Thermodynamic Properties of Pure Fluids Determination of thermodynamic properties of a fluid that cannot be measured directly necessitates relating such properties to measurable quantities. In this chapter some new thermodynamic functions are introduced and the equations giving the interrelationships between various thermodynamic properties are discussed. These equations are derived using the method of partial derivatives. The frethod of Jacobians for the systematic derivation of thermodynamic relations is also presented and the method is illustrated with some typical examples. Relationships formulated in this chapler ‘would be useful in evaluating numerical values of all types of thermodynamic properties which in turn, are necessary for the practical calculations like the evaluation of the portant processes. Using these relations, the thermodynamic properties s like pressure-volume-temperature heat and work requirements in industrially imy of pure fluids can be evaluated from the measurable quantitie: relationship, heat capacity data and coefficients of expansion and compressibility, 6.1 CLASSIFICATION OF THERMODYNAMIC PROPERTIES Thermodynamic properties of fluids can be classified into three broad groups: the reference properties, the energy properties and the derived properties. 6.1.1 Reference Properties Also known as primary properties, these properties are the ones that are used to define the ar of the system. They have absolute values, as against energy properties, which are mel relative to some arbitrary reference state. Examples of reference properties are temperature, press¥ BERRA eerrony, OF these, temperature and pressure are intensive, and volume, and ¢iltly are extensive. In addition to these, in dealing with the solutions, the composition is als° as a reference property. 6.1.2 Energy Properties ‘The four energy properties are the internal energy (U), enthalpy (H), the Helmholtz free eet (A), and the Gibbs free energy (G). All are extensive thermodynamic properties and are iow relative to some reference state. These are referred to as energy properties, because, the ‘elthese thermodynamic functions indicate useful work under certain conditions of reste ‘i eelnanarlesrens teen mmmes aneee B sec tz work function and are jefined. Both these functions involve entropy in their definition and in many cunche aaa to work with these properties rather than the entropy itself. PEEPS 62 WORK FUNCTION (HELMHOLTZ FREE ENERGY) me ‘The Helmholtz free energy (A) of a system is defined as one A=U-TS 1) where U, T, and S are the internal energy, temperature, and entropy of the system respectively. Since U, T, and S are characteristic of the system and depend only on its thermodynamic state, Helmholtz free energy is a state function. Since U and $ are both extensive, A also is an extensive property. ‘To understand the physical significance of the work function, consider an isothermal reversible change occurring from state 1 to state 2. Then from Bq. (6.1), the change in the work function accompanying this process is AA = AU - TAS (6.2) ‘AA, AU, and AS denote the changes in the work function, the internal energy and the entropy respectively of the system during the process. Since the process is reversible, the heat absorbed Qp= TAS, and Eq. (6.2) can be written as AA = AU ~ Ox (6.3) According to the first law of thermodynamics for a closed system, AU=Q-W A} Substituting this result in Eq. (6.3), we get AA = - We or Wp =-4A (6.5) Te right-hand side of Eq, (6.5) is the decrease in the work function. The equation therefore i ing a process at constant temperature is:; A en ‘en ene, ic) heme ioe We eAe + spoetlng cnet ofa It is because of the fact that the change in Gibbs function G measures the net mi known as the ‘free energy’. cate For the electrochemical cell that we have considered earlier, the total work obtained (Wp) includes electrical work and the work done against the constant pressure of the atmosphere (PAV). ‘The latter work is always done whether the process is reversible or irreversible. Thus, the maximum electrical work that could be done by the system undergoing a given change in state is less than the total maximum work, ~ AA, by the expansion work and is measused by the decrease in the Gibbs free energy, ~ AG. ‘The value of AG in any process is quite definite, no matter under what conditions the process is carried out, but only when the temperature and pressure are constant the free energy change would represent the maximum net work available from the given change im state, 6.4 RELATIONSHIPS AMONG THERMODYNAMIC PROPERTIES ‘The method of partial derivatives is used here to develop the important thermodynamic relationships. The major thrust of this section is to express thermodynamic properties in terms of measurable quantities. 