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43_ GENERAL STRATEGY FOR DERIVING THERMODYNAMIC RELATIONS. inthe previous section provide the bass for ( own Se. 42 a efor fe ion elaine ete and pressure is * sesmn ase Star vear eee fnctions thus far defied is given in Table 4.4 thes are introduced as more compien clases of s}slems are encountered andthe pendent variable, since these variables are most frequently encountered in forall the other state function in Table 4.4 a Fane ents ag leis ce i een ad Zr derived wt tf ves probed in is ton ‘These relationships are the reciprocal relation me 429) ( 2), (i), (i), 43,1 Entropy and Volume Relations to T and P hip Between ts volume, temperature, veva.p) a The corresponding differential relation, analogous av Mars nap ‘Te coefficient relations for this equation give oC) (3) sn be expressed in terms ofthe experine nd - “The paral des variables and to temperature and pressre ‘Consider no the analogous problem forthe entony a 433) aS= Mar + war ‘cwaton can be writen a partial derivatives so that. as (28) are(2 ar), (Fe) 4” 439 “The second coecen, relations, Recall Bq (4.26) v= (8), --Gi),— valuation of requires shor thermodynamic aga sy been evalu in the consideeton of Maxwell 435) reversible process, he second law connects the heat absorbed with the ange in entropy: 30m = Tas ep 3) (8), ‘presare proces, for which AP =0, ean be writen * tme=1 (2) an Wah equation (4.34) 80m = 7 “Te eat absorbed fora const 430 ‘constant pressre process are the eat capacity at constant pressure BQeur =CrdTr (419) Comparison of these two expressions for heat sbsorbed at consent pressure demon: sts thatthe coefficients of dT must be the same quantity in both equations. I is ‘cvelaed that 46: - " Creat (ys )-4 Iain for he vaiaton of ereopy with temperate ‘Measurements of there tant forthe experimental ev aa sesan) tse Sar—vedr rand a are known a functions of temperature and re ) au) nthe process used to determine Cy, the own variables are the temperature, which SQ mv = Cray “The heat sorbed ir velated a the sate fonction S = SCT.) ‘is measured, ad the volume, which is held cons to the enropy changeot the sytem which 3 nominees wenn BS “To conver Fa. (4.6) forthe enthalpy to «fonction of 7 and P,substute for a8, a eer vat] var wed in detemining Cy, 6V = 0 and sd collect ers Hen,P) dt =cyaT +V0—TeNd? (442) ‘Sinan, a, 4.8) is ensily converted toa function of T and P by subsiting for as asy=(®) an ir), the stcond law as embodied in Eq Fm = F450 = 7 (, AF w Sat — Pua = VAP) Bonen ems Fak) dh =-(4PVe)dT + PveAP i Gite fee eneey fenton fs sey expressed in ems of the independent ible Tand Pin the vorsion orginally deriv “Tis collection ofall state fanetons expressed in terms of T and P just derived compa as) in these equations contain the following factors: au = Tas - Pav as TP which ae the independent variables specified in any Experi Cr, assumed o be available in N=O.P) dw =Tassvar Sand V, which ean be evalated as functions of T and, given, B nd Cr Fee) af = -sar Pav aa the intl and inl slates for» process traversed by a sytem are species heir temperatare and pressure, knowledge of the values of, Band Cy permite USP) dv =(Cp~PVaMT + VIPR-TavdP (Ast) encorncwams moras 57 1 funetions accompanyi by the fact that they 1 Bguaing ike terms MoXp AM My = Zr MoXp AN Yew Zr im which Xr. Yr ZrsXes¥p, and Zp are obtained) are expressed in terns ofthese variables. rie erors are clearly € osedtwith thi acti since bemodynamic qua Vand 7. es found AZ m= MUXrdT + XpdP)4N UydT + Yd] coetcims, Xp. Xp. Yr. ¥p are the colficients of and in the ons for dX and d? in Table 4, 4, Collecting terms 42 SIM AN y]dT 4M Xp AN YLdP 5. Obtain 2 » 207.) from Table 45 2 = 2ydT + ZpaP listed under steps 4 and Sar alemate expressions for 2 = (7?) ‘he coefficients