb eve dU eg ave Aye 2. moxinum will occ \ V=-& ~ - 60 = O°125m? ab — QAx80o Umax= Sx Catbv' )v! = &sxis = \+SX (M16 0~ 800 x0-725) or2S- BSXIS Umax= 503-a5 KT EX= A piston cylinder awangement is shownin the Figure, contains aivak 850 Kia, 300°C “The SOvg piston has a diameter of o-1m A initialty Pushes against the stops-The akmospheric pressure is loo Ka and temperature is ao% -The aylinder coats as heat is transfered tothe ambient.P ose ca) At Whak temperature does the piston begin 6 to move down? Bede crn iy Cb) How Far has the piston dio pped when ft thetemperatwe reaches ambient? eh Solr oe Let weight of piston be W A=areaop piston PoA +We P p= tor WK rooKtay SOK9x- BMS TExCon x 1000 4 P= 162-45 KPa lok The the temp eratwe T= 300+213 ;Petezus [ Pve NRT} Pp 280 PV nR T= AW oY 312-33K Tv We assume that pisten descends down in @™ fore so gas Pressure is constant - Displacement Work at constant pressure. _V. = constant T Ve Te = areas vy ON 573 Pi Ve= MRT, p= Wx 312:33 S43 Mi= SOX573X a8 4 Ve= (Be. 902k: 31233 ASO X1000 “513 \pee Volume of gas= WT KON) KOT = 69 63ux107> Vea 1-963 x 1073 x 392.33 = | 5uums 513suum? => h= 0-219 66m Orop I height = d-aS-9- 1966 = 5-34cm EX= fin evacuated botHe is Atted with a valve through whidh air from akmosghae (ibax,aS®c) is atowed+to Aow slowly to Ail the bottie. TE no system heak is transferred to or from the aly in the bottic, what will be its temperature when the presswe inthe bottle reaches \bor? TP¢ne bottle Miialy contains o-a3m> of aly ak YOoOmMM of ttg and asc ,whak will be the tempetalure be when pressure yeaches 160mm OF HgCatmospheric plesswe)? The property relations for aiv: Py'= @-aG7(t4+73) pwhere Pisin Keq Wis wa. U= 0-18 (E+a73) where Wisin WI/Kg and tisin ec. Flowis in but flow ouk =a Ma=Mass of ait mpipe Work W= 0 M= inital mass GFCV mpe= AND oF CV In pux of energy to cV= Maha Maha= CMp-m; ho (Me-M ha = MeUe —MUy h=u+eV e=o hq= ou foray h= Cpt Cp= 1-005 KT]KGK We CyT Cy = 0-118 K3]kg au vat CY > ueCyTtrec at t=o UO I. C=0 us Cy TAh Lp = akt=0 h=0 @ dt he pT since intial Mass=a , Muy=o ° (mp-yba= Weve H=usPy = O-TIRCE+AIZ) + 0.287 4 (b+.a43) h= loos t Cp= 1005 R5)Kgk Tyeha= MF Ue = 298K ha= Up Ta hax 1-008 Ta= 0-118 Te Tee ue Tee © f F & To Yan evacated bottle v Riye= m Cast) T Téommm Hg = 1oVses KPa TS Iygu uuomm tgs 58-662K Pq TD W= 8F622xX0.03 287x298 = 9-02056 Kg Tw delesniao — _ ti Th Te Bees ee eae TE0X298 To= 5IU-T2KEX+ fin aly line ak 300K and o-SMPa as shown is connected tog turbine thak exhausts toa closed initially empty tank of som? The tuvvine operates to a tank pressure of o-SmMPq -ak which the point oF temp-is 250K. fissuming entire Process tobe adiabatic dekermine tuybine work - For alt use the property relation as u= ote (b+a32) = 00S (t+a43) a Bh oye in KS[Kg j tin Po SH Maha -W = meg my eee Inteina) energy is changing only in tank MWe=Maq Chasto de balanced if w=o0) hae boos (300) = 3018 KT [Kg Ue= 0-718 Caso) = IVS KT| Kg 6 Ma= Me= O-SxXlO°x 50 ° F ——________ = 348. us kg 281X250 W= Ma Cha-ue) = 3uf-4u3 (30S- as) Wr 4a-5y MTFi Second low of HK Second Law of Thennodynamics. “themodyna All the processes ip nature aye ditectiond) in nature. Sfontaneovs process aluays move towards egili bum. Fuld Flows fom higher regianto lowe yegion , heat vans Fors from hot body to ctd body, Wass Aig fuses From high conc. to low concentration. JF reverse has to hapeen then externa) Source (s required. A moving wheal canbe biought ‘prest by application of frictional brake , by doiny so beak is generated. Phy sicalty Kinetic enemy is converted to intemmotecwlar energy, But to set this wheel in motion by cooling blake & wheel isnot possible. Thele are many examples where both can be done- heating & cooling OF body , expansion & compression oF gasthese process are such that te Yhey are exeatted in both the directions then, though system comes back to initial position) condition Ane Sonoundings doesnt: This gives vise to second taw- Thenmay vesewoly @ Heat Engine- Ibis a dewee which operates in q thermodynamic cyde which gives mechanical work by taking heak from highe soure catted thennal reservoir / source- Thermal reservoir is on ingne capadty body whae eveni¢ heat is taken out ov taken in the temperature. vemains constant: aos w= O, x po W= 8,-6, whee G, #0 ~ (eenipit is idea} Thennad erfdendy pe heat engine detemnines its bemcity to convert heck to work, Q=* = O-9. 