6.4.1 Exact Differential Equations Let z be a single-valued continuous function of two independent variables x and y. z=flx y) ‘Then the total differential of z can be written in terms of its partial derivatives with respect to independent variables x and y as tana? a a «(5 #+(5) 4 ec) ! “ differential equation of this type is ‘an exact differential equation. The value of | 4 ai ‘only on the values of z at these conditions, i.e, Mita) a Be Rte tee Uy aa lt bo grat can| 210 [A Textbook of Chemical Engineering Thermodynamics valved functions ofthe thermodynamic state, and dA and dG can be treated as exact diferent, Equation (6.11) can be written as dz = M dx +N dy (6.12) where M = (db/dr), and N = (&/dy),. Also, we can write (= ay (6.13) a A property of exact differential equation that we will be using frequently is shown by Eq, (6.13), 6.4.2 Fundamental Property Relations The differentials of energy properties form the basis for the derivation of a large number of ‘equations relating thermodynamic properties. These are developed below for systems of constant ‘ass and composition in which the only external force is the pressure and the process occuring is reversible. The first law for non-flow process is provided by Eq. (2.5) as dU ease, the heat and work terms are related to the properties of the W = P dV, so that Eq. (2.5) becomes “(dU = T dS - P dv (6.14) Equation (6.14) can be treated as the combined st. for reversible processes. Using the definition of enthalpy dQ ~ dW. For the present system as dQ = T dS and ‘atement of first and second laws of thermodynamics (ie. H = U + PV), the differential of H is dH = dU + PdV+Vap (6.15) Combining this with Eq. (6.14), we get —|dH = T dS + V ap (6.16) In a similar way, starting from the definition of Hel i si mn Imholtz free energy, Eq. (6.1 |, and Gibbs free energy, Eq. (6.6), the following relationships can also be derived, stent dA =~S dT — Pay (6.17) [4G = Sars Vv aP oa Equations (6.14), (6.16), (6.17), and (6.18) are the func ifferenti: ! (6.17), . damental di ations hie seas til ease emRrorerc in terms of te four reference proper V, 7 ands eant® Be Ole ty HoPertics is functionally related we « sesned feces abies example Eq (6.8) shows that acne st ene ‘| hus P and Tate the canonical variables or special variables for Gibbs fre function are Vand Te taanen ' ; Y bier sdy ita gatrige See aah © G43, Manas Equations voor Fi r iL. -Maxorell's equations are helpful in replacing unmeasurable quantities appearing in thermodynamic ‘equations by measurable quantities. Using these relations, the partial derivatives of entropy with respect to pressure and volume are expressed as derivatives possessing easily identifiable physical | meaning. Bach of the four Maxwell's equations is derived from the exact differential equations nf ‘of the four energy properties. Consider the exact differential of internal energy, i.e. Eq. (6.14). At constant volume, it becomes i Differentiating the above with respect to volume at constant S 2 ee (ee 6.19) | was \av), At constant entropy, Eq. (6.14) reduces to (> Differentiating this with respect to S at constant V : 7 FU oP ! SV. (ep (2, ‘Comparing Eq. (6.19) with Eq. (6.20) and utilising the properties of exact differential equations given by Eq. (6.13), we get a (2) (2) ne : Wh les nat rs: ws 3 fb evry ia | This is the first of the four Maxwell's equations. ‘The remaining three equations are obtained in | 4 similar way starting from Eqs. (6.16), (6.17), and (6.18). The results are given below. tae212 A Textbook of Chemical Engineering Thermodynamics Mnemonic diagram. A square drawn with