3 P-v_T relations of fluids Learning Objectives his chapter will enable readers to # define a phase; 2 understand the widely used J know the method of obtaini understand the crit quality of a mixture; know more about pressure-volume diagrams and use the lever rule and to estimate the properties know the kinetic theory of gases approach to der calculate the P-vT properties of van der Waals in terms of critical constants; 805 and the estimation of van der Waals constants 1s know the method of determining the parameters of a two- i oe ee & two-parameter equation of state from a know the equations of state: Beattie—Bridgeman; virial; to understand phase diagrams; of two phase mixtures; Benedict—Webb—Rubin; Redlich—Kwong and gain familiarity with the iterative techniques in the evaluation of vapor and liquid volumes from ‘equations of state; ia + know in detail about the law of corresponding states and the reduced equation of state: « understand fully about the generalized compressibility factor correlation * © know about Pitzer’s acentric factor; ; © use the two parameter and three parameter com, of volumetric properties of fluids; pressibility factor correlations for the estimation Understand the generalized equations of state: Redlich~Kwong (RK); Soave-Redlich-Kwong (SRK); Peng-Robinson (PR), and the Lee Kesler modlifcation ot BWI « Gtosiate the volumetric prope ric ies of gases through RK, SRK and PR equations of state; and use the genteralized virial coefficient correlation, ; of processes we are concerned with the estimation of energy change of a system while it exchanges energy, in the form of work and heat, with its surroundings. To estimate work and heat interactions, it is essential to have a knowledge of the properties of the system and the relationships that exist among the various properties. The properties of interest in thermodynamics can be broadly classified into two groups as (i) Measurable Properties: The properties like pressure, volume and temperature which can be directly measured. (i) Nonmeasurable Properties: The properties like internal energy (U), enthalpy (H), entropy (S), Gibbs free energy (G), etc. which cannot be directly measured. The properties are independent of the path followed by a system in reaching a given state and the changes in the properties depend on the initial and final states of the system only. The property has a unique value when a system is in a given state. Hence, the nonmeasurable Properties can be estimated in terms of the measurable properties P, v and T. Therefore, it is necessary to develop relationships between measurable and nonmeasurable properties. We have also noticed that for a simple compressible substance, only two thermory -amic prop- erties can be independently varied. That is, there exists a relationship between the three Propertics — pressure, volume and temperature. The P-vT relations of fluids are discussedaa Chemical engineering thermodynamics ve measurable and HOAMEASHEADIE prop, en ct i er while the relations bemwe' in this chapter while the relati q presented in Chapter 7 3.1 Phase aining several chemical species. Before we g A chemical engincer deals with mixtures contain thorough knowledge of the Proper the properties of mixtures, it is essential an vontains only One chemical species. Sometin®t pure substances. A pure substance is one WHET ng im chemical composition. For eq, pee jeal with mixtures Which do not undergo &FY TN ri during compression/expansion and heating/cooling unaltered. In such cases the ai which is a mixtul can be treated as a pure substance. However: ‘ it can be present as a mixture of liquid and va a from that of the vapor. Such mixtures of variable ‘substances. - i Tee, water and steam have the same chemical Specie’ bo Solids can exist in differen different states of physical aggregation as solids, liquids 2 FPeolor) as well as in rhombic for . allotropic forms. Sulfur is found in monoclinic form (orange in forms — graphite and diamong, (lemon yellow in color). Similarly, carbon exists in the allotropic Father, The different states in The properties of these allotropic states differ widely from cacl h OWE iform throughout Bot which a substance exists are called phases. That is a substance which Vaitstance or a'plia h in its physical state as well as in chemical composition is called a hanger 7a each mae b od In a system consisting of more than one phase, the phases are separated fro ya phase boundary. All substances — solids, liquids and gase: Tens Pure ©. Similarly, matter is found jg ¢ — change their molar volume when their pressure and temperature change. Depending on the nature of the substance and the applied pressure and temperature change, the change in the molar volume may be large oF negligible. If the change in the volume is negligible, the substance is usually called incompressible. This is true for solids and liquids. However, the change in the molar volume is sufficiently large for gases and hence we shall focus our attention mostly on the P-v-T' behavior of gases in this chapter. The P-v-T behavior of substances can be represented by means of graphs or charts as well as through appropriate mathematical relations. 3.2 Graphical representation of P-v-T behavior Consider a solid substance at a given temperature. If energy is transferred as heat to the solid at constant pressure, the solid expands and the specific volume of the solid increases with increase in temperature. The path followed by the system (solid) can be conveniently represented on i temperature-volume diagram as shown by 1-2 in Fig3.1(a). With continued heating, the system fcaches state 2 where the solid starts melting. At this stage, the system contains two ghane ceesolid and liquid — which are in equilibrium with each other. If the heating is cor Bases more and more of the solid phase converts into liquid phase and the temperature s sontinied, remains constant, The overall specific volume of the system increases till the state 3 the system Where the substance is present only in the liquid phase. The amount of ener; te 3 is reached, wrase of the substance, for the complete conversion from solid phase to liqui +e absorbed by unit temperature (from state 2 to state 3) is called the latent heat (enthalpy) of fi hion zat the ‘same » With further : feee Ses i Po relations of fluids 45 cating, the temperattire and specific volume of i sh ein the ar bess 0 toi IF the heating i ont se al ae i ad jd to vapor phase at the by unit mass of the substance, for th the vapor iaehaln) of poration. Upon farther hea 3) cle the tree hea {shown in Fig.3.1(a). If similar experiments are renee eee ne system follows the path jous constant pressure lines as shown in Fi on ied at several pressures, we obtain the vari os (b) Fig31 (a) T-v diagram showing constant pressure heating of a pure substan Fie ance, S-solid, L-liquid, V-vapor: Py > Pp > Py of a pure substance. (b) Tv diagram for a pure In Fig.3.1(b), in the regions marked S, L and V, only one phase — solid, liqui is present. In the region marked (S++) both solid and Tiguid phases co-enst in ehuiliriame whereas in the region (L + V) the liquid and vapor phases co-exist in equilibrium. Along the line marked ‘triple line’, all the three phases — solid, liquid and vapor — co-exist in equilibrium. Along the path 2-3, phase transition from solid to liquid occurs, while along the path 4-5 phase transition from liquid to vapor occurs. The states 2, 3, 4 and 5 represent the saturated states where the phase transition either begins or ends. The curve AC represents the saturated liquid line whereas the curve BC represents the saturated vapor line. A point on curve AC represents that the substance is in the liquid state at its boiling point at the specified pressure and such a liquid is called saturated liquid. Similarly a point on curve BC represents that the substance is in the vapor state at its condensation point and such a vapor is called saturated vapor. It can be observed from Fig3.1 that during the phase transition (23 and 4-5), the temperature as well as the pressure of the system remain constant. At a specified pressure, the temperature at which the phase transition from liquid to vapor takes place is called the saturation temperature. In Fig.3.1(b), the saturation temperature is T; at pressure Pj, whereas at pressure P; the saturation temperature is Ta. The pressure at which the phase transition from liquid to vapor occurs at a specified temperature, is talled the saturation pressure. At temperature T;, the saturation pressure is P, [see Fig.3-1()]- The system at state A/, the overall specific