2 7 oowe Gen ak ideal conditions, WE #1 as Q,#0 So, Kalin plank statement of a&4 tow gives “Teis impossible for aheak engine to Produce Nek work in acomplere cyde if it exchanges heat only with bodies ak a single Fixed temperature.” eteat pump. - A detice that trans fers heak TT fiom colder region (sink) to hotel region by using mechanical energy 8 Exs Refrigerator (wn?) W - 8 i= W+8> € Sau wes) [ET w G28 (wa) $0, claussius stakement of a4 low gives Wat. ’ Peis tmpossible to constuck a deuce which 10 pekaking IMawde, Will produce no effect other than transfer oF heat fiom a coaler to hotter body"! efeversible process. - Process where system is yestoved toils initial state withouk aFRecting Soundings Consider a system ak o temperate Ta heated toa temp. Tg -Sowe showd pronde system heak Te =Tg-TP we want to coo) — \ Th ieback, we need a system totake usay heat Weneed Ty < Ty «Now the sormundings suffera gennanent change. Soif we want evensonpunding 40 have sarne temp. they have to be connected. Causes o¢ Trreversi bitity WW) Lack of thennodyfamic eguilibvium. — Mechanical equilibrium, Cd Pp) ~ Therma) eguitibrium, CAT) ~ chemical eguitibriun, (di) when df =0 aT=0 dp=zo Gi) Dissipative effedts~inechanical friction BAL nau process are ~ fid viscosity ieversib}e ” - magnetic hystevisis “No perfect reversibie nda stidty Processes” -Aechica yesistance. byocess parfeckly reversible Revusibie in the limit Mechanica work De=0 oto (de) transfey dT=0 bT20 (47) treak Wansfer ~ mass transfer dC =0 eco (da) v chemi) potent ay e Reversible teak transfer process consider amass of woker at 20°% ,weneed twhedt it to 80°C by Placing sourd® oF 100°C ° ‘ et 2 SOUR temp ° a t aoc ee | one | a \ degree OF ireversibllity can be reduced by tempeature bsHeak ak infinite sina) change er nant cr . 2 “y [ a cy * ms : [oo-0%c] fs = [rood Roast] Lo | r °C al efarerible Cyde/reasible heating leoolirg Reversible heat engine Rewsible heak pump @ Covllary-T of second low. caynoles theovem:." No heak engine can be more efficient than a revesible engine Spaakihhg betweer the same temperakue limits (the temp.of heak addition & temp of heat rejection) and ail vevelsible heak engines apetating bekweer -the Same temperature limits have same erAdency "! Heg- reversible heat engine “He = Trreyorsibe heatengine Sige 8, breve Ne >1L v + erpfuentyTye Wa ne Ww © Sia 8, cose) assume = W>NR TR we yuerse the process rit wit) tun to heat pump, so link Gia and §, aS irneads. SO Sourte canbe resaoved W>We (getting work more than need J Soadditionas amount of woYk= W-We. Soit opaates with single sink which is NO& gassible & Violates Kalvin Statement. TE? NaQ is wrong. cose) EF MR B= , two engines are rasible casei) = Na 7 for same working limits ‘Reversible process is a theorekical eppect!e Hbsolute thermodynamic scale of Temp erakwe. consider reversible heak engine. Ne= FCT. T2) Np= W = Sa-Qe Si Sir Ng=1- Sen Sig F(TrT2y= 1- Gag Sig Se =e Cut) “Ratioop heak @teradions is a Rincon Qin OF temperanke yy Rroyersible engines” Co qT Heak engine A & Ug 9 1-9» Heat engine B —> reversible QO 6@) SL. F(T Ae) = Sw | Sr Fe ‘ =) Oey C2. F(Te.75) = $C) We= 02-3 83 $73) JF We remove heak sink Tr, then HER & HEg ae connected i series So, 2 heat engines Will Produce a Work oF WA +We Operating biw Tiand T3. for that egttivatent engine, 8, RCT) 173) ar ) ee 1173) = ' 93 $(T3)FE(CtyTe)s FUT) F (m2, 73) This hagpens ony if E(TT2)= (1) ¢(T) Ftz)= TL Oy km 9, pou ae oe 8 S, A pey asibie = 2B 4 mean teinp erature op heat ‘ addition & rejection = G& pum = Sl = SO WG-8. (coP) —wW=Gi-g, CP refigeratoe= So Oe WOO, COP) pump = 1+(Cop) vefiigemtor TN ! RHP Fo, I= Balt, (cop) CO gmoe = 72 | Tit ae tow can we acheive reversible process | close ty it? Camots engine.e Comots Engine This engine isa vevelsiple engine & consits of four Ai¢perent processes — ; (i) Reversible isothermal process of heat addition. (i) Reversible adiabatic Process of expansion. Qi) Reversible isothermal process op heat rejection. W) Reesibte adiabatic process op compression. ANpradtice this is condeved ip the following way. Considel a piston and acliader as shown ak diferent stages frum akc a sarah gaiesible 45 a adi abanc o. Z a puccess ssotner ©} process DIVIFIFITIWIT TT fepepeseeie ct ete he \-9e -1-Te jr 4 st 144 Diagrams are not to saley jwle “ cai wos! ol got hen * L (2a) P _ veyorible &8=9 a adiabane Ry Nt) aes (P4NgiT2) G, Ta HEg= Reversible ae a Ae =0 peak engine Si 4 682) <9 Tv T2 TE ayde parameters 's reversible , ule can express itas point function a in differentiaste form. §'ds=o ds= dG, S=enbopy Tv OS= f d8p a JS= Aange oF entropy S.