the diagonal arrows pointing upwards is shown ig Fig. 6.1. The sides of the squares are labelled with the energy properties in alphabetical orjy (A. G, H, and U) starting with the topside. The corners are labelled with the canonical variabeg ‘of the energy properties in such a way that each energy property is flanked by its canonica variables. s a P Fig. 6.1 Mnemonic diagram for thermodynamic property relations. The above diagram can be used as a convenient tool for writing the differential equations for the energy properties as well as the Maxwell’s equations. The differential equations contain the differentials of its natural variables and their coefficients. The differentials are obtained from the variables adjacent to the energy property under consideration, and the coefficients are obtained from the variables that are diametrically opposite to these variables. The sign of the coefficient is to be decided from the direction in which the arrows ate pointing. If the arrow is pointing away from the canonical variable, the coefficient is positive and if the arrow is pointing towards the canonical variable, the coefficient is negative. For example, dU is written in terms of its canonical variables dS and dV. The coefficients are respectively T and P which are diametrically opposite to $ and V. Since the arrow is pointing away fom Sand towards V the sign of T is positive and that of P is negative. Therefore, dU = T dS - Pal: To get Maxwell's equations, Fig, 6.1 is thus used: Consider, for illustration, the topside of the square. The partial derivative formed by the canonical variables is (AT/AV). The suffix to be use is the variable that is diametrically opposite to the first variable, i.e. S. Then one of the P derivatives in the desired relation is (A7/0V)s. The other derivative is obtained from the opposite side of the square in a similar way.. This is (QP/0S)y. Since the direction of a¥* being opposite, ic. towards 7 and away from P, the sign of the derivatives will be opPos"™ ‘Therefore, or) fap (620) wv |, as jy Nexampce 6. ‘The molar volume of an organic liqui i ae v v ganic liquid at 300 K and 1 bar is 0.1m its coefficient of expansion is 1.25 x 10 K-!. What would be the change in entropy # pressure is increased to 20 bar at 300 K? What assumption is involved in the solution?Taman Prparios of Pre Fs | 248 ‘Solution ‘The coefficient of volume expansion is defined as vee od 1 (ov Pala, Since, this is equal to 1.25 x 103 K+, av ‘a = 1.25 « 10°V = 1.25 x 10% m?/kmol K Consider Maxwell's relation Eq. (6.24), which gives wv dS =-|—|] dP [m, AS = 1.25 x 104 (P; P;) = ~ 1.25 x 10 (20.0 - 1.0) x 10° = - 237.5 Ikmol K The change in entropy is Ii is assumed that the derivative (8V/27)p is constant in the pressure range 1 to 20 bar. 6.4.4 _Clapeyron Equation The Clapeyron equation predicts the dependence of equilibrium pressure on temperature when two phases of a given substance coexist. It is given by Cagle ar TAV bag where AH and AV are the enthalpy and volume change accompanying a phase change. It can be derived from Maxwell's relation Eq. (6.23), which is applicable to any closed, homogeneous or heterogeneous system in equilibrium, with an external pressure. Consider a single component system containing two phases, say liquid and vapour, in thermodynamic equilibrium, By the, phase tule, the system is univariant, i.e. only one intensive parameter can be varied independently. The equilibrium pressure (for the present case, the vapour pressure), is dependent on temperature only and is independent of volume. Thus, the partial derivative (@P/0T)y in Ea. (6.23),can be replaced by (dP/d7) without the constant volume restriction. Moreover, (0S/9V)r = AS/AV, where AS is the entropy change’ when a given quantity of the substance is transferred from one phase to the other at constant temperature and AV is the accompanying volume change. (AS/AV) is a constant at a given temperature, for both AS and AV are extensive quantities that are proportional to the amount cof material transferred. As we are dealing with equilibrium and therefore with a reversible process, AS = O/T = AHIT. where AH is the change in enthalpy during the phase change or the latent of phase