volume of which is usr is a mixture of saturated liquid at state 4 with specific volumé vy and a saturated vapor at state 5 with specific volume vo. ‘Another convenient chart which is quite often used to represent the P-v-T behavior of a pure substance is the pressure versus volume diagram shown in Fig.3.2. Here the liquid and¢ region, where both tiqy nd the two-phi b and v iC is called the saturated liquid curve andy nd 1+ Meant temperature Lines (or isotherms) are shown 1,” ley ‘The const J that the isotherms 1; and 7, 2 Ts 7 2 split ‘can be observed : eae necis the saturated liquid i conn quid and say, coment decreases a8 the. temperature sig maa fine segment reduces to @ point. AC poin, nt guid and sutured vapor become identical yng we oF ished from each other. The point C is called the critical Ping, epepresents finest temperature and Pressure TX aid oa int repres a cenitical po xist in equilibrium. The temperat ture and pressure corresponding t0 the ey 8 a eymperature (Tz) and ertical Presse (P), respectively. The ison ont ri he i point is called the critica ue isotherm. The critical constants of = the critical C InN gesented in the Appendix (Table A-1)- 5 cannot De Critical point Fig32 Pv diagram for a pure substance. ‘The isothermal compressibility (x) of a substance is defined as -: (3), el It can be observed from Fig.3.2 that [9P/9v}r or the slope of the isotherm in the liquid region i very high. In other words, the isothermal compressibility of the liquid is very low and hence th Tiquids are often treated as incompressible. In the vapor region, the isothermal compressibilit is quite large and the vapor is highly compressible. ‘tye substance existing at state M (sce Fig.3.2) is a mixture of saturated liquid (state f) an saturated vapor (stage g). Since volume is an extensive property which is additive, the mok volume v of the mixture is equal to the sum of the volumes occupied by the saturated liqui and saturated vapor. Hence, one can write @ (Ny +N,)u=Ngvg+ Ney or Naty Npy @:PT" relations of fluids 47 or VX AAA Nv 74 Nay where vy = molar volume of satura ~ichange in molar volume due to vaporization mlurated vapo N,_= mole number of saturated vapor, Ny = mole number of satur ‘The quality of the mixture can be expressed ag ted liquid, vy = molar volume of XN, Ne = quatit ; NyaN, 7 Wality of the mixture Gay ee ay or Nj+N,~ my+m, @5) ‘That is, the quality of a mixture is the ratio of the mole nu 5 i to the total mole number (mass) of the mixture, Any eee eee i sis nditive) of the mixture can be expressed in terms of the qu ations similar to En. Fo example, the u= Xug+(1—X)uy= uy + Xugy 66) where u = molar internal energy of the mixtu liquid, uy = molar internal energy of the satur, internal energy duc to vaporization and X = re, uy = ated vapor, uj quality of the mixture. ‘The Eqns.3.3 and 3.6 can also be used to esti a - . Equation 3.2 can be rearranged as estimate the specific properties of the mixture. N, v—y, . -vyH=Niv-9, or Ae ery 3 a Ny vg—v G7) My Y= ¥ OF ny 8 (8) molar internal energy of the saturated 4u;—uy = change in the molar Equations 3.7 and 3.8, commonly known as the lever rule, the saturated vapor to the saturated liquid in a mixture is line segments f—M and M—g (see 3.2). The constant ‘To understand more about the critical point, let us con: a transparent, closed and rigid vessel is initially filled with a small amount of saturated quid and a large amount of saturated vapor such that the mixture is available at state 1 shown in Fig.33. If energy is transferred as heat to the mixture, the mixture follows the constant volume process 1-2-3-4, since the total volume of the vessel as well as the total mass of the systen are held constant. In other words, during the heating process the molar (specific) volume of th mixture remains constant. Upon heating the mixture, the quality increases or the mole (mass fraction of the vapor increases as the liquid vaporizes and the meniscus separating the liqui and vapor phases moves down. At state 3, the substance is cent per cent saturated vapor ar with- continued heating the system (contents of the rigid vessel) reaches state 4 which is in vap: Tegion, If the rigid vessel is initially filled with a mixture in state 5, then upon heating the syste it follows the path 5—6-7-8 as shown in Fig.3.3. express that the mass (mole) ratio of equal to the ratio of the lengths of the quality lines are also shown in Fig.3.2. sider the following experiment. SupposeConstant quality, lines Fig33 Pv diagram of constant volume heating of a pure substance. 8 “The quality of the mixture decreases (Xr = 0+ Xe < Xs) with the addition of energy as heat and at state 7, the substance is cent per cent saturated liquid. That is, the meniscus separatin, the liquid and vapor phases moves up till it reaches the top of the vessel. With continued heatin, the lignifance moves 10 the state 8 which is liquid below its saturation temperature. In the two the sufstayesed above, one could observe the movement of the meniscas because of the large cates ce between the densities (and hence the refractive index) of the liquid and vapor. On the sirer hand, if the rigid vessel is initially filled with a mixture in state 9, the system, follows the path 9-10-11-C-12 upon the addition of energy as heat at constant volume. In this case it can Pate rved that the Variation of quality of the mixture during the heating process is negligible till the system reaches the state C which is the critical point. Therefore, the meniscus separating the liquid and vapor phases appears to be stationary at its original position. As the system approaches the critical point, the difference in density between the liquid and vapor decreases aeeraakes it difficult to distinguish between the two phases. At the critical point, the densities whine liquid and vapor are identical and one cannot distinguish the liquid phase from the vapos phase. With continued heating the system reaches state 12 which is above the critical point. 11 aeeee ce one observes that the meniscus is stationary during the heating process and sudden} disappears at the critical point. Example 3.1. Calculate the specific volume and specific internal energy of wet steam of qualit 0.8 at 150°C from the following data. vy = 0.001 090 8 mi/kg; vp = 0.3924 mi/kg; uy = 631.63 KI/kg; uy = 2558.6 KI/ky Solution We have v= Xv, (1— X)vy = 0.8 x 0.3924 + (1 — 0.8) 0.001 090 8 = 0.3141 mi/kg ua Xuy+(1—X)uy = 08 x 2558.6 + (1 — 0.8) 631.63 = 2173.2 ki/kgrelations of fluids 49 2 If the spe Example fic volume of we of the st from the following dag, NC MEAM AL TOO is 1.42 m'vkg, determine the qu ity vy (OC) = 0.001 043 7 mig Ny LOO) = 1.673 mk ‘solution We have ve Xm += Xv, or (Ney or 142 = 1.673x + (=x o.001 043-7 or X= 08487 crample 3-3 A rigid vessel is in ; Beam tor at 100°C. Upon beatin ie mixture of saturated vapor and saturated Wie volume of water atthe eric pote ne eases through the cities state, Given that the Eee peaieretects equal to 0.003 17 mi/kg, det he fio of saturated vapor to the saturated liquid aa te. mi/kg, determine the volume ratio Oca in Example 3.2 liquid with which the vessel is initially filled. Use the ally filled with a jon The mixture follows a constant volume i ‘al mass of the mixtu "sa con: ; Process, since the total mas ixture Solitthe volume of the vessel remain constant. The mixture passes through the critical state. on Passes through the critical state. ve=v Gnitial) of 0.003 17 = Xvy-+ (1 — x), or 0.003 17 = 1.673X+ (1—X) 0.001 0437 or =X = 1.2717 x 10-3 volume of vapour _ Xv, 1.2717 x 10-3 x 1.673 volume of liquid ~ (i — XJ; ~ (1.2717 x 10-5) x 0.001 o4s 7 = 24 Example 3.4 ‘The specific internal cnergy of a particular liquid—vapor mixture i ji ote ° apa por mixture is 2000 kJ/kg. Giver the specific internal energies of saturated liquid and saturated vapor at the same coneiions'as 850.6 Kikg and 2593.2 kJ/kg, respectively determine the mass ratio of vapor to liquid in the mixture. Solution The lever rule gives my Ute g, My _ 2000 my Uy—u my 2593.2 — 2000 1.9376 In addition to the temperature—volume and pressure-volume diagrams, quite often it is con- venient to represent the P-v-T behavior of a pure substance on a pressure versus temperature scale or phase diagram which is discussed below. A plot of the saturation pressure of a liquid as a function of temperature gives the vaporization curve T-C as shown in Fig.3.4. Similarly a plot of the vapor pressure of the solid as a function of temperature gives the curve 1-T'and a plot of the melting point of the substance at several pressures, gives the curve 2-T’as shown in Fig.3.4. The solid, liquid and vapor regions in Fig.3.4 are marked as S, L and V, respectively. The point T represents the ¢riple point, where all the three phases — solid, liquid and vapor — co-exist in equilibrium. For a pure substance, the triple point temperature and pressure are fixed. The triple point temperature and pressure for a few substances are presented in Table 3.1, The point C represents the critical point. The curve 1—Tis called the sublimation curve along which$0 Chemical engincering thermodynamics M Critical ‘oint) Fusion — curve <— sublimation 4 curve T T Fig.3.4 P—T (or phase) diagram for a pure substance. 