-s, = f aL ja reversible process, t aoe S 88R C incomplete integral ) 1 oT(on (S83, < fnel $89 fF Whokisthe value of § so for an inesverible prices. This is given by davssius ih quality, «clausius ineguatity Ag d&g => dg eg § a i f > § T Temeans f 49 ID 5 pot point funchon ‘8 fg £9 ot a poi fundion A # 8 Cnot a point ) foi + fo - fe 89 [88 cos 7 . r 8 §9 ¢g,-5 £88 ¢ & J alts Als@ Proof of clausius inequality. @9 1, Wp= Sia- Grp bin YS W= 8)-82 We w @ Poco F 88K W5 Orn 82 ‘ Now, N=i- 82 = Npei- Soa as S\ Sig n< fe > Sic > S& 2.T Sr Sag & 7 8. _ @ a ae fae ds> 28 T T bS>0 ds 70 For any process, 4g 2f so a as= (S89 4X J all 2 AS= 8e + OS change of entropy _ change of ehtrony _, change of entropy dive fora system Awe to change of to internay imrevessi bility heok Fora reyersible process, ASi=0 &g = for An qdiabatic reversible process , os=aSe= f y Hea} Wandter foran wen ersible adiabatic fitcess, DSexq AS= OS; and OS; >0 e Tsentopic process weknow §8 ods T SQgztds G = [ Tds =area under ane t [Rwersiple and adiabatic)© Concept oF an isolated system. @) AS =O foran isciated system ~ <0 p= univege. \ System wo » | Allinteracting systems | - taken together as an isotated system. oY SK Fm ors 5) isorated = system * 05 ) somounds Tsol (OS)isotored= £605) gy interacting system (2S )utem 7 0 Cineversibie) 5) system ZF (Ste Rewetsibte) (4 S\aniverse 2 0 v Pandple OF increase in entyn py The entwopy change due to extema) inevelsibility because op heat Hanser may have any sign dSe>a Heak wansferred into sy stehy dseco — Heak Nansferred gut of system dSexo No heak transfer * A % + 1 re T gro \ ont | 7 i ce Fedde’ , rejected , ! i | t © SF 0 ss” 0 ss?&8 (28) system > fa (65) system = 5a 4+ 5S; (70 far ineversible process ) (=0 for revesible process) when @S) sytem 7° { & +08; 20 FT for a veversible process, 89 >a 3 §&Q>0 T foraniweversible precess, when 6§>0 , 6 heating 68 bar] £8 | aS; , oS70 Ja os T T Trreversibitity aith in a system ig Gite OB) read irreversibility Arreversibiity with blw system & Sonounobrg is extemal 1 | Aerual cydes canbe consideted as intemally Srevelsible bub ney ore extemally ineveisible. © Principle of Mhecrease of entropy, Consider o reversible heak engine , T, >t, We 61-8, ‘ few, §ia_ 84 in § 88s ' Too 7° Greversibie ' Q\ 8 2) <¢ Se sg an Ta § 7 <° ' x We can consider thak system as isolated system , be a , ; e cause wo Coming ov oF system has nothing do to with enhopy (4 s Juni verse zo 5), = -S1 @s)g= So. TI Ta OS) ye = 0 asit operates ina cyde process PS)univese = OD_ + One +O5)gCS) urwerse = = +o+ S Fora heak engine & its thema G5) universe ZO YRSENNOIS , =-¢ § ©S)univese™ fe EK consider two bodies oe ingmite capacity Ti? Ty / ' QS) univ = 2 gS \ = Sp Fl OS)g ' a a = Zon + Or ‘ YL Ty “Th = =3 bur nn = ODuiv= 6 (4-5) fora spontaneous heat hansfer from one vesenoir to anoth withouk any other effect in sompunding 8( 474) 7° for yeversible process, Ti = To © ©S univ =o CS)univ > 6Ext consider an another system of Tr & Te OF Same specific heats 4 ne ene sy item n @ ) 1712 » 50 Ty decreases & Tr Increases both reach Fralvalue Tp sothak no heat trans fer takes Place. we (T)~Tp) = pre Op) So,now Te= litte a Te= litte 2 BS) yriv = Ca FO) F Ae = (meat +f mcd T Th T hh T This means, Te> ia frithmeh'c Mean > n uae Geometric mean Dita ar Now consider simi\ay system but connected by heat engine, we ne O ME Engine will stop BY G fn T=. =Tp v TR tps reverible heat engine(08) univ = Sq + SHE + Oe (OS) g= mC \n Te. 1 Ss = 9g= me in Te CS) ye=o te (OSuniv=o ~Srevesible engine O= We tn Te Tt Tee Vtite Crecess stops when it attains geomefnc mean) . e Important ptoperty relations. from first tow, §Q= dus sw (cosed system) for a yevelsiple process ina aased system withomy pdv ae §Q@=Tds Sw=pdv Aus PAV Property reation vakid for any