change. Substituting these into Eq. (6.23) we get the Clapeyron equation, Eq. ELS tee Ae be” ‘Sivall gr gparcemgamcnh ins “= eed ee"in the solid state, both ‘of mercury is 9.7876 ki/kg, ‘ : ‘mercury: ‘Solution The Clapeyron equation (Eq. (6.25)], can be rearranged 4 Ret mi 2 ys th <=ll ap Assaming tht VAP remains constant, the above equation ca be intgtated af noe BA) sonienoa ma! yank fs tripe aH Here, T, = 234.33 K, P, = 1 bar, P; = 10 bar, AH = 9.7876 kJ/kg, we can obtain T; as below. AV = V~ Vs, where V; is the specific volume of liquid mercury and Vs is the specific volume ‘of solid mercury. Then a = 25888 x 10° m/kg in B_ . 25888 x 10°° = 10 - 1) x 10 = 23% io eat ti eich oo aed 805 x 10) ‘The melting point of mercury at 10 bar, T; = 234.39 K. 6.4.5 Entropy—Heat Capacity Relationships me ‘Maxwell's equations provide the partial derivatives of entropy, with pressure or volume. The Partial derivatives of entropy with temperature are provided by the entropy-heat capacity relationships. ‘The specific heats at constant pressure (Cp) and constant volume (Cy) are discussed in Section 2.7. These are defined as under, sitiogieagee item leanrtoe iors. RL Bigg Bortsnon rie! iat © 16K orbit ar rca githl OUR ot Horm dele nc. 1) and (6.32) is in the determination of entropy change of a system ‘volume respectively, for a specified change in temperature as=f cp 2 ‘temperature, the above equation can be written as AS = Cp na ES (6.33) 1 ;Emperature, the required integration can be performed analytically provided Cp function of temperature. In the absence of Such a relationship, graphical integration alues of Cp/T are plotted against Tor, and T, (or, between In 7 and In 7») will the increase in entropy of solid magnesium when the temperature is to 800 K at i atmospheric pressure. The heat capacity is. given by the nia 34 by init p= 26.084 5.586 x 10 T 4 28.476 x ip’? — alee boyrovtes Saibe If entropy were treated as function of temperature and volume, then S = AV, Dand as as dS =| — — ea wea] (6.36) Substituting Eqs. (6.23) and (6,32) into Eq. (6.36), we get tee ap yf > (= vee 637) The partial derivative (AP/0T)y appearing in Eq, (6.37) can be expressed in terms of (OV/QT)p and (VaP); which, in turn, are related to the coefficient of volume expansion and compressibility of the substance respectively. This is done as below. Let the yolume V be expressed as a function of P and T. V = f(P, 7). Then the total differential of V can be written as or ys av ov yor ot an oa wvs| 2 arr ar ae ete (il (FL eps Soe At constant volume, dV = 0 so that the above equation becomes “po [So] r=(B or mm gy expe 4 i he As This on rearrangement gives avian) PN ay ap (OVIAT)p _ ($I: = aviary, | } (3), ee) When Eq, (6.38) is substituted into Eq. (6.37), we get the differential equation for entropy os a ¢aviary (avian), = Cy ave z werd whitey) Tu 32% 7 yrs, a: as- ar=(h 8) ar Bea re ere i « oe Pressure and Volume on U, H and S$ relations for the estimation of various thermodynamic Properties of a fluid ina es a toppers a peecee = cop ana representing these effects are given below in terms ea | effects are contained in the equations developed in previous sections. a The effects of pressure and temperature on entropy are given by the Maxwell’s eal ‘Eq. (6.24), and the heat capacity relation, Eq. (6.31), respectively. They are reproduced below, — ’ aS). 52(20) ws eh 7|, ee (A lesa aT 7em The effects of temperature and volume on internal energy are obtained from Eq. (6.40), which reduces to the following forms under constant volume and constant temperature restrictions. a dU = Cyd (at constant volume) — | : ~ avIat) ney ot A a le T ad dV (at constant temperature) (645) %ede ene CRT ae ep PL gah 1H +) Rap Apinay eES v-7| VY (6.49) (s oP - (= } ia ‘The method of calculation of entropy and enthalpy of a fluid in a given thermodynamic state using gs. (6.24), (6.31), (6.48) and (6.49) is explained below. Other thermodynamic properties easily follow from these values. It is assumed that the following data are available. 1. The pressure-volume-temperature relationship for the fluid either as an equation of state or as a tabulated experimental result. 