7 is called the fusion cu, the solid and vapor phases co-exist in equilibrium. The curv a an curve T-C is called along which the solid and liquid phases co-exist in equilibriu ist in equilibrium. vaporization curve along which the liquid and vapor phases co-€xi Table 3.1__ Triple point temperanures and pressures of a few substances ‘Substance T(K)__P (kPa) ‘Substance T(K)_P (kPa) ‘Acetylene 192.40 119.59 Methane 90.68 11.6920 Ammonia 195.40 006.0755 Neon 24.57 . “43-1960, Argon 83.81 068.9 Nitric oxide 10950 21.9180 Carbon dioxide 216.55 517.971 Nitrogen 63.18 12.5700 Carbon monoxide 68.10 015.372 ‘Oxygen 54.36 0.1520 Copper 1356.15 000.000 079 Silver 1234.15 0.0100 Deuterium 18.63 017.065 Sulphur dioxide 197.680.1675 Hydrogen 13.84 007.039 Water 273.16 0.6115 Hydrogen chloride 158.96 013.8655 Zine 692.15 5.0060 The liquid at state D (see Fig.3.4) can be converted into vapor by constant pressure heating and the system (liquid) follows the path DEF crossing the phase boundary at B. The liquid we state 1D can also be converted into vapor by reducing the pressure at constant tempers tng a shown by the path DGI crossing the phase boundary at G. Similarly, the eaur ee pee be condensed into liquid by cooling at constant pressure (FED) or by isothermal c Hy (PIE), Im each case the phase boundary is crossed either at B or at J Thovenn a compression to define a liquid as a substance which can undergo a phase ehange by redecseg (oer is fempted constant temperature and a vapor as a substance which can undergo a phase ohvectt's, Pressure at constant pressure, Let us now consider the substance at state Mf Phe eee ha7BE BY cooling at at state M are above the critical temperature and critical pressure. ‘The eegeeT® aNd Pressure does not undergo any phase change either by pressure reduction ee gute substance cooling at constant pressure. ‘Therefore, based on the above defimieen att “MPerature or by substance at Af either as tiguid oF as vapor. Usually, the term fluid fn go's, ANNOE classify the State Af or in the regions L and V. It is possible 10 convert Med J Us A Hiquid without ever crossing the phase boundary. One much paty itd IMO vapor gr vancePow relations of fluids Si 3.3 Mathematical representation of P-v-T behavior The most convenient method of rej mathematical expression, The Presenting the 7 7 1 behavior of relationships of the type ubstance is through a S(RwT)=0 are called equations of state. Several equations of state have been devel ped so far for several pstances and many more are like! ul leveloped so far for several aoe of state and the dae gael 10 be developed in future. It is not possible to discuss all the equations of s 'Scussion presented below is limited to a few equations of state only. 33.1 Ideal gas law Consider air at normal temperature and pressure. It coy i : ce tains a * * molecu per cubic metre or, the volume available per Tea 10a me The diameter ofa ” molecule is 4 x 10-24 m?. 4 molecule is approximately 0.2 nm and the volume of each molecule apehuinatiy Oto ne. ae Oe Oe een ean aubied by the molecules themselves is negligible. This also shows that the distance between two molecules is much larger than the size of the molecule. These molecules move at random with independent velocities. In the development of an equation of state for a Ba it is reasonable to assume that the volume occupied by the molecules Pu=RT 9) where R = 8.314 J/mol K is the universal gas constant. Equation 3.9 is known as the ideal gas law. This law is valid if the density of the gas is sufficiently low. It was found that the behavior of many gases at sufficiently low pressure (in the limit P— 0) can be approximated by Eqn3.9. This is only an idealization towards the actual behavior of the gases. Experimental methods were also used to develop the equation of state for a gas. Based on experimental measurements Boyle in 1662 stated that the molar volume of a gas varies inversely with pressure when temperature is held constant. Stated mathematically vol/P or Py = constant (at constant temperature) (.10) which is known as Boyle's law. In 1787 Charles found that (a) the molar volume of a gas is directly proportional to temperature when the pressure is held constant, ic. vol (at constant pressure) (uy and (b) the pressure is directly proportional to temperature if the gas is held at constant volume, Pat (at constant volume) (3.12) Boyle’s law and the Charles law can be combined to yield the ideal gas equation of state Eqn.3.9. It can be shown that for an ideal gas, the internal energy is a function of temperature only, i.e. (3.13)Chemical engineering thermodynamics This fact is proved in Chapter 7. | . sume occupied bY ONE Mole of Ieulate the vo 7 Example 3.5 Using the ideal gas vapor at 427.85 K and 0.215 MPa. Solution We have RT _ 8314 x 427.85 55 x 107? m* P= pate ioe = 16.55 x 1078 m » 33.2. van der Waals equation of state ic behavior of the gases ang deal gas law is only an approximation or idealization oem or real (nonideal differ free only at low densities. The P-v-T" behavior of actu Foe been made to accurate he unavailable volume fo, In fact Clau: the first to take j 7 ular motion iB the ideal gas mig mt account the unavailable volume for Bice ‘of radius r, the centre-to-centre distance between Sea rea ae hear fore, a molecule canno, Troe molecules at the instant of collision is 2r. Therefore, Teach another mole eben org core from the centre of th molecule such that its centre lies within a distance of 2r from_ n 7 thee molecule. That is, the centre of a rae ne ctnied from a spherical region, called unavailable vole tsiom Of radius 2r from other molecules as shown in Fig.3.5. Then the total ailable volume or : Stor number) is given by” the excluded volume b for molecular motion of No molecules (Avagadro’s _N 4 p(n) — 16 gtr? = SF Non @.14) the actual volume occupied by the motion is (o~ 0). If the correction for ooh jose IME actual Volume Available for mofoanne® the Clausius equation of state given by ‘deal gas law, it cede . ces 10 Pv) =RT * Gis)PT relations of fluids 53 In the kinetic theory of gases, the are_no intermolecular forces between Malistic since there are force: jolecular forces of attra leat gas law ix the molecules f attract ee ny pai les. The : are attracted equally in all directions : to the container wall experience a net hws the observed pressure is less than the (opie container wall exerts less force on the wall. Teton in pressure fs proportional to the presse, i absence of the attractive forces. ‘The red cen to the. wall ¥ of molecules per unit volume [No/] in the id to the numb m ye al i er of molecules per uni avety are attracting. Therefore, the sedsennr Of molecules per unit volume in the next layer, w duction in pressure is given by adjacent to the contai 27 Ropusive force Force Distance between molecules \ Attractive force jig36 Intermolecular forces of atraction and repulsion beoween a pair of molecules. oe (2 1 (No)? or pr=p+a' (%) P+ (3.16) pie where P’ = pressure exerted by the gas in absence of the attractive for = pr : n ive forces, P = observed pressure, and a’ and a are constants. If this correction is incorporated in the ideal gas law, one obtains , (P+ 5) (v—b) =RT @.17) which is known as the van der Waals equation of state. The van der Waals constants @ and } can be determined from the experimental P-vT data. Equation 3.17 can be rearranged as RT a G.18) vb Equation 3.18 suggests that a plot of P versus T at constant volume gives a straight Tine with aslope R/(v— 8) and an intercept —a/v?. The van der Waals constants of a few selected gases ate presented in the Appendix (Table A.2).thermodynamics s4 Chemical engineerin in general, gives three vay, J, volume ands 0 Tange of valucs of P ang vot bic m: Pa . However, 19 of Pand 7 it gives three | me other rn The van der Waals equation of state is cu! volume for a given pressure and temperature, gives only one real value for volume and in so values for volume. ee ay 1< Te three real y, and where TST