a Process as there anly state also, W= UtPV a dv= du+ paV+vdp bur from akoye du+p aV=Tds dW=Tds +vdP Tds =dh -vdp and Tds=dU+Pdv frinevasible Process, SQF Tds Sw #rdVExe @ heat engine opemtes betweeh maximumand minimum temp-o¢ Gre and GC Wespectively, with an eFfidency oF TO1 ap the appro piake carnot efficiency “Tk drives a heak pump which uses vivors wate ak uyec to heat a block ap Aats in whic) temp -to be maintained is arl°C- Assuming Hak a temp. difference of ite exits bbw working Auld & river wate on one hand, and the yequived room temp. on another, and assuming the heak pump te opaake af reversed camot cycle, buk aati COR OF SO-+f-07 ideal cop- Find dy Heak Ip to the engine perreat owt from heat pump Gy whok would be the heat required input tothe engine ie the yeguived teme-difference in heat pump is reduced from 141°C tos S A» Su 8, rt alle ee @) Su = 483 (we oie [333K 277-4 K [ore = x 2osft- i 4 Tenaine S TLengine os (1 2) W= 0-323 x8) =OS( |- 333 quu Qu= W COP doump Nengme= 0-323 WLaaeAaBPr T= Caney) Usasieag= T= 266.3 K Te 29-1 N= 305-2K(COP) pump = 0-5 (COP) igen) 2 OSX BOSD ——_--"——_ 305-2 -2663 = 393 fox (CoP)iaeod Thastobe rejected Y TPhas tobe taken Qu= 3-93 W 8u = 0- 32% 3-93 Gy a les output Now ie TNs (A1M-4~ UH) = 273K ql= AQ +y-Y= Qae-Sk Ceer)yp= OSX _AakS 290-5 -an3 = OSXW-1058 = 9-853 Bur &S-852W Oux 85-233x% 0-3218, 91 oy 00-6322. KS] Ky outputEX An electic cunent of (OA is maintained fr Isecond Na © yesistoy of a5 ohms -while the temp. oF resistoy is maintained at ance «for this whakis tne enhory change of unease & enhopy change of yesistoy.the same caxrent is maintained foy same tresistoy burnow thermatly nswlated, whose initial temp. is n°. Te the resistor has amass oF o-olKg anda specific heak OF o-8U KS] Kgk And eNrropy change in wsistor & enhopy charge op unwerse? BUS COT dtt= change in intemal energy. cole CONsidey sormundirg temperature = are == Aecinc work is tyans foned in & vaecls heak to Somundirg , carve 98 uniy =2 Watecnc ) CS)uniy =2 (© SYsystem™ * GBS univ = OSoyo + Os sonwanding ¢ OS )oy=0 Lsteody stake ) §= ph Wotectn’c because 5T=0 2 2 COT=U=O =f *At= S @ =~ At=100%2SX1 =-asoos Ceo ting owk) ODSyniy = 5) sonourdings ~ 8592 = gay os) Qt a3 A— Watechicar= - 25007 V by Wwtlaw, O= pu~2S00 TYTN bU= 2500JT = MCpoT g=0 S00 = 9-81 K O-SUXIO* AT OT= 1-300 > Te= 592-62Bs)univ = OSsys + CP sruntig ° sTe = sig = J imeat 2me in Je re ‘ TT t Ti 597-6u DS) yryy = OS)sye= Orie SU I CS uni @ )sys 300 = 5€STK + fivailabinity | Available Ereigy | Energy. — — w (WCB) + Qiejectog Q —> 9 — > q (weg) Onabove basis we define high grade energy and low ene grade energy “High grade energy canbe convetted to tow grade energy but Vice Verso is not possible. Here, @ cannat be comptetely converted to work -buk work canbe converted completely to heat: Wok —> High giade enersy Heat —> Lowgiade energy Cadsoinaudes inhamo\eaulay enetgy , Chemical energy ) Why beat completed cannot be converted to work? Tmogine we have equal quantities of these tWo forms of energies (work & heat) with us- © LOOKS of work energy (leks sayin formop aledicity) W) tookT of Heat energy:Lets say we wont -to spend these energies for heating equal quantities of water which is initially ak sovpunding temperature oF about au’. case) start spending heat energy first: @) since wate is in epuilibvum with soundings, initicd temp erature of water = temperature o¢ sompunding =au%e. Heat energy ak & below ave doestit have ahy +ve temperate gradient blw hark soulce & waker,so no heat tvansfor takes place place-this js ced uNaNailable onergy and is dissipated to aktnosphere. Heat energy ok atmaspheric temperature is catied datum heat energy: Any abjeck in atime sphete doesnt absorb datum heak as there is ne tempetatwe gradient b uk accepts heak ak teme: higher than Sormundings- Heat eneigy above akmosphelic temperature is led available energy- Lea's say ak auc unavailable enelgy is OKT, So when you tyto spend LookT of heak enelgy, you can only spend a maximum of GokT- Works MMagy an cther hand doesnt depend on akmos pheric fomporature - low grade ehergy Work —> High grade enegy Low giade eneigy causes loses so it cannot be converted to High glade eneroy complekely,Low grade energy Heak/ Intermediate anergy continuous