2. The heat capacity Cpo at pressure Py and temperature Ty, 3. The enthalpy Ho and entropy Sy at temperature 7) and pressure Pp. Assume that the properties are to be evaluated at temperature T and pressure P. This state is represented by point B in Fig. 6.2 T ‘Temperature. Fig. 6.2 Evaluation of enthalpy and entropy as functions of temperature and pressure. ‘The entropy (S,) and enthalpy (Ho) are known at temperature Ty and pressure Po, the fluid ‘in this state being represented by point A in Fig. 6.2. Since S and H are state functions, AS and AH for the fluid will be the same when it undergoes a change of state from state A to state B, as the AS and AH calculated for any process occurring between states A and B, We can, for convenience, ‘devise a two-step process for bringing about this change so that the enthalpy and entropy changes ‘in these separate steps are easily evaluated. During process AC the fluid is heated from Ty to T ‘constant pressure Po (step 1) and during the process CB the fluid is compressed from Pat : T (step 2). AS and AH for these steps are evaluated thus: Joy, Weal ne ps eyyedod 6 HT and S’ be the iis and sais » ‘at point C. a iernia Ht egcdua>. yin 9 “ LAST a tyfound out which gives the within the brackets in Eq. (650)ot Wen the Ae 4 “fF aesanpe 1H “Im on wo m C, : as= fe par = fe 23 442x107 are Let H’ and S$’ be the enthalpy and entropy values after step 1. Then ° H! = Hy + AH = 0 + 14.748 x 10° S/mol. ~~ Sf = Sy+ AS = 192.4 + 28.02 = 220.42 mol K ~~ ot (Joma Since nitrogen behaves as ideal gas, V = RTP, a = (orl, Step 2: Therefore, AH=0 £1OE as=-f R aE = 8314 In00 = -38.29 Ynol K Enthalpy: anid sith ae 4 H =H + AH =H = 14.748 x 10° Smol 7 - ae 5 = 8 4 AS = 220.42 ~ 38.29 = 182.13 Jmol K UsH-PV=H- RI = 14.748 x 10° 8.314 x 773 = 8.321 x or 2-08 oY ae oA Wr ay aB Ailes, tort “4 225.0) - ~0043 2 AS Went S08 = 7. ae CORE) = r na : vale ; ; oe 7 ; ae ee aw oo . or Vv — 0.043 area | ‘Substituting Eqs. (i) and (ii) in Eq. (6.47), T RT 365° 365 oe ee oe Hy av |, V 0.083 V- 008 V—0083" v2 Integrating Eq. (iii), we get vs dV ae au = 365 [ eos (i) + ve Here V, is the initial volume of the gas which is evaluated from the equation of state. 365 nedtratl [so x 104 + pe | Me = 0.043) = 8.314 x 373 FE i Solving this, we get, e ¥ a NS ONS ae Similarly, Vo is the final volume of the gas after expansion. 7 I ae ab : x10? + 3 She — 0.043) = 8.314 x 373 it ‘ BEG ET bb oh mT ~ A= = A i. E i 3 m> : Gh a (ha)| (a) The 7 eRe we Proposed change is assumed to take place Pressure, bar Temperature, K Fig. 6.4 Changes in the state of the gas in Example 6.8. Step 1: Process AC, isothermal at 300 K Step 2: Process CD, isobaric at 1 bar. ~ : Step 3: Process DB, isothermal at 400 K ~~ Since the equation of state is P(V ~ B) = RT + (APT ov or differentiation yields,4 i 0° + 0.2877 Cry = 0.59 x 10°$ m3 (bar)/mol K 5 x 10-5 m® (bar)/mol K = 33.55 J/mol K mss(8 ab GP om in = hat Sy ra ; t ~ ear | aes ar },\ av If the P-V-T behaviour of the fluid is known either as an equation of state or as a graphical Fg, (6.54) can be used to evaluate the difference between Cp and Cy over wide ranges of ten and pressure. (6.54) can be written in terms of coefficient of volume expansion () and coefficient of compressibility (x) which are defined as below. ‘ pe 1 fav Ba lw © WAKO Jp. 9) (ee MaloP which means that (0V/7)p = BV and (2V/0P) = — KV. Using these in Eq. (6.54) the following equation results: create ( ay | Bie fc (6.54) and (6.55) are aaa valuable because most of the laws under statistical thermodynamics on specific heat deal with Cy, though these are rarely experimentally. These equations provide useful tools for calculating Cy from experimentally d values of Cp, NEXAMPLE 6.10 Show that for ideal gases Cp ~ Cy = R. Solution For ideal gases, PV = RT, or V = RT/P. Also, RT (2 RT aosi ify Saar aT RTT mee r 1= 2a(V = by RTV u rien Waals constants. The van der Waals equation is P+—|(V-6)=RT = of ah )idleats “Combining Eqs. (6.31) and (6.32) we see that as (CBA asian ya CIT ue In order to express this ratio in terms of P-V-T data, let us assume Sz as as * hae : [ze] «+5e] ; At constant entropy, dS = 0. That is, Rearranging this equation we get a GIG a Byfalioming 5 =f v, 1) and proceeding as above, we can