Alues cT>T. a of volume . _ Where T'> T only one real value tg equation of state is sh volume exist. der Waal M own, he van ery, for volume. Morcover The PT behavior of a gas which satisfies # c therm at Te T. gives three valves oi Spservation. The practically Tealizabje segment 12345 is not in agreement with the experiment®’ coment 2-3-4, the van der Waa variation of volume is shown by the dotted line 1-5. In 10 Ue at constant temperature Which equation predicts an increase in volume with increasing PIS" | Seg in Chapter 10) it can be is not realistic. Based on the stability criterion (which is CAT’ tem should move along the shown that the system is unstable in the region 12345 and ae volume v% is inadmissible, The straight line path (dotted line) 1-5 in this region. Therefore, ie t value Ug corresponds to the ould be such that the area gment 345). smallest value vy corresponds to the liquid volume and the eae : vapor volume. It ean also be shown that the straight line path 1-7 ‘0 otithe region I (segment 123) is equal to the area of the region Fig3.7 Isotherms of a van der Waals gas on P-v diagram. Example 3.6 Calculate the volume occupi t pied by one mole of n-octane K the saturation pressure is 0.215 MPa. Assume that n-octane follows the cea gat 127-8) K where of state. The van der Waals constants a and b are 3.789 Pa(m*/mol)? respectively. Solution The van der Waals equation is cubic in volume. Given the astion . volu r Tis straight forward. However, calculation of volume, given P and T requiec cation method. The equation can be rearranged as given below for an iterative wales ti a0 lation,” RT b w= Cex aay *PvP relations of fluids 58 _ |, = volume calculated in the ith iterat eration and Weration: initiate the iterative calcul; inerieta by the ideal gas law. Herat 1 = volume calcu ted from the (++ 1)th 0, vm can be taken as equal to that r ained OF the difference (v4) — %) is le: lions can be carried out till the converg: is ob ') is less than a preset value. jergence 1s _ BE 8314 x 427.85 ; vo P 0.215 x 10° ~ 16-55 x 10 m#/mol RT rn ee . (P+ a/e), * @Pranp*? o 11 + 2.37 x 10-% or yy = 15.78 x 10° {ozs x 10° + 189 (6.55 x 10-47 similarly, calculations can be continued to obtain Iteration 2: v2 15.69 x 10-8 m®; Iteration 3: = i + : vs = 15.68 x 10-7 Jteration 4: U4 as 15.68 = 10-* m* ‘The calculations show that convergence is achieved in four iterations. ‘The volume of n-octane = 15.68 x 10? m*/mol. Example 3.7 Caleulate the volume of one mole Tiquid noctane at 42785 K and 0.215 MPa. The Example 7 Cdgnstants are a= 3.789 Ba (an/mods # = 2.97 = 10 me and 0.215 MPs Th Solution To calculate the liquid volumes Eqn.(A) of Example 3.6 can be used for iterative Siculations. The calculations of liquid volume can be initiated with vo = RT RT weet §" @renp*? viet hey + 2.37 x 10 or vy = 2.90 x 10-4 m® a = 7 fo. eS B10 + 15 x 10° + G37 x 10-4) Similar calculations can be carried out to obtain Initial value: v = 2.37 = 10-* m*, First iteration: v = 2.90 x 10™* m° Second iteration: » = 3.16 = 10-* m*; Third iteration: v = 3.30 x 10-* m? Fourth iteration: » = 3.39 x 10-4.m®s Fifth iteration: v = 3.44 < 10~* m? Sixth iteration: v = 3.47 x 10 m*, Seventh iteration: v = 3.49 x 10-* m? the volume between sixth and seventh iterations is ns can be terminated at this stage- ‘Therefore, the m®/mol. Jt can be observed that the change F< 10-6 mi/mol only. Hence calcula 2 olume of liquid n-octane is 3.49 x 10$6 Chemical engineering thermodynamics mics, cubic equations of state are extensiy, ime of the liquid or vapor can be caleutara®Y However, such calculations are tedious 94°) age, din what follows, to determine the Toots, feng In chemical engineering thermodyna predict the properties of fluids. The volu an iterative technique as explained above. x ich i jaine . Squation, The cob eguatons of say ean be expressed 3 general form as y which can be rewritten as Z4+0Z?+BZ4+7=0 (ay where Z= Pu/RT 6a) Ca Bap Gay 8=A+wB?—uB—uB? (2) 1> AB WB? —wB? B24) A=aP/(RTY (225 eee (326) Substitute P waace : (3.27) in Eqn.3.20 to get rae (3.28) where p = 6 — (a?/3) ‘ Ey = (205/27) — (8/3) +7 : oy Let D = (97/4) + (p3/27) ea If D > 0, there is only one real root and it is given by q wo g ow 140 —~£_ypy""_2 gt vd} +{-§ es (332) If D= 0, there are three real roots and two of them are equal. They are given by An-a(Q)"-$ wan-()""-§ o.Pe relations of fluide 57 1D <0, there are three unequal real Lots. They are riven by Zy = 2r¥/9 cos(0/3) 5 (3.34) 7 = 2 cos (2442) _ 9 (35) 2a mom (82) 2 030 where cos 0 = —3 4)" G37) ( #)" 3.38) The values of u, wy a, 6 and y for the cubic equations of state are presented in Table 3.2. Table 32 Values of 4 w, a (7 for the cubic equations of state Equation of state uw, @ wan der Waals 0 0 -I-B A =a Redlich—Kwong, 1 0 -1 A-B-B? —AB Soave-Redlich—Kwong 1 0 1 A-B-B —AB Peng-Robinson 2-1 ~14+B A-2B-3B? ~AB+ B+ B? Example 3.8 Assuming that n-octane obeys the van der Waals equation of state calculate the molar volumes of saturated liquid and saturated vapor at 427.85 K and 0.215 MPa. Use Cardan’s method. ‘Solution We have aP_ _ 3.789 x 0.215 x 108 <3 A= (RTP ~ (6.314 x 427.85)? et 12 210 bP _ 2.37 x 10-4 x 0.215 x 10° es ae eee @ = -1~ B=-1~ 14.3246 x 10-* = -1.0143 B = A=64.3813 x 10-5 7 = —AB = —64.3813 x 10-5 x 14.3246 x 10-9 = —9.2924 x 10-4 2 p = pe 64.3813 x 107? — Gorasy 0.2786 _ 2a3 a8, -2x (1.0143)? 1.0143 x 64.3813 x 10-9 4 . en 1S x 10" ~ 9.2004 x 10-4 = 0.0564 hdChemical engineering thermodynamics Since D < 0, there are three unequal real roots i oD r=($) = 228% — o.028s ( 27 7 _ 0.0564 1 _ 9965 oF PP 0=4.8° cos 0 = 1.0143 _ 9.9474 oy 4, 1013 _ Zi 27" cos (2) — $= 2 x (0.0283)"eox(1.6) + 3 «+ 1.0143 _ 9.0187 Zr = 2 cog (2 *) — 2 = 2 x (0.0283)"/* cos(121. 3 3 Zs = 2r' eos (#8) _ 9 x (0.0283)"* cos(241- ated liquid and Since Z = Pv/RT, the smallest value of Z = 0.0187 corresponds sais ali oz O.oage largest value of Z'= 0.9474 corresponds to saturated vapor. The mi has no Physical significance, Therefore iz 427.85 vy = FET _ 0.0187 & 8.314 x 427.85 _ 5 994 19-4 m¥/mol P 0.215 x 10° vp, — 0:9474 = 8.314 x 427.85 51078 any ‘a OBIS ie = 15.675 x 10-* m*/mol The values of the van der Waals constants a and b can be obtained by fitting the experimental £7 data to the equation of state. For approximate calculations, the constants can be determined by making use of the fact that the critical isotherm must show a point of inflexion at the critical Point, as indicated below. At the point of inflexion ap’ arp (5), moos (F ye a (3.39) Applying the criteria given by Eqns.3.39 to the van der Waals equation, we get (2 RT Me oo) 7. ~~ Ge — HP . (6.40) oP 2RT. _ 6a _ 4 (& nr (eb) us (3.41) At the critical point, the van der Waals equation is given by r+) ve —b) = RT. ‘ . ( as (3.42)a relations of fluids 59 grote fe B tHE critical VolUME, One ean solve Eqn . 40 to 3.42 simultancously, to obtain ah Te= pegs area © me canan (3.43) ancenatively, one ean obtain the constants a and b in terms of P- and mT, Rte , a oP. * BP. (3.44) rane eitical point 1 can Be observed that Pate _ 3 _ 9.375 Pete (3.45) 33.3. Beattie-Bridgman equation of state several attempts have been made to represent the PT 8 aT data mi cul ich resulte: in the develop’ ta more accurately which resulted ment of a large number of equations of sta y empirical and only tc, Most of the equations of state are a few of them are in wide use. So y . Some of the equations of state are presen pelow. The Beattie 1 equations of state are presented “Bridgman equation of state [34] is one o} : : peor gases upto a pressure of 25 MPa, This bales is new empirical equations of © bBo 2 r(1 5) (v @ p&=RT(t a) ( Bo- ) Ao (1-2 G48) where Ao, Bo, a b and ¢ are constants. ‘The Beattie-Bridgman constants of a few sele! whe presented in Table 3.3. cted gases able 33 _Beatie—Bridgman constants of a few selected gases” am = Gu mC) Bex th ox ik tai (Sr) (m3/mol) _(m*/mol) (n3/mol) " i Sane eat Tro acct bas Seis most ula—s7e870 mune (go 24620 guzso 340000 Carbon dioxide 0.5073 104.76 72.350 660.00 ranane o.sost 400 toiso 0000 rales fens tse Nsom 22680 Metin jon 1800 0.000 oot riydrogen 0.0000 2098 8390 sot Metiane 0.2307 52 Sih 1830 Neon b.oats 20.60 0.000 tol Wises bursa ose 202.00 Omeen ousit oat soe 8.00 mFontane Seen 33400 sao 400000 Frommns ‘aos ___181.00 oso 120000 Fen aaNet TO. carn CF ad Hg, RBs Molecular Theory of Gases and Lituids, Sohn Wiley. Ne York cases),0 1 cecring thermnodynarnics 1 engineering thermodyn! rhemical engi" o ¢ «4 of state G tion 0 in equal ; pemmme ters ict-Webb-Rubii ains cight parameters and is 5, 3.3.4 Benedict fstate contain Me quation of state [35] j,i, WR) equation OFS The BWR od! S Bivens The Benedict-Webb-Rubin a Mey t hydrocarbons ™y The Benetipresent the P-v-T data 7 oe one ] good to rep! ¥) (a (2) gal 5 } Ge, RT 1 [er(m+5) —(Aot+ 57 po BTS 2 BWR constants for a few selecteg 5. ants, The ‘ Coy ay by cc and 7 are comstanisy A 136), here Lee * Chemical Engineer's Handbe are presented in Perry : ion of state 3.3.5 Redlich-Kwong equation pis in wide use. THE RK equity ation of state [97 “The 1wo parameter Redlich-Kwong (RK) equation of S of state is given by Gay AT a _ pub weed) Pa crimental PT dat hi db pirical constants to be determined by fie Da tiie ah nae where a and } are empirical constants to Ble. Hence, e equa ‘ate, However, such data is not usually avail ih , tame equion of ae, owen, ah da 6 Spon o the gos, Making we OF the fa that the critical isotherm must show a point of inflexion, it can be shown tha 0.086 0.427 48 1724 PTVE _ RT (3.49) ob Fe The RK equation of state can be expressed in the general form as given by Eqn.3.20 and the required parameters are presented in Table 3.2. The RK equation of state is also cubic in volume und henee the calculation of volume from a knowledge of P and T requires an iterative Procedure. Alternatively, one can adopt Cardan’s method to determine v. The following example illustrates the method of calculation. Example 3.9 Calculate the molar volumes of saturated vay 0.215 MPa and 427.85 K assuming that th The crit ipor and saturated liquid of n-octane at fluid follows the Redlich-Kwong equation of state. constants of n-octane are J; = 569.4 K and P. = 24.97 bar. Solution ‘The parameters a and b of the RK equation of state are given by 0.427 48 x (8.314)? x (669.4)25 Sy PTV 2a97 & 10" x (427.85)? — = 4-426 m° Pa mol-? b= 086 64 IT. 0.086 G4 x 84 x 5694 4 a 0 P. OT = 16F = 9.1643 x 10-7 m/moy Let us use Cardan’s method to determine v, and uy. aP RTry = 6 0.215 x 10° Tea = 0.0752P relations of fluids 61 bP _ 0.1643 x 10-9 x 0.215 x 196 S314 & 497.85 06 x 10-8 = 0.0752 — a 9.9306 x 10-8 — (9.9306 x 10-8)? = 0.0652 4 = AB = —0.0752 x 9.9306 x 10-3 = 7.AG78 x 10-4 0.0652 So 74678 x 10-4 0.0531 (0.0531)? _ (0.2681) wD gg = 8.8155 x 10-6 0267 0-2 (3 M2 _ 0.0531 1 cos 3(- Ss < apge7 = 0-904 or 0 = 607° 3 e . Zy = 2"! cos(0/3) — J = 2(0.0267)"" cos (7) +} T4+8 P s and P= BSramics chemical engineering teresa ° — : w os 07 prot of Z versus Fr i Prctonstant 7 . EGEND fs Isopentane a cal § ntteptane eee & nitrogen aa 8 Carbondioxide - © ectane ® Water © Bute "age curve based OF — Gita on hydrocarbons 7. 40 30 30 7 a 1 3 o . Reduced pressure, P, ‘Reprinted with permission from and T, for several flui ; (6) American Chemical Society. where T is in Kelvin and P is in atmospheres. It can be observed from Fig.3.9 that Ze = 0.27 xp = Land T, = 1 That is, the critical compressibility factor for all the fluids as given by the compressibility chart is 0.27 whereas tl ility factor as predicted by the van der Waals equation of state is 0.375 [sce Eqn.3.45]. The critical constants Tr, Pz, ve and the critical compressibility factors of several fluids are presented in the Appendix (Table A.1). It can be observed from this table, that the critical compressibility factor varies from 0.20 to 0.31. This indicates that the generalized compressibility chart given in Fig.3.9 is necessarily not accurate in representing the P-v-T behavior of gases. ity chart by incorporating a third Fig.3.8 Compressibility factor as a function of Pr ‘Su, GL; Ind. Eng. Chem. 38, 803 (1946), Copyright (194 the critical compressit Several attempts have been made to improve the compressit parameter in addition to P, and T, ‘i “According to the two parameter law of corresponding states, the reduced vaj ail the dy must be the same at a given reduced temperature, The redieed vapor pressure, Show that the reduced vapor pressure curves differ from one another in the slope The 5 oor ro Sduced vapor pressure curve has been taken as a characteristic third Gee of ter by Pitzer [42] in correlating the P-v-T behavior of gases. a =65 > z dappssanduay porgesoueg, "9 #990 Puy oot 17 wosjan wos uopsquued yn pardopy ol 5 (eS61) Ur mET-KEIDOWN ‘GOL-E0E LION ‘19 10A BuuaarnSus JowAYD ‘nSHELD 4g sof ung apgwseuduog peryesrwey (e) ors 44 ‘emssaid paonpoy ov T zo66 Chemical engineering thermodynamics 20 Reduced pressure, P, where P= PS/P, = reduced vapor Pressure at T; = 07, The acentric factor w is defined such tine its value is. equ, ae to (spherical molecules). The acentric factor indicates a measure of iat, {0F the Simple fyi Potential of a molecule from that of a simple spherical Molecule, Any nes the intermoteeai’s i umed to be a funey; Perty r and acentrie factor. Tigo"! the the oF the fig, ding states which tells that all fluids hay; b ralPT relations of fluide 67 ”, 10 12 14 16 20 22 jaz POstone Fig310 Reduced vapor pressure as a function of reduced teed temperature. Z = Z (Ter Pr w) iter and co-workers found that a linear equatio: ; Pompressibility factor. The linear equation i ion in w is usually adequate to express the Z= Z° (Tr, Pr) + wZ" (Ty Pr) ei oss we pian pemon ap "2 sy Te meow the dof Single ie areed on the data of nonsimple fluids. The generalized correlation on os : pa ad 3.18 ae te peneraees area ssi 24 = 20 (ha Poesia are Pp) is presented in Figs.3.13 St may be noted that the correlation Z° = Z° (1,, P,) is based ; be notes QF a Z° .) is based on the data of simple fluids. THe 228 CTs, P.) presented in Figh 3.11 anid 319 paeeae Ue aye cimple fui TiMesponding states. Usually, the contribution of the correction term Z! in Bqn.3.64 is small Srence, for a quick and approximate estimation of the P-vT data of fluids, the two parameter jaw of corresponding states (Figs.3.11 and 3.12) can be used. F P Example 3.10 The saturation pressure of water at 180°C is 1.0027 MPa. The eriti orwater are T: = 647.3 K; P. = 221.2 bar. Calculate the acentric factor of water. constants Solution The acentric factor w is given by w= log PSln-o7—-1.0 and T,=T/T. or 0.7=7/647.3 79.96°C ~ 180°C. or T=0.7 x 647.3= 453.11 K or T= PS _ 10.027 Pe 2212 PS (at 180°C) = 1.0027 MPa = 10.027 bar and PS 0.0453 Therefore, w = — logy (0.0453) — 1.0 = 0.3439{2 | CH titi 040 06 OT oe i Reduced pressure, p, O95 97.1.0 Fig3.11_ Generalized correlation for compressibility is drawn based on the data of Lee, BL. and Kester foo encore MO aC ee Fe 10 the tanPMT relations of fluids — 09 Reduced pressure, P, ibility factor: simple fluid term, for pressures Pr Fig3.12 Generalized correlation for compress > LO. The chart pean based on the data of Lee, BL. and Kesler, M.G., AICHE}, 21, 510-527 (1975).qo Chemics ‘hemical engineering thermodynamics Reduced pressure, P, acest rei NS Fata Figs renege, tee BL. and Kesler MiG Al ion term, for pressures P, < 1.0. The chart 1, 510-527 (1975).PvP relations of fluids 71 0.30 i L 2 3 4 5 Reduced pressure, P, Generalized correlation for compressibiliy factor: correction term, for pressures Pr > 1 0. The chart Fig3.14 I. and Kesler, M.G., AIChEL,, 21, 510-527 (1975). is drawn based on the data of Lee, B.7 7 Chemical engineering thermodynamics . avec and 4.98 bar using eof negctanl Ce paranetee compressibility fag i (by three PAY Son, at 409° Example faample I11 Catewlate the molar vo Cae a compressibility factor correlatic M. For n-octane, 7. = 569.4 K: Pe 24,97 bar and and 409.41 Solution we ty 5694 ve (a) 7, 3.1. Thea Read 7° = 0.96 at T, = 1.2 and P, = 0.2 from Fik- 3 m3/mol = 0 96 x 8.314 x (409.41 + 273.15) - 10.939 x 10 mism 4.98 = 10° 12) Then from Fig. () Rea ) Read 2? = 0.01 at 7, = 1.2 and Pe = 07 = 0.964 0.96 + 0.398 x 0.01 % = 2° +z! 314 x (409.41 + 278-1 4.98 x 10° ZRT _ 0.964 x oxide. The tank is left in iis found to be 91.8°C, ipressibility factor Example 3.1. sce pled with 180 ke carbo” di 12 A rigid tank of volume 1 m° is ae 1th Ture of the 13 4 ‘two parameter Com the vicini vicinity of a furnace and after some time, ‘Make use of the Calculate the ressure loy CO2. correlation, Fee Con fen spa Ke and P= 73.87 Dar Solution 3 fe number of CO2 in tank, N= Peery mess oth COT 10-8 elma es v= (4090.91 5) =2.444 x 10-4 m%/mol, [180/44 x 10-)] = 4090.91. Molar volume ©! The pressure developed can be calculated from the relation (A) Z°RT nce a knowledge P If is to estimate The two parameter compressibility factor correlation gives Z° = Z° (Tr P,). Hel of P, is needed to determine Z° from the correlation. However, our objective itsel the pressure. To determine the pressure, Eqn.