comersion through o Ydic Process [| | Maximum amount is MM mum amount leee obtained as heak as lowgrade energy Lo v awoilable energy / Non awa ability | non available eheigy auailabitity ~> work pofentia) CSornundings) Consider tne following system o¢ carnot engine -~T\ Wmox = gy (| =} TY 5 ens Leanot * Maximum T, auditable ts ambient tem peratute (es) WS Qa ata Ss Winax- (*- 7 in To Available enetgy of G, att, = $1 (1-1 ~Te) witty reference toa Sorounding temp petature oF Ty. Qa 8 Te. ' ly ee energyNow, FX To and heat fiom T\is tansfewed to T, due to Prackicay digheulties ty heak engine as shown. @ : | Available energy OF Q, at T wrt To cy Nate = © (¢: Te | 1 ) =O) an “| \- Te a 8 ( a) oy Th (Ke) © ausitoble energy is gyeater than © 2. This always advisable to take heat fiom To source itsele o Tyyevasibitity ina process - @S . 5) system + Cos) Sonpundings : . Yung CS\univ 20 generation op enhopy ov production of exthopy (as) sys + (0S) Sony = Geneiation of entry py my Change oF enbopy 4 ek enbory ow | = Generation o 9F a System onbory Nans fered ouk erkopy F from the system (82-81) + (Z) = GS )univ con ° yy J \ (OS) sy HJ ss) Iptemay drevenibity . (48%) ™ 6 05) sys +f a OS; +89 = OS To oOwhere ps=entopy change due to intemal & extemay ineveisibitity T= System temp. To= Sovunding temperate Now, al) the three equations ave Sy nonymus. CS) sys + OS) gow = CS) univ CS) sys + Net ehhopy oukRow fiom = Generation oF the system endopy @s)eys - f = os — oO COS)univ = 08 = Generation of entopy Twrevasibiity, L = Ty nhory generation) = To (3 univ Vv . T= Too To= reference temp - here wehnow Ay= 8 (1 Te) [st | i Ba= 9(-B) me Te a ~4) Te fa TT va Ai-A2= 8 (te ©3) univ = C£)+(4 = 8(7-+) \ Ineveribitiry = To Sjuniy = 729 (4-4) Ta Tr© Availability ofa dosed system. Q= Aur+w ini Wiad G= Us-Ui+W Bo Ue . (ea -S))- + 20 ro rs PoTo Qs TF (0-8) > WE UUs + Tol So-S1) WS (Wi-ToS)) — (Uo - To So) Wusom < CU 4%oV) Tosi) -( Uo +BY ~To So) Waax = (Ur Pov, “Te S))- (Ue tPoVg ~To So) P= Wrlov- Ts (system + sonoun ding variable) Wmox= di- 9, d= availability function fdlabiity (A= 4) ~ Specific availability = u+ fous © Exergy balance in 0 desed system Rote ee hy \ Vit; S, MN? Ws [row bs u ad ‘ a sed \ dose ) 0 SMe) \ _system oS yim) Thfrom fist = @= U-Uy +w Exergy balance, Tnina) availabiity Ay= Wit Po V.~1,5, Fira) availability A, = UettoVs Tes, faltability coming aut of the system = enelgy Howing as work 8 eneigy flowing asheak T : 1- 7 Te a= af 2) \ R= W-Podv (work energy) — — > W-fte Cva-vi) FNailabiity coming te the sustem = & ( ae) 4 Pectease “availability = A2-Ay Aa-Ar= Ctr t+Po¥s ~ToS1) ~CuskeVa~ToS2) = (Ur-U2) + Po (W-V2)-Te(S)-52.) No auailability tanspored W fe (v>-M)) = © (1 ~ te) ouk Aouk = G4 Ua Us FPoVe + Pov 6 4.9, TH (hy-A) ~ Bout = To f (S2-s)~ & TH Pana atieantt oe ew @S)uniy | o- Ay= Dy Mout -E C0)Open system , Mev = awe mi, > mass censewation 3 ngow i f _aha at ag ieee i ou = 1 sw Su Urt Puy vas Zz. ma ) vowume 7” oe cs “ Da. urea [Men Far) OF taow . po W9z 86 mn ? ™“ Mem =m ee Ty! To =oulSide temperature energy baance, dee ni, (uP te +92) + $8 =m (uate tue ae z dt 2 +922) ~ Sw at ak steady state d Ey 7 At > Carte virus 4gz1)7 (U2 FPve +e 4922) = ie Sm Sn ae KAP, ae specific flow availabilites. Afley ‘ ° : ean e tg S$ (\-m | ~ tu - an, - 1 at ve TH ge 2 Fa T= T0668) yuiy = Toor ok steady state ARey a dat = \-T. — —-& Op-ae= Ho i ( Soe ) sm ™e sensible Heat effects 60) —No phase transitions, no chemical reackions -no changes in composition causes temp. oF system +o change. we know Specific internal enetoy, u= f(T V) since Uis dependent on more than one Property du = ae dt + (2) uy oT v Ly ak constant temp ature ak constant Volume buk fon ae Cy = Specific heak at constant vatume dus CydT+ (S) dv T fora constant volume process, iSochoric, AV=0 for inco mpressible Auids, ideal fluids at low Pressures, dv=o ~ dus CydaT fora dosed system SQ= dut tdv 'FAV=O OBQ=OU for mechanically wwelsibie constant volume process, G=dU bus CydT=Q Th &= bus f Cydt TT Te 9: fcvat qTalso, enthalpy, He eCRT) dv= (3), ¢7 + (33), ¢e He Mp AM= CpaT + a) dP ap lr fovisobavic process, AP=0 for ideal gas system atlow pressure dP=9 dAh= Cat Th dH= (dT nN for adosed system, reversible, isobavic process, steady stake Q= OW Th ge f ¢ at i te G= [ SvdT .