show that . a BEG aa Substituting the partial derivatives given by the preceding two equations into Eq (6.58), we se that Ce _ (OS/0P)y (OPIOT) 5 _ wie siiale baa Gy” O9ay OAs wy, Itis to be noted that it is impossible to write the ratio of heat capacities | Seca cores nt : Ts. i aad Effect of f oe"Show that Cp and Cy of ideal gsr ar ndpendent of peste and volume, Solution Since PV = RT, vsti ela On substituting these results into Eqs. (6.62)-(6.65), we see that Oe) AMER), ( Co | a “Pj, \ Wf |v), | oP ‘This means that, for ideal gases Cp and Cy depend only on temperature. EXAMPLE 6.14 A certain gas is found to obey the following equation of state. Fn OE iB Pr 2 r (a) Develop a relation to predict the effect of pressure on Cp (b) What is Cp— Cy? Solution Equation (6.62) gives the effect of pressure on Cp. The partial derivatives in this equation are evaluated first. DVa\niupR wa 2Cr.. 180 12D wv RT oS ‘=, of ele Bache 79 r (a) Substituting these results in Eq. (6.62), ip eens are ee a he OD & i BRR ABi yi IS dS =| — Isl dP + ‘At constant S, we have Rearranging this, we get _OSIAT)p(ATIOV)» _ pty 3 (AS/0P)y— (ASIAT)y(ATIAPy Cy“ OTIAPyy—* (WV = BYR Wj, aP)\ _ _(SIOV)p Cp. (TIAV)p PIRG gf Ee =- x -/: Vind This can be written as pa Pog -b din P=~din(V-b)” din PV - by =0 ie. PV - by? = C where C is constant, * en Coefficient As discussed in Section 5.3, the Joule~Thomson expan: employed for cooling and liquefying Of gases. It involves adiabatic throttling of a gas. The enthalpy remains constant the Process. The Joule-Thomson coefficie is the fall in temperature associat with, a unit se in pressure under this condition. i volo 4 gas cools on throttling, so that the Joulé—Thomson coefficient is positive. H Bi ctu ccinis i tg bee the expansion OT THE Bas. ally at a state the point=f) -v) Fivienil on (Sa ee 7 ee the Joule-Thomson coefficient is zero for ideal gases. Solution For ideal gases, (V/IT)p = RIP\The right-hand side of Eq:(6.70) therefore becomes. zero, which means that the Joule~Thomson coeffici (u) is zero. .> EXAMPLE 6.17 Prove that the reversible adiabatic expansion of a gas always results in a temperature decrease. Prove also that this decrease in temperature is greater than that from Joule~Thomson expansion between the same initial and final pressures. “ 0, which means | (AT/OP)s > 0. That is, the temperature decreases with decrease in pressure in a reversible Process. Eliminate (2V/dT)p in Eq. (6.70) by substituting into it Eq. (6.71). i ar) ov eee PB \aP )y. Op ) pam ou onion fe et ti hari y ail ? — Taney y= yu, v), ue ‘The Jacobian of x and y, denoted by [x, yW/[u, v}, +e fe (3) (i Ee) ee mel ov), NOVA art shh > ge Oe The following are some of the properties of the Jacobians that are useful in the thermodynamic relationships. Property 1: [x oak x) Property 2: a ‘at Property 3: [ax, By] = Ne vd , Property 4: In Jacobian notation, the partial derivative (Ay/dx), can be expressed as 2) 1 ea) ax), (zl ybonnestT [nyl _ fa ys 4 . eres: RUIN lpn mm Property 6; The exact differential equation, dz = M dx + N dyin. terma-of, id fz, u) = M[x, u) + My, ul 5 Property 7: The exact differential equation, dz = M dx + a, ‘may be put in ar (as oy BAY . Wa aS hei a an pitamnnisoteataak te bosoms od ano enoiseupd 4 Haw, 4 te aes 7 awen nidenuideadd WFD Ceres) AA gy bodiam ot oh : V2 Using the property 1, this becomes ‘st * (P.V)__ 18.7] mv Try so that a iP, y=-15,7) or (2, M= 17, 5) nal Heat capacities Cp and Cy. The heat capacities were defined by Eqs. (6.31) and (6.32) af 9), Ge (88). & OT je Te One OF se of salt Oy Coefficients of expansion and compressibility. The volume coefficient of expensed HM and coefficient of isothermal compressibility (x) are two other measurable quantities like heat capacities at constant pressure and constant volume, They are defined as In terms of Jacobians these become REARLE 619 Dene the foie | “eave, we see that all"oe decane is faction OF temperature and pressure, then eeitioRgES Nak (634) be Pyne i) yataalgadt fi notation, Eq, (6:34) becomes SP) pp, TI ra en the heat capacity relation, Eq. (6.91), we have (6:96) «oi eae Maxwell's equation, Eq. (6.90), and using the property 1 of Jacobians, om (s,7) Vl _ WP wT) (Pl ca wot