(A) can be rearranged as PePe ZRT 9, go P=P.P, FR 2.444 x 10~* x 73.87 x 10° x F or Zo= e Saatore+ aa) 09 ® Equation (B) shows that the state of CO2 in the tank should li ight lit ow r lie on a straight i ‘of 0.595 when Z° is plotted against P, and the line passcs through the ei ee T _ 91.8 +273.15 =12 T= 7 = 3012PevT relations of fluid 8 } OF COs, ie straight tes fing he wus Pe plat an trea 35. 'Now ee Ses nthe curve Te Passing through the origi qrerefore . Ln a Reduced pressure, P, 78910 igad Sketch for Example 3.12. 3.13. Repeat Example 3.12 by making use of the thi crc ili bane 3 eter ie three parameter compressibility factor Solution The pressure P is given by BRT gp ga Pe _vPePe 3 7 2Ad4 x 10- x 73.87 x 10% x P, ? RT” RT Fe = 0.595 P, 8.314 x 364.95 or Pp = 2/0595 w The term Z1 is a correction factor. As a first guess one can assume its contribution to be negligible and obtain Z = Z°. The value of Z° can be determined as explained in Example 3.12. The result is Zz 0.725 0 — 0.725 Tee = me Z=072 and Pe= Soe = Soar 1.22 Now read Z? = 0.1 at T, = 1.2 and P, = 1.22 from Fig,3.14. Then Z=Z°+wZ" = 0.725 + 0.239 x 0.1 = 0.74954 Ohemnlond eneineering thermodynamic From Bgn (A), we get Z _ 0749 | 0595 ~ O55 ~ 1.26 Now read Z° = 0,728 and Z' = 0.12 tT, = 1.2 and P. = 1.26 from Figs.3.12 and 3, Now read / Bug Z = 0.725 + 0.239 x 0.1 = 0.749 From Eqn.(A), we get The calculated value of P, in two successive iterations matches, Hence, P= P,P, = 9.308 MPa, =P87 3 1g, ao 6 3.5 Generalized equations of state The compress ty factors Z° and Z} are complex functions of reduced temperature ang Presa nd itis not possible to obtain mathematical expressions for 20 et in etteea F and 2. This is a serious drawback for numerical calculations ee illustrated by Bxampiee’ ot The recent application of the corresponding state Principle is the development of gene. equations of state, eralized 35.1 Generalized Redlich-Kwong (RK) equation of state The Redlich-Kwong equation of state a v(u +b) G48) This can be rewritten as (aa) at T+h) RP oPPT relations of fluids — 7S Zz (3.68) ¢ Egns.2.67 and 3.68 can be convenienth in be substituted in Eqn.3.67 to obtain a reviced fire values of 7 do not diifer appreciably in su uations 3.67 and express the compressibili 2 equation of state. Recall that Eqn.3.60 also is of the form Ze (1s) wine from the van der Waals equation of state and il ft alge Conergy coat obtain advantage of 4 generalized equation of state is that it permits the evaluation of Poi data of ses from a knowledge of T. and P.. An iterative peat cet etl OL et ne ee om ample erative method of calculation is illustrated in the ly used for iter: ations, The calculations can 68 to obtain the value of h. This value of h value of Z. The iterations can be continued ‘cessive iterations. function of T, and P,. is known as a generalized obtained prample 3.14 Calculate the molar volume of n-octa Erm fmeralized form of the Redlich: Kwong equa eer st O25 MPa and 427.85 K using n of state, solution For n-octane: T: = 569.4 K and P. = 2.497 MPa, T 827.85 ove. Pion 7.7 569.4 ~ 9754 P= 5 = FIs = 0.0861 T= assume Z = 1. Then 0.086 64P, _ 0.086 64 x 0.0861 1 x 0.7514 SITE 10, “ = ( h_) 4.933 98 T+h) 737 @) 1 7 ( 9.9277 x 10-8) 4.933 98 . 1— 9.9277 x 10-8 — \ 1-4 9.9277 = 10-3) (0.7514)3 ~ 9265 Now, substitute this value of Z in Eqn.(A) to obtain 086 64 x 0.0861 0.9265 = 0.7514 h 1.0715 x 107? Substitute this value of in Eqn.(B) to obtain 0.9305 1.0715 x 107? 4.933 98 ~ (re rorisx 10?) O77 The calculations are continued till the value of Z does not change in successive iterations. The results of calculations are summarized below: Initial guess: Z = 1 Heration 1: h = 9.9277 x 10° and Z = 0.9265; Iteration 2: h = 1.0715 x 107% ant Z = 0.9305 eration 3: hk = 1.0669 x 10-? and Z = 0.9308; Iteration 1.0666 x 10-? and 7 = 0.9308eermoayrnamich aot engineer ved after four ite} nem ions. pgenwe f acne’ 9308 x 8.314 X 127.85 _ 15,3999 x 10°° m*/mol cone paid x 10° quation of state _Redlich-Kwong (SRK) ¢ 1 the two parameter Jaw of corresponding law. To improve the accu an the ideal gas ken as a third parameter by Soave [44] ang 3.5.2 Soave ‘A generalized equation of ASSET behavior of fluids better tha predicted data, Pitzer's acentric factor is tal tion is modified as Redlich-Kwong qua RT a 3, (3.69) 272, ae OAtTASR Tia Pe G7) 0.08664F Te ave "e Gry Va=1+80-VT) (3.72) (3.73) S = 0.48 + 1.574w — 0.1760? Equation 3.69 is com: Equation 34 monly known as the Soave-Redlich-Kwong (SRK) equati cleats can be conveniently expressed in the general re Ae eaaeoe of state. The . parameters are given in Table 3.2. In terms of the Tonoressibalty taster fad the lor the SRK equation is given by (3.74) Z~2Z?+(A— B-B)Z— AB The Soave equation is wi ‘quation is widely used to predict the properties of hydrocarbor ns, 3.5.3 Pe ii eng-Robinson (PR) equation of state | is also widely used to predict the propertie 0 di f Sof he Pen; The Peng-R. g—Robinson equation of state [45 Ben, 07 xygen etc. The generalized form of the Pe! ng— hydrocarb ons and i Roos and inorgani ma inson equation of Tate if given by i xy Rr @ : (3.75) P _ ee 6 UF + ob here a = 0.45724 2° Téa (3.76) 4 = 0.07780 222 F i (3.77)Poy M relations of fluide 77 Jeol 4 Ss - VT) OS S = O.BTA O44 1.542 266 — 0.269 g2Q7 3.99) Peng-Robinson equation ean also be are expressed in terms of the compressi y factor as Z3-(— B)Z74(A M2) 2 — (ARK ary (3.80) seample £25 Calculate the molar volumes of saturate 7 ames K and 0.215 MPa using the Sone uturate n t'569.4 K, Pe = 24.97 bar and w = 0.398, d Tiquid and sa Redlich-Kwong equ: urated vapor for n-octane 7 ion of state. For n-octane, solution Let us use Cardan's method to calculate the molar volumes, A2785 og asrg, pp, _ 0-215 x 108 = po. TOTEM P= SI = 0.0861 = 048+ 1.5T4W — 0.1764 = 0.48 + 1.574 x 0.398 — 0.176 x (0.308)? = 1.0786 a = 14+S80-VT)P = [14107860 — VOTETA)p = 1.2079 0.42748R? T; 0.42748 x (8.314 x 569.4)? x 1.3079 = Pe 24.97 x 10 = 0.08664RT, _ 0.08664 x 8.514 x 569.4 ae DE eX 0-4 1626 x 10-4 aP__ 5.0180 x 0.215 x 10 A = (Try (B.314 x 427.85) = 9-084 bP _ 1.6426 x 10-4 x 0.215 x 10° -" B= Rp Ba1d x 4a7.e5 — — ~ 99282 x 10 a = -l B=A—B-—B? = 0.0853 — 9.9282 x 10-3 — (9.9282 x 10-3)? = 7.5371 x 107? 7 —AB = —0.0853 x 9.9282 x 107 = —8.4688 x 10-4 7.5371 x 107? — 2 = —0.2580 ne 5 = -04 20% of 52 4, 18871 x 107 __ 5 soe x 10-* = —4.9797 x 107 a= Boa ttat 3 2 p® _ (4.9797 x 10-7)? (0.2580)? _ ae0se p= Ly Ra G9TOT x 107% _ (0.2580)" _ _1 6121 x 10 4° 27 4 27 = fae a [2880 @ 2.5220 x 10-7 an 27 277x1? _ 9.98 30 x 10-7 2) eos 2 x (2.5220 x 10°)" V Shemical engincering thermodynamics or 0=9.14° 2 x (2.5220 x 107)" cos (12 1 7452 x 107? ‘3 cos (243.05°) 4 1 = 6.7452 x Zs = 2r"/¥ cos (243.05°) + 7 1393 x 10-7 “ Therefore Z°=0.9191 and Z 0.9191 x 8.314 x 427.85 _ 15 996 x 10-* m'/mol a 0.215 x 10 1.3393 x 10? x 8.314 x 427.85 _ 9 9916 x 10- m°/mol ci 0.215 x 108 , u Example 3.16 Rework Example 3.15, using the Peng-Robinson equation of state. Use Cardany mple 3.16 Rework Ex 15, method to determine vy and vy. le 3.15]. Solution We know that T; = 0.7514 and P, = 0.0861 [see Examp! ) 398)? = 9.4570 x 19~ 374 64+1.542 260.269 92u? = 0.374 64-+1.542 26x0.398 —0.269 92x (0.398) 19-1 S=0. (+80 — VX)P = [1 + 9.4570 x 10-1(1 — YO.7514) |? = 1.2677 a a = SHOT ARPT 2a _ 0.457 24 x (8.314 x 569.4)? X 1.2677 _ 5 ono P = ‘24.97 = 10 b= 2077 80RT. _ 0.077 80 x 8.314 x 569.4 ec yareoscio Pe 24.97 x 105 aP 5.2023 x 0.215 x 10° as = 8.8398 x 107? RTP ~~ (8314 x 427. Bey = 88398 x bP 1.4750 x 10~* x 0.215 x 10° Ba bP 3 RT 8.314 x 427.85 eerie 1+ B= ~1+48.9151 x 10-* = 0.9911 8.8398 x 10-? — 2 x 8,9151 x 10-3 x (8.9151 x 10-8)? = 7.0329 x 10-2 B=A-2B-3R2 7 = —AB+ 8B? + BS = _ 8.8398 x 107? x 8.9151 x 10°* + (8.9151 x 10-3)? 