-.. Isochonie process Tt Te g= [ GAT ..... Tsobawe process Ts buk empivcalty, Cp= AF bTHCT 4... To Q= ONs ff Casbte cT*) AT. -negiecing other t, tenn s Ta = a u 3 Q= oH= (orton eek Vy,Qaok= ACEW +h TW) + $ (2- TY) @) a ge oW= (a-W (OF BCHHT) +g v Ces £4) OW= Ce) yCT-To) Te bh +T> @y © Entre py changes for an idea gas. fora dosed reversible system, dus d@g-Pdv wetnow = h= u+PVv H= U4eV A= du +edv +vdP Av= dH ~Pdv -vdP => dt~ dv =d6_-pdvivde dg g= dh -vdP foran ideal gas, dy CedT and V=RT/p ASa= CpdatT- RT gp P AOa . pat _ a dp T T 7 me 46e _ gs TTtT fo 6s GY at fae R TT A oT e, p Te OS _ f &dt_ inks R oF RT ' The above equation vaates onty properties & hence ad itis independent oF path for anisentroplc process Crevebible adiabatic), as=o TF Cp= constant for a given range o¢ temp erature o= Cp int ~ Rin kr 2 Tj a In To _ es Cp Tee Rin fe ieee cpa near) R nT = tn) q Th a BopForan idea gas, Cp—G=® G2) coe -1 gL ty Cp r R/ whee Y= fe -\= yz UF act % Pa) 7 ace (4) e Tdeal Wark for a steady stake Flow process Weknow, GO eeee lees o( he V+ 9z) fm Sm a SQ- Swe o(hsytsgz) m Wetnow Bos { 88 Sw = oth v +92)m - TOS-m) Je we take Kinetic enelgy Y Potennay SeIQYy Ge negligible Wider = Cob ) ~ TQ am) Nideal= 8H -Tas -s ishypothetved . w N wor voguired = — 42a Wactucy Lom produce. ackuas WideasSome amount o¢ work is lost due to ine vetsi bilives: Wackuad = Wideat + Wiost Yost "Wide +4 aduay Wada = o (hat Ve4gZ) m -8 Wigegy= 6 C44 v4 92) — TWH sym Whose = Te S)-m-G Wiost= TSg Sqgzo A The greaker the inmeversibility of process, greaka is ps production, grearer amount oF energy becomes unavailable \/* Thermodynamic Property Relations 8 Weknow First law Fora closed system, homogeneous fiuid, Yeversible mechanical wort, Property Relaki« dU= ABT AW yoy AW = -PdV AGyy= TAS dus Tds-PdaV for n nales d(wu) = T d(ns)-Pd(nv) The mbave equokion iS app\icable for any system as omy properties are present. We aso Know enthalpy h=U+ PV dh= du-+ pdv+vdP dus dh- Pdv-vdP dh- pd¥-vde = Tds - edv dh= Tds+vd? fxr Nmoles, d(nhy=7T d(ns) + (nv) dPwhat is the practical significance of enthalry ? — Sumop intemal energy & produckop pV. As — Replecks the capacity todo non-mechanica) work & capadty to release heat — measuring changein ethalpy altows as to detemine wheter avxnis endothermic | exothermic. — calouate heat of wn — Measwe heok Row in calorimetry — Minimum power for a compressor Consider a gas inside a rigid box, whose intemal eneigy is W- Since it is i vigld box it experiences No fortes. When itis released fiom box & exposed to atmosphere the Sormunding aly tries to Crush GX with attnospheric pesswie ”. Ihen to ocupy avolumeV the gashas to do some displacement work egal to PV to ocelpy thet SPace by pushing atmosphere out of that volume, Hence, combined effeck YW= Ut PV wha is the practical significance of emhopy? — Entropy Tansfer ocarrs in forms of heat! inass transfer — Entropy teks mMOXi MUM Possibility OF existing ase f 48 Entropy = uneuoilable energy T Temperakure, Din entropy tnplies a hansition fiom ardered to disordered, form BS=O0 (adiabatic, ydrc, eg™) OS>0 Natura) ProcessWhakis the Pract cal significance OF gibbs free eneigy? 6) ~ MHelgy auailable ina system to do useful work. — pigference oF Intend energy of the system & unavailable energy (energy lost to sonptuindings) al — AG adermines divection & extent o¢ change - —vsed foy systems where P &Tis om — Determine spontaneity oF process SG=0 eguilibium oe SSuniv > Spontaneous 6G Tds= CydT + T (28) dv ov T from maxwell lation os) (2 \y ds= Gd ar Tass & Tr T (aR) av Fst T-dS equationnow take S= s(TP) As= (25 wr (2), 2° Tds= Ta) at +85) a = lin 36, & Mm (3 , Sq ACutpv) =dW (88), = Cah), °o an =tds+vgp constant P (8@)p= Tds = 13S * (3), tds 3s S= pdr + 7 (3S) _ ae SNE = max) arly ), Tds= G@dT-T (av % (Fp 7 Ns and T-ds egtation Die Noromeentdet Cedt —T (av) dp OT/p Tas= Cyl T+ (28) dvGat - T(x “e Cte Cudt + T( ab) dv &) T (Cp-cy) dT = T (35) 92 +7 (2b) av ap= a ( av) ae + Tt (22) av | 7=1C ey ee oT/v oy ae Re ar + (2 t), av a he 7 (By 0 Ae) a > Cpmcy = Gn > neu y fox bath equations bur /aP ar). (av C2), _ tee oa ar Geo (SY () +e (Sena) a <0 forall substances G-cy >o cy Now foyan idea) gas, Py =nRTm na = =n v (e tp P NO-OF moles as Cp Cy FT. OR mRT mR p mR Pee v* Q-cy= mR Waker ak u%e (Vv) _ =C . (Sap “trey * Volume expansivity [3 = L (av p Vv on ¢ Tsothermas compressibility Ky Ue = fae = av. T Vv ap) Vv ( Ys © Tsentwpre compressibility Ky sat (3). Now , Gs -pV ee (.