yo (Gall, -By Maxwell's equation, [P, V] = [T, S]. Therefore, (7) _ WPI a vn wT oa Using Eq. (6.81), Eq. (6.102) may be written as svoda. ae (ST) _(V.P]_(W.PYIT.PI__ W.PVIT.PI __ @VIOD)p WT) 7) W,TVE.P] WV TIP.T]— OVIAP) Substituting Eqs. (6.101) and (6.103) into Eq. (6.100), we get 1 i (IAT )p dav (VIAP), We can use Eqs. (6.93) and (6.94) to write Eq. (6.103) in the following form. _ __ W.Pyer.Pl_B W.TVIPT) x (6.103) aie T Using this, Eq. (6.100) may be written as" z ween Jacobians [S, P] and [S, V| may be obtained using Eq, fx, u) Ly, z] + Ly. 4) [z, J + [z, uJ xy) = 0 = x =S,y =P, z= V, and u =T in the above equation. ? ea IS. TP, V1 + [P, TI LV. S) + IV, 71 IS, P} = 0 - On rearrangement, we get a fata [s,Py= — STU VI + IP. THY. SI _ IP. THIS. VI- 15. TP. ae W.7) V.7) _ a i core 15, F) _ [P.7)1S,VJ-(S.7IP.V)_ _{S.V) _ (5. T11P.V1 xe 7, PI) (7, PIV, T} V.7) (7. PIV.) The above result can be modified as fai 3 (S.P]_{S.VI_ [7.S11P.VI P) Vy) tr Pur.V oe From Egs. (6.91) and (6.92) we see that = ' (S.P] _ [5.¥J] Rem 2. Caen = ca {Fe P) irv)} <<, ao I — (6.106), we obtain G-G 2-7 ESUAM (7, PUT. Vv} equation, Eq. (6.107) can be written as Cp 2G = TH PUEM) (7. Pir, Vv)tn terms of partial derivatives, the above resi gives aly Z opr Teta) of ar}, (av ‘substituting Eqs. (6.93) and (6,94) into Eq, (6.109), we get 2 6 -eell a (655) EXAMPLE 6.20 Using the method of Jacobians show that GH | sonnet a DVL y | Solution The differential equation for enthalpy in Jacobian notation is given as (A, w] = TIS, w] + VIP, wi] (6.87) Let w = T. Then (H, T= 11S, T] + VIP, T) (6.110) The property 2 of Jacobians permits us to express the (QH/OV)r as oH) _{H.T) 54 (#)-ira eit sanhetad'® NY Substitute Eq. (6.110) into Eq. (6.111). Then aan sri acd oH) _{H,7)_ TIS,T]+VIP.7) oe Le v.71) wn pee ‘ing the Maxwell’ ition, Eq. (6.112) becomes soubor (G12) ee Using -well’s equation, Eq. (6.112) aie oH TV, P}+VIP.T) aglts Pi) ort wR (ae JF Lap yeRp OT wry” iia teas a nares the aEq, (6.115) becomes a TWP VIR.TI | TaViaM)y —V a0 GeU ilo Sa ak (6.116) may be rearranged as 'A ’ Gaal inf >.C.». alaMeeD whore Cis, of integration that same dimension as pressure, usually or bar. 7 461 Standard State for Fugacity ee Bos ‘Consider the molar free energies of a gas in two states both at the same temperature. Let G; and G, be the free energies and f| and f, be the corresponding fugacities in these states. By Eq. (6.119), ~ the change in free energy is ae AG=G,-G, bi (6.120) i The free energy change can be experimentally measured and by the above equation the measured free energy change gives the ratio of fugacities fy/f,, The fugacity in any state can be evaluated if the fugacity is assigned a specific value in a particular reference state. For an ideal gas integration of Eq. (6.117) gives the free energy change as P. “Bae (6.121) i Whereas Eq. (6.121) is applicable only to ideal gases, Eq. (6.120) is valid for all fluids i al. It follows that in the case of ideal gase P,/Py, o fugacity is direct i pressure. The proportionality constant is chosen to be unity for convenience. That is, /1P = 1 oF {= P. for ideal gases. The fugacity is always equal to the pressure for an ideal gas. However, for real gases, fugacity and pressure are not proportional to one another, and //P is not constant. As the pressure of the gas is reduced, the behaviour of the real gas approaches that of an ideal gas. ‘That is, at very low pressures, the fugacity of a real gas should be the same as its pressure. So the gas at a very low pressure P’ is chosen as the reference state and it is postulated that the ratio of fugacity to pressure at this state is unity. Thus the definition of fugacity is completed by stating that es perfectly. By this choice, the stan ¢ The standard state were chosen as the one for which f is d state of different gases would have different and complex properties. If the st were the gas at zero pressure, the free energy would have become ~ o° at the ‘of the hypothetical standard state standardises the interaction bety ‘Selting them to zero. Since all intermolecular absentSane > ge * og i eee mde Yfiss_uy vo? etet2 bebe hag fe Reed suwerc09 2 pes Tie RB foes os A603) : premiesespaitt ni asi) v0 and f = 4P, we can write the above equation as {Elo G= OP + RT In Fy + RTIn 6 (6.124) For ideal gases, by Eq. (6.120), G = G+ RT In P/P?, Combining this result with Eq. (6.124) we see that the free energy of a real gas = free energy of an ideal gas + RT In @. The quantity RT In @, therefore, expresses the entire effect of intermolecular interaction, ; Since all gases becomes ideal as pressure approaches zero, we can say that f>P a P30 HI o: g>1 a P30 - 6.6.3 Effect of Temperature and Pressure on Fugacity ea 23), G? and f refer to the molar free energy and fugacity respectively at a sepa ‘where the gas behaves ideally. This equation can be rearranged as Ptadet 4.5% a) eng Sait bak duiedt ipo uv ap cea pet na ve pops = pa i eahaltties are empirical constants, 2 8.14 Using the generalised compressibility factor method, explain how you would make a generalised condition of enthalpy departure for a range of pressures. 6.15 Describe the 7-8 diagram of a pure fluid, Given the equation of state or the generalised ‘compressibility charts, explain how you would construct the 7:5 diagram. Give the relevant thermodynamic relations and the reference states used, What additional data are necessary? 6.16 The melting point of benzene is found to increase from 278.5 K to 278.78 K, when the external pressure is increased by 100 bar. Heat of fusion of benzene is 128 ki/kg. What is the change in volume per kg accompanying the fusion of benzene? 6.17 Carbon tetrachloride boils at 349.75 K at 1 bar, Its latent heat of vaporisation is 194.8 ki/kg. What would be the boiling point of carbon tetrachloride at 2 bar? 6.18 The variation of vapour pressure of benzene with temperature is given in the table below. nk 280.6 288.4 299.1 ~«3152 3336 ”«353 Pibarx 10? 5.33. 800-1330 -26.70 5333100 Estimate the latent heat of vaporisation of benzene and its vapour pressufe at 393 K. Is it possible to approximate the vapour pressure as an exponential function of temperature’? Does the Clapeyron equation suggest such an approximation? 6.19 If the pressure inside a pressure cooker is 200 kPa, what is the boiling point of water inside it? The normal boiling point of water is 373 K and the latent heat of vaporisation of water is 2257 kJ/kg at 373 K. 6.20 The vapour pressure and molar volume of water as function of temperature are given below: TK 490 500 510 PS, kPa 2181 2037 3163 Vo, milkg 91.50 « 10° 75.85 x 107 63.23 x 10° ge 1.18 x 107 1.20 x 10 1.22 x 10 Calculate the latent heat of vaporisation of water at 500 K using (a) -(b) Clausius-Clapeyron equation, “F271 ioe sing, wis We Toto ficient!) fis input te hag Ge eg ‘ -¢*)% Tea snyeatesagivens ey: KV = 0.09, - mYkmol bar PT that for any gas whose volume varies linear! with temperature at pe given the Joule-Thomson coefficient is zero, % 7 = eae Rraleate the ey emPtessbility factor of oxygen varies ‘with presswe Sh given Belews Evaluate the fugacity of oxygen at this temperature and 100 bar, P, bar 00 4. 7.00 10.00 40.00 70.00 100. z 0.99701 0.98796 0.97880 0.96956 0.8734 0.7764 0.6871 6.32 (a) Calculate the fugacity of CO at 50 bar and 400 bar, if the following data are applicable at 273 K. +o P, bar 25 50, 100 200 400 800 1000 Zz 0.9890 0.9792 0.9741 1.0196 1.2482 1.8057 2.0819 (b) Using the values of Z at 50 and 400 bar, calculat CO. From these determine the fugacities at these with the previous ones. fe the van der Waals constants for Pressures and compare the resiilts 6.33 Calculate the fugacity of methane gas at 322 K and 55 bar, given that the critical constants are 190.7 K and 46.4 bar. 634 Calculate the fugacity of nitrogen at 800 bar from the following data at 273 K. ee = P, bar 50 100 200 400 800 1000 l : PYIRT 0.9846, 0.9846, 1,0365 1.2557 1.7959 2.0641 $i 6.35 Find the per cent increase in the fugacity of gaseous oxygen per degree rise in in the neighbourhood of 298 K and 200 bar, if under these conditions, the Joule-Thomson heat is 1457 J/mol. (Joule~Thomson heat = Hy - H.) - 6.36 Estimate the fugacity of gaseous propane at 12 bar and 310 K using the P, bar 17 34 68 10.2 7 V,m'skg 0.3313 0.1609 0.0754 0.0468 0.0382 Also compute the fugacity of propane at 310 K and 70 bar given Of Propane at 310:Kulgs19 bane ithe A! em i 1 te