4 (8.9151 x 10-3) = —7.0789 x 10-4VoD rations of fuits — 79 corny a? 7.0329 7 1? — ¥ = 02571 1907 pa? TT NO me 4 FPA VO? 7H ; 4.9584 10-7)? — (0.2571 | ; fish to _ onsen” -1a677 v0 0.9882 or 0.158% Radian & = 2(2.5088 x 10 con(0.0511) + 23H) =O.9151 spcrrltem (220882) — $a rz 1 pd cog (AZ E1833) _ : a secrete (ERE) — 8 moans 0 therefore Z* = 0.9151 and Z¢ = 1.2106 % 107 0.9151 % 8.314 427.85 S 0.9151 * BAIS AAPTEY _ 15.14 «1 * “ 0215 » 107 als 1 Onan ioe! 1.2106 % 10°? » 8.314 x 427.85 1.2106 «1077 * 83x eo 0.2003 » 10-? m*/mol ye 35.4 Lee-Kesler method Lee and Kesler [46] developed a modified Benedict-Webb-Rubin equation using Pitzer’s acentric se anc ine compressibility factor of a real fluid is related to the propertics of a simple flui (oo) and those of a reference fluid. n-Octane is selected as a reference fluid in this estimation Glocedure. The compressibility factor Z for the fluid is given by Za Zo SZ" 2) G81) where Z = compressibility factor for the fluid; Z° = compressibility factor for the simple fluid: pili factor for the reference fluid; w = acentric factor for the fluid and ota (n-octane) which is taken as 0.3978. Phe campressibility factors for the simple fluid (Z°) and the reference fluid (7+) are generated Soeenin Ses Jods) om puPee 8, 6, DY Bots * capt Gey * (a+80 Chemical engineering thermodynamics where T, assure expressed in KPa and P= critica, De ee eae to be calculated); T. = 7/7. Press mperature (K) of the real fluig yes where P, = P/P. = reduced pressure (P = pre me expressed in kPa of the real fluid for which the anal is temperature (T= temperature (K) and Te = &i a GB, 6) Pov /RT. 5 | ' ¢ Lee-Kesler constants for the where v = molar volume of the simple fluid, mame 86 are presented in Table 3,5, “Pl fluid and the reference fluid to be used with Eqns.3-8 Table 3.5 Lee~Kester constants for use with Eqns 382-386 Retorence Tait : mple uid Simple fluid “Reference fuid Constant Si pl 0.016 901 0.041 577 Constant by 0.118 119 30.202 637 9 cs be 0.265 728° 0.331 S11 c 0.08. eS 0487 36 bs 0.154790 0.027 6ss dy x10 0.155 485 ot 033 6 bs 0.030 323 0.203 488 dy x10" 0.623 689 a 0.023 674.4 0.031 338. 5 B 54 a 0.018 698 4 0.050 361 8 7 0.060 167 0.037 5 Jn this method one determines T; and P, using the critical properties, Suh the simple nad determines ve, the reduced volume of the simple fluid by solving Eqn.3.82 wih the simple fluid Rekuints. From the value of u2, the simple fluid compressibility factor 2° i then, calculated, OExH using the same values of T, and F,, Eqn.3.82 with reference fluid constants is solved to obtain v2, which is now represented by as v/!. Then 2", the compressibility for the reference fluid, is given by gn Poul (3.87) ge Knowing the values of Z° and Z®, one can calculate Z from Eqn.3.81. This equation can be rewritten as Eqn.3.64, where _ @R~ Zz?) =F z G88) The values of Z° and Z? obtained by this method are presented in Figs.3.11-3.14. 3.5.5 Generalized virial coefficient correlation The gencralized compressibility chart shows that Z = 1 at P = 0 and at low pressures Z is aPw relations of fluids 81 pat cons at temperatu or acto Shion TE Hence at low to mode he terapratares Heng 9 moderate pressures, the volume a ied after two terms gives vine vit 14+ BP (3.89) R ting for BY from Eqn.3.52, we get suits BP _y4 (2% Pe 14+ RT RT.) T (3.90) lar molecules, the correspondir jon is used to estimate ie BP. po +ut RT (3.91) senmauing Ban .ot 8 gn3.90, We got BP.) Pr 2=14\ RT) Te oP H14 BE +e @.92) sre Pitzer’s correlation for Z gives Zo 4 ue an Comparing Eqns.3.64 and 3.92, we get 3.93) G95) 0.172 7} = 0.139 — Saar 3.9 pt = 0.39 — Siz 3.96) -rhe generalized Virial coefficient correlation is applicable at low to moderate pressures and (OF non-polar gases only. 3.6 Summary 1m the thermodynamic analysis of processes it is essential to have a knowledge of the Properace ae ee eeta the relationships that exist among the various properties. The propertics <40 aasurable POPES. THe prone, ialpy ete: exnnt te died asurable propertion. siggy! sirable and nonm are measurable and the properties like internal enen There exist relations between the non-measurable mone the measurable properties MA a eah state as well ag j A-substance which is uniform throughout botl i ieee Can exist are songtt She * composition is called a phase, The three phase wien can be found in di vapor, Solids ean exist in different allotropic forms CO iter widely frome well as in graphite form. The properties of allotrer be classified into two groups asm exist relations any they represent different phases of the same solids yy means of The Pa—T behavior of substa epres Ht ns th Ang also through appropri ematical relations: i gemperature as well as the very, When @ substance is heated a e080 ee eT ransition, the temper the substance incr well ascs till the phase change Geary Pressure remain constant, The quantity of 6h for complete conversion from solid to liquid phas heat (enthalpy) of fusion. Similarly, the energy NeGesn H, transi a st temperature ane erature, Press YaPOr ean co-exist in equilibria. The (em PCa ene ee iG er Point are called critical temperature, critica’ Pr liquid at its boiling point, at a specified pressure, (NEAT f Saturated liquid. A vapor at its condensation point ' The isothermal compressibility « is defined as A (33) Gay v lap, ° erma essibility is quite low for ids and hence the liquids are often treate, I incom be TR thy compressible since x i very Hage. The quality (X) of a mixture is defined as * a Gs) m+ my where my and m, denote the masses of liquid and vapor, in the mixture, respectively. The molar volume and molar internal energy of a mixture can be estimated from the relations xy absorbed, by unit ma Hye same temperature is called tne ss Of the substane, ion from liquid to vapor phase h both liqui critical point represents the high nd volume corresponding tq 414 ail volume, respectivety Me se transition begins) j A turated vapor. d v= Xvg+(1— A) = 9 + Xdyy 3.3) u = Xug + (1 — X)uy = uy + Xu 6) where vy = vp, Uy = respectively. The lever rule is iy—uy and the subscripts f and g, denote the liquid and vapor phases, ven by > my _ vy (3.8) my vyav The P-v-T behavior of pure substances can be represented on the diagram and on the temperature versus volume diagram. temperature diagram, a phase diagram can also be used, O1 Me, Pressure versus volume In addition. to the pressure versus a phase diagram, the sublimationp. PF relations of fluids | gepresents the e0-cxistence of solid ‘ . wre pists and v: eore€ gents the co-existence of solid and apor phases in equilil repress the co-existence of Tiguid und guid phases in cnhitcton 1m and the fusion curve rer inates at the er fecal point. The sublimation ene” (it cauilib nar, The veporandon curve res aa cabin, Dhases in equilibrium. The vaporization curve ed the triple vet IM iple point where ene equilibrium, Tt co nernere the thres phases Hig possible to convert kee Srossing the phase boundary by following a aati Bn Reena eae ‘ oe om “ - which takes the “the erica ic on th ete ey eres i ume Pe one a emcee that the molecules of a g attics mid cvs ges so Ps ahi ey he teenie methods ho were employed 10 Sty the Pact beh ares that the molar volume of a gas varies inversely with en temperature 6 hel oc i ian presuove when tebperature B held urve and the v porization curve 1 vod, of PY = constant (at constant temperature) @.10) cares’ law states that the motar volume of « gas f directly proportions to hi roportional to temperature when seiere is Kept constant and the pressure is direc t ena PI directly proportional to temperature when volume vat (at constant pressure) @ap pxT (atconstant volume) @.12) Boyle's and Charles’ laws cam be combined to obtain the idcal gas law. ye Gehavior of real (nonideal) gases deviate from that of the ideal gas law. van der Waals attempted to take into acount the yowme Gecupied by the molecules and the attractive forces attemmen the molecules and modified the ideal gas law to obtain (P+ 5) (@—bR)=RT Gan which is known as the van der Waals equlyoo of state, The parameters a and b are called wie iy Waals constants. The paramere vation Of account the intermolecular forces and Ne parameter b is related 10, {he Palaljed volume or the volume unavailable fo ‘molecular motion, rametjranis a and b depend upon the malas Une gas and they can be determined (fom timated in terms of critical constants by making use of ie camnust show a point of inflexion at cri jcal temperature. That ° 39) They are given by 27R?T2 RT ea“) =P BP.E Chemical engineering thermodynamics For a van der Waals gas, at the critical point 0.875 p-y-T' data more < 7 sent the P-v-T acct Several attempts have been made to represent HE NO oe cer nee the development of a large number of equations © Beattic—Bridgeman equation of state: 2 Cc tBe) — a 1- potent (1-2) (vr p22) -a0(1-5 7 where Ao, Bo, a, 6, ¢ are constants. Benedict-Webb-Rubin equation of state: aaa) _ 1 fg (p41) enw P AEs 3 [nr (os+2)-(40+3- 3) 7a { AG we } Gay, where Ao, Bo, Co, a, 8, c, a, 7 are constants. Redlich-Kwong (RK) equation of state: ar a a ae ae (3.48 v—b vw +s) » 0.42748R? 72-5 0.08664R Te where a= and b= SE 3.49) The cubic equations of state can be expressed in the general form given by aT a P -=— SS (3. v? + uby + wb? G4) or Z+4+aZ?+6Z+7=0 (3.20) Pv where Z = 72 3.21) firial equation of state: Pv Bie D ; RP TI+tS+ G+ ate. (Leiden or pressure explicit form) 3.50) Pu D 1p24 pips i . RP =1+B'P+C'P?+D'P> +... (Berlin or volume explicit form) @51) MDwT relations of fluids 85 |, BY, Ct, D! are al coeflicients which depend on temperature and D. The vi D .