-@T)V (Sr); = (Ky P- Br) vyA= Cp dts (\- PT)VdP fo rvin COMP essible dats As= @ at-evde auia Similarly, d= CvaT + (& T ’) dv | constant Composition ds= “v a4 & av T Kr% Solution Thermo dynamics. 1. chernical potential. wetinow fora single phase fluid in closed system with no chemicoa) ea ckian , dg=vdt-sdt > (S$), =V and (28) - s° but fv an open system whichis interacting with sorroundings the above equation isnot vaticl. Before understanding this we shail look To some Physic insight of temperature and pressure. © Physical Meaning oF temp erature. Enetgy exchange blu 1 and 2 ! iS E+ El= Cipta Vv, vy | dE, +dE,= 0 Cas total enetigy —— L------ is consewed it remains constant deta - 9) de,= -d&, ak ee™ entropy is maximum, ds= dS\+d5, = 33) devs 8 de, ~ 8 dey ge ok ae, ogy Oe u ds= (+, -t dei 20 Tit d& GEST - Sd RT RT 7 @= H-Ts a 4—) = N_ap- s - 4H aT RT er Hot sfarS= H- @ v K RSMeans R RT ORT alsa, vs H- PV Yolo PV 80, S/eq > gehevating function to calauate properios Residual pretty op gas|substance, Mea Pye M(t P) = m8 CTI0) f v Ls ideal vesidunay property ‘ead vi 2 v-vis Residual volume= Rea) Volume- Idea) volume of gas at Same PT. WIE Uda pyig , URE UR Leu | GAL Wh _zorMost gases behave ideaty at high temP. & low pressure, So a limit of presswe >a lim UR = fim u = tim Ud "0 Po P36 as Po V0 ,S0 decrease jy intennslectlar enelgy is experienced. ©. KE= PE=0 V= u's lim yk 2G P30 tim, R ti : ig Ves bn y= tim v V= volume P30 P30 30 See 2 Cie ee gry at Z=COMPressibilihy P20 Ps0 fackoy elim (2)RT _ P30 p ‘O. tay s Using L-Hospitals wie tim yR slim 82 = slope og Zvs P cure ak - R50 ps0 OP I+ constant tem p. Nice ee lim (U8 4 pv) 0 P30 im 2 lim gh a Mtn pve t70 ®>0 R20lim ¥® 26 too R Now, a(S Inv) — oh at P RT lin 2tstfen} | - P30 aT P gh constant, inde pendent oF T. RT Tocondude, : 2 950 eso ct live 6% - constant (ind ep endent of T) P30 R eno < = generating fundian 4(4)- VE ge- 8 gy aT RT RT - VE ap . ditions, ak isothenmna condition AC - Pe f P Ttegvating , 7 By of yh on weamita sf a(S) = f uh at o ZRT VISE RTp buk y= ZRT ' g ZA) AT vee Zeb - ~~ ” RT Pfacsh)- fea J=constant independent oe Lose f (EY ap Ca ee RT 7 e > Hh 0(6%,) | = (s+ { =par) Rr or IP ———e aT P & e e - f &) at Q oe oa) (2A) aP 2 =7T RT a oT P ? AT « f vA La AT Pp > ‘Se ~ arf az| a at an af 0 ap ° choose Teo as it doesnt appeay in dif cetence Trow to convert vesidual gmperties to total properties? We Know A= ania + ow® hm j J G aT + on “ e n&= -eq™ f 52), ae oO So caleulote HR ak stake | & 2 take diFwrence we get onfig z and 22 + SQ use buk we need Cp za ‘0 @ Coe R+BT 4+ cT + OT &use ZS T cuwe ak constant P. Now, yp g= os'3 4 os8 osh.z She os® -w fz - food 7 Tr 219 os= f ’edt— Re inka iy Pi Sol such way we canuse properties terelate the problem ¥Vivial Equation of state we Know = PV= AXbPH cP ~K... PV a(i+ bea chery oo. ) Q=RT from experiments a _ 14d p+clP™ where b! & cl are vit) coerficient Wooly Boye Rt Veer 2 Ds Bo cs coe RT ety fv Le C compressibility) i = Z=\ fovideod gas.PV _ 48 ea I+ OP Y cominient, same RT oy acuurayyas Z= 1+ 8° Vv iV t+ Boy fo better accuracy AT Vv ye Beard B= Second wna coerAcient c=thid Wii) coefRaent What is significance op z? a Z<\ More Attyacke ores duetolow P froin principle o¢ conesponding stakes, pure gas ak same reduced Pressure &T should have same Z- tye and We Cle cecritical value T «© Residual properties fiom vivial Equakion of state (Eos) @ we know Ze I+ BR oS re RT => zil= BP p RT R eee pe eeay ZA BL RT SRT P RT froin stakis Nica See emadunanis, Bis independent of P&T of = fa = BR RT RT GR _ pp RT RT a( G8 8 alsa, (S2) : . at le v hy ) ne —t a(* her) RT oT P Substituting, GR _ Be RT RT HARE = 7 2CH) | + -pr aC bir) RT R at Ip wis -PT (L ab UB RT RW aT TeSvs -h RT R da TE we Know Band dB we can caleulate ali wesidual AT Properties Also, Qe A= U-TS Ae vi + sh Rt RT RT V= H-PV oh. wh—ev aR wf py® + gh at RT at RT aX 2 eB _ & ge = $8 ~ £ dB _ p(zijey eT RT aT Rat a ge Rat= e ER Dg tte Ceonstant temp) z= I = p= ERT np es Inzet- Inv Vv RT dif ferentiaking , emer cz fa) aw P SRT de pt de _ av o ZRA Vv de dz eu P Zz er in generating function, z 4 - feos ay) a we Hnow lim y = 0 P>0PM = eo fen -9) “eT 130 V3 00 z?