of dT and dP in bot equations are respectively, @), — G, begins with «verbal satemen sesa.y) as= Mary Nav ase Mar nev 4s = MaP + W(VedT ~ Var) Santee gen 2 co oe wine a 6 is NVa=Cp/T M—NVB = MeNVaece/T —1p=—Ve emus (i) <7 H-(8) (8%) “The check, Ths, the equ aon Is CPB _ye)ary a= (Ge- a) er + 9) fn Heimtoxs free ‘ha vohone Ferry) ar =Mar+nav dF = MAP -4N(VadT ~VBAP) dP = NVaaT + (Mt - WV BAP af = ~(S + PVaMiT + PVBAP Nae (5+ PVM NYB= PVE ‘he genera relation that (Cy mentioned in Set. 4.1.2. By inspection, the coeticent ofa (sr), (6-4) [was shown Eq, (440) thet this oeticint is related to Cy a8) ar), ins Bor MCV = PVITKUPICID = V for save for oto: au = Mas 4 Nav Tate 45 (Cr/T oT ~ Vad NWVadT ~ vA) Tae 45 aH = Cpa 4 VN Taye Irena of rstonsconsined iTable 45, ln uch ese reaange the gore aption ofa ef he pend varie sesr¥) pation by B andthe boston bya MCPAIT + NVeR = CoB as 4. Soe for a arm Zas- Zoav as» hero (ore%) soon cos Te 4, Ths, an 25a, bes ae tows forthe nye, he problem oe he process cased aS » 0 of hi eqetion fen 62 nemnonancsmasnenis co on fo an Ideal Gas come wnat worsaras 63 To. fo ane fequenty ecure in ayes of ; : c= cr= ae as) eos monic ch gu ols ut sng slo ti fed at tons eae) = 30 aay Aa tm Cy bah same it ds Ine his vam E45 ein f te consponng vai or Cr s sn gece . aan v (455) JIM conti of canbe igi by ean nthe stn, hi goin ed va=ce-rv (2) =cp—n= cv ‘system containing 1 mole of substance, then x = 1 and Pva=Cr~PV (7) =Co—R=O rverr 36 as the molar volume of the gas (volume occupied by one * he experiment vate cm be copie or lows Arey the definition of the volume coefficient of the 7 “ i a apt (2%) 2! ry (a) ot ween (57), > ar | \@-z | am . of compres, : Piet gw) == 1a (er ol fo ea! gas a for a0 eer satin The ge in v ary (ae), oa 7 ternal enesay of an ideal gas for any process can, without exception, be computed ro Ba. 4.52), ‘A similar reso can be obisined for the enthalpy function. Recall Ea. (442) “The kinetic theory of gates demonstrates that the heat capacity of an idea fom Table 4.5, indepen their Hanh) aH CAT +v(~TaydP aa) the efficient of A? is Found to be va-raav[i-r(2)}0 and Bg, (4.42) becomes gas) CpdT 40-4? Cpa hey occur at constant entropy. (Ths conclasion is iabaic process since entropy i prodaced within the system) example 48, One ol of el gs nally temper 7a copying olame i comprested everably and abate fame, Compute the Bal tener, Tf te yen, Men the varies T= 1839) oem we ete resins he general case in Example 46, yelding Ts Te re Las. Teav ax Soe ‘Since the proce under sy is enrop, 5 = Oa =-Zhevs (es) CoB § ora ea eo = 1/T and mina P dough the equation aT TCA »(i) [Beret] -orwn ne “ -an % i inal temperature at the reversible adiabatic compression is Iropy when a monstomic ideal gat experi ‘The final temper the end of | oe npr cay) Nextt i i tg an, alle tha tai gas ep diab raperare dog, Ts phenomena he bs or ome eigen cys. onpenion of the gx ae Ws wempertre: us» yee Pp ‘The rest examph the daar: proce ‘Then whatever Algcteaic manipltion ofthis equation simplest: wey” relatenship expressed in ems PV%= cont, 4) epoca: the ever adit copes: feat variate to deste ie path favorite sample problem in every om [Lom «Ve 5 one ay emncomamcnanas wonaons 67 Since no transfer occur between system snd ts suroundings, the contribution to expands mus be entropy production xsing ofthe proces that eviderly eur far fom eq decoding tothe second lw To complete the specifica this process, 5Q = 4W = 0: Ths, the itera! energy of the system U the inter anne change during the proces, and AU = temperature, Eq (458, Since the ine as= Sars Sev 2 Tart the isothermal reversible proces comer evauteo nd Pn 8, r= Bavy = Bavy emwoomasec wus we nmanort 69 core 2 Relationship reir: $= $V), Ba (449) Cob

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