¢ only. The virial cocflicients are related as (3.52) 3.53) BC +2B° we sn (3.54) se von 68 wwaals equation can be expressed in terms of reduced parameters as 3 = (Fr + &) (Bur — 1) = BF (55) ach is Known as the reduced equation of state. The reduced parameters are defined as Reduced pressure, Pr = P/P. fi C2) Reduced temperature, T, = T/Te a Reduced volume, vy = v/%e cane ‘the reduced equation of state leads to the two parameter law of corresponding states which The {hat all fluids when considered at given values of T, and P- will have the same value of Ur wee compressibility factor Z is defined as ‘Actual volume of gas o _ Actual volume of g88 = 3.59) Z = Yolame predicted by ideal gas law — RT/P G59) sthe reduced equation of state can be rewritten in terms of the compressibility factor as 27P, P, 2tPe_) (Pe 60) (2+ ae) iG am) Cn This leads to the two-parameter compressibility factor correlation Z = Z (Tr. P,). To impicy the accuracy in the predicted volumetric properties of gases, the three parameter compressibility factor correlation was developed. Pitzer’s acentric factor w is defined as w = —logio Pe’ l7-<0.7 — 1.0 G.62) where P= P,/Pe = reduced vapour pressure at T. = 0. ‘She econtric factor w is defined such that its value is equal to zero for the simple fl argon, Krypton and xenon (spherical). The acentric factor indicates a measure of deviation of the intermolecular potential of a molecule from that of a simple spherical molecule. hyChemical engineering thermodynamics cis th cntaonaldercd The three parameter law of corresponding states ie Z, when considered factor «, will have the same value of compressibility ac of T, and P,. That Zz (Ts Pew) d Pitzer’s corre! tion is given by Z= 29 (1, P) 402" (Tr, Py) y ibility gi = compress ne ang” where Z° = compressibility factor for simple fluids. 2 il ty factor as rand p term. An equation of state which expresses the compresswe i’ equ * called a generalized equation of state. The genci fi 3.67, 1 ( h ) 98 , Ih T+h) par 2 3.68) Where fh = 0-086 647, ZT, ~ ave—Redlich—-Kwo, ions. The Soave ng * ulations. NS CAuations can be conveniently used for iterative calcula (SRK) equation of state is given by 3.69) pa RT wR We (3.70) 2748272, whore = 24878822 7%6 . G71) 0.086647. aa G.72) va=14+s0—yT a $= 0.48 +1.5740 — 0.1760 ibility factor as The SRK equation can be expressed in terms of the compressibility factor on 2° — 29+ (A—B- BZ AB=0 ion of state is given by where A= aF/R?T? and B = bP/RT: The Peng-Robinson (PR) equation of state is gi ae A (3.75) i v@ +b) + ob) a (3.76) where a — 0.457242 72a RT. FZ & = 0.07780" 5° _T retations of fluide 87 yart+sa—vT) ¢ = 0.87464 + 1.542260 — 0.26992, cam Robinson equa (3.79) ee 1 EAN also be ex ‘The pe eray Pressed in terms of the compressibility factor as 2B)Z~(AB— Bp) 9 and Kesler modified the o 2.80 Lee and K adified the BWR equation using the Pi ae Lepr equation is given by ing the Pitzer's acentric factor. The modified Pte (3.82) (3.83) (84) (3.85) @.86) ba, er, C2: C8. Cay ds do, 6 and dye bas bay bay 6 ind -y are constants. ro diflerent sets of ‘constants — one set for the simple fluid and th reference fuid are given by Lee Kesler, From the above equations oe ere pei Emple fluid constants and ZF can be obtained with reference uid constants, Then 2 0 ae set fluid is given by fe stants. Then Z of the Za 2+ GZ" 2 PS @.81) where w and w denote the acentric factors of the real fluid and the reference ccti whore Lee-Kesler method, n-octane (w!" = 0.3978) is selected as the reference flan The generalized virial coefficient correlation gives me BP BP.) P; 2= +R ter) (3.90) 91) (3.95) (3.96) The generalized virial coefficient correlation is applicable to non-polar gases at low to moderate pressures.s 9, What is Te 4. 6 penmostserarnic® rable thermodynamic propertics? ire lines, for a pure substance constant pre: ion? owing ) of vapor gram, she Jatent heat 4 liquid? int? Ipy ( y of a mixture? w What is mi ever rule? ded volume? fan der Waals equi ion of state equal to the volume o, of the molecules? eUPicg 5, , cant by exclu! 10, What is ™ exclu mt parameter & in the ¥ 11, Ts 1m ecules? IC not, hiow is it related 1 the volume of | 12, What is the physical significance of te virial coeflicients? TF What is a compressibility factor? ic factor? sponding states. 14, What is an acentri 15. State the law of three Problems steam of quality 0. 3.1 3.2 3.3 3.4 3.5 3.6 37 38 parameter corres It is desired to fill 10 kg wet a5 at 200°C in a tank. Calculate the a ine tank and the internal energy of steam in the tank, The specific internal energie. saturated liquid and saturated vapor at 200°C are 850.57 kI/kg and 2593.1 kI/kg, Fespess eared TT m? volume contains 2.5 kg wet steam at 120°C. Determine the quai: ality ains a mixture of liquid water and vapo, fhe vessel contains only saturarct ‘Also determine the mass ot of steam in the tank. ‘A rigid vessel of 1 m° volume:initially cont Aion e: When energy is transferred as heat to the tank, 1 vapor at 250°C. Determine the mass of steam in the tank. the tank. turated water vapor at 200°C. Alll the valve, falves liquid and vapor phases initially contained in Aa certain instant a steam boiler contains sal fhe temperature of the boiler reduces to 110°C, of the boiler are closed. After some time, t oe ane oily losses as heat (0 the surroundings. Determine the ratio of the mass of ligui ae te case of vapor in the boiler when its temperature is 110°C. ad Sapese's pressure cooker initially contains a mixture of saturated liquid and saturay Seppe Pee 101.325 kPa. If enough ice is added to the pressure cooker and the id ie closed, does the mixture in the cooker attai i i i ie je mixture i cooker attain the triple point? Explain why or why Draw the pressure-temperature diagram for water and show the regi i ions of solid, liqui and vapor phases. Sketch the path followed by water for the following cases: (a) aaa ty of liquid and a small quantity of vapor at 100°C and vessel is filled with a large quanti the vessel is heated. (b) A rigid vessel is filled with a large quantity of vapor and a small avant or ee at 100°C and the vessel is heated. cylinder of volume 0.1 m!® is filled with ethy sn wlene to a pressure of 8: z Determine the mass of ethylene in the cylinder using the Meal gas law. nae culate the van der Waals constants a and for n-butane; ethylene; acetylene; ammonia and carbon dioxide from the critical constants T, and P.Pw relations of fluids 89 problem 3.7 suming that ethylene obeys the v: n der Waals equation of state. MErative method to determine the molar volume of ethylene gas. The constants @ «geen in Appendix Table A. 2. are Hhat_ ethylene obeys Van der Waals eq nin ion of state with the constants given aie ‘Table A.2, rework Problem 3.7. Use Cardan’s method to calculate the molar SOME: Gg 1 me volume is filled with $ kg ammonia at 300 K. Determine the pressure yar ASNca by ammonia (a) using the ideal gas law, and (b) assuming that ammonia obeys the * Qagals equation of state det Miiquid and vapor phases of ammonia coexist in a state of equilibrium and exert ores MPa. Determine the molar volume of ammonia vapor and ammonia Sjcce conditions, assuming that NHj follows the van der Waals equation of state. at erative scheme to determine the molar volumes. SSpiem 3.12 using Cardan’s method. “quation of state is given by (p+ gig) @- BE ere a and b are constants characteristic of the gas, Develop relations 5 to determine the where ais and # in terms of critical temperature and pressure, __ gta ar equation of sate f given by 335 ° po bese (Rize) = PT where @ and 6 are constants characteristic of the gas. Determine the relations to evaluate whefd gin terms of Te and Pe. a6 Express the Beattic-Bridgeman equation of state in the pressure explicit virial form. 3. 6 Extink of 1 m® volume is filled with 3 kg ammon! 3a7 ‘at 300 K. Determine the pressure A Ja0g by ammonia using the Redlich—Kwong equation. actuate the RK cquation of state so t uid volumes. 2 ase of NH a 2155 K i195 MPa Determine the oly volumes The waited vapor and saturated liquid using the RK equation of state, Make use of the of sive scheme developed in Problem 3.18. jg0 ini desired to store saturated ammonia at 321.55 K and 1.95 MPa in a tank of 10 m* 20H is ee Safety considerations dictate that no more than 70 per cent of the volume can Yolumied with liquid. Determine the maximum mass of ammonia that can be stored in the be tittSee Cardan’s method 10 calculate the molar volumes of saturated vapor and liquid. Amume that NH follows the RK equation of state. g21 Show that the virial coefficients B’, C', D’ of the Berlin form (volume explicit viria) Qhustion) are related to B, C, D of the