\ & spitting the above integral, R zm v Gre f (edz _ f (z-1).av RT t z oo wv af i f a ib )dz- f EY av RT \ (2) J v Gk kgf r GQ" Pdaz-ftdz-f ree f ie f a dv A v GY 8 cet (Cinz-tm) =f Ebay at con a g Vv GN = (e-Nelnz - f Edy , at 0 Vv gensty p are as Ye Ye Ge (2n- Inz- ( (2) dp RT - Vo@ C P30 8 4 dp az Mo. aT fej 7 RT fF |p +7! fh £ ey S$". Inz-7 sz.| de _ (zag R a Lx pP i om bik Z= [4 BP+cP> — P=densityGS _ aber cer Ine & RT 2 wo eG ae)e) ) e Typical PVT behavioy og a Fluid. Tsotherms : >>> > =Vvapor dome Consider an example of piston and cylinder assembly Wiwhich Wanidis filed. Liquid is below evitical temp. This point is T as shown. As we withdvaw the pressure ay pistonup Wards, yowmeis oO 8 © Dd vo inaeasing & Cresswe is lowered. we will wea a Stage which hits Points M ie, Vapor dome. trere first bubble OF Vapor is formed. ‘ Vquid M= saturated vapor ITE LB | wenid s 3 | tiquia | j | N= Satu\abed Kear || __! Vapoy TF we with draw piston even more, volume Keegs thaeasing & Hi Point N- AE POINE No most or it WII be vapor except one drop OF Nauld: So,if We Iawase tenp. CD density ¥ AB densityAt T=Te wecan reach a point where vapor & \iguid density differences Ue Negligible. O= critical point So, change ag presse in liguid phase doesht change volume hak much buk changes in vapor phase significant: This shows Wemds are Faiy In compressibie- cubic equation af stake captures PVT behaviay op Fluids. \;Vander Waals equation o¢ stake pe RT La b= fon Zero sige op moleatles is taten V-b V* — sinterackions within moleailes is present interns ap cubic Cquakon, z= 0V pve (-bP-RT)V* + aV ~ab=0 Ty z>y z*(-1-p) +B 2zZ-2B=0 ... cubicin Zz. If we save the cubic equation wo get -> 3 real wots -> 1 yea) Wok at T7Te Done ralwot TeTe > dred wots T=Te > Z equal yea wots (vapor dome) Homie get a &b Parameters? Te we take critica point o, itis aninglection point ( First & Second dervatives are Zero i.e. nettha inoeasing fundion nor Aexreosing.for Pvs V cuwe ak constant T és) Nadthem akically, ae | ae a Bb axe independent OV In. 8 wo of: teme- and pressure a= A RTE be LRT Gu 8 Pe Po=antical Messwre — Tc= Critical temperature © TwWo-parametey theorem oF colresponding state. Atthe same reduced conditions atl Pulds behave similany. Vander waa) Eos assures thak att fuids behave similany Tr= veduced temperature Ty= Ret Te Re Ry = reduced temperature. Reduced parameters means how Fay away we are from critical conditions - Guk th reabiy thisis applicakte for simple pinids (fainy Sphevical Anongotar tke AY, Ke, Ne). To Account for polarity, difference in Sizes acenhic factoy is IMboduced Taled three Ratameker theorem oF conesponding fas) states Acentic Facor= Wy - for simple Auid Auids a same Ty aa is almost same NO We Ar nonsimple fuids. Sak W= ~l-InP fix Simple puids Ings] == oo YI 904 At same Ty & frig two Auids haye same w they behave Simnilamy. So, wis inbrditced in Eos fx more rigowus teatments OF Auids.* Generic cubic EoS P= RT at) gt y ARTE boLRT, V=b W+eb) (v4 ob) me = < Eos 4H) o]e a y Vanderwaus cos : c 0 0-125 OUT Redtich y : ~ Kwon Wl? \ : ONS Q [S086 6Y Jou anue Red ORNS | an Kwong ae | 0 [OOP66Y louse Peng t og ( ) + J Robins on Tow 14V¥2]} I-Va. | o-one poe f ib ey (Tw) =(\ + (our sy sruu—o swt) (12 y)* See Cw) = [14 (O-su6y 4 \-5e26u-o-26n2w) (YP ). Redtich Kwong eguation. Lo a v~b TOS (yb)V whee a= auc Resa = 0-0867 AT. Re Pe 3. Redlich Kwong Soave equatia ny pk _ y pe AT _ att) a a a V-b —-VVAb) < . SiMete Auid sg [cena =-a8 — an (be) 3 : RT Ge g-yeinz FOP _ Inci- be) RT RT = z-1e 49 - In(z-p) RT gh ~tn(1= be — oP ao zZ-1- nz 3) cao St ee eet Need eee OD z (8) ae = bP oo. & RT R72 R Gu bP ~ S$ anz -In (1~ T \-b& R £ Now, 4 az de —= TSS + 71 AT LF, we 1 - af \-be RTU- Reng Robinson equation P= RT - aa V-b VV4b) +b(v-b ) @ Residual Poperies using van der Woals Eas. Pp wetinow GF = z-\-Mnz+ f (20 aP i S=denshty RT ° Vander Waals, equation ts P= RT og | v-b va ve Yar” RT AV Je RT earner Ses V=b ve ev 7 a Sie bere Ure stor von r ae a eee VoL 1 P sn 1 RT ze aaa gC I-be RT O ce oe ene be i-bP RT z= _ bp \ ~ a 38 i~be aT £ £ So, f(z) ad _ Gay - 4.) ap so £ J bp RT Be z = +b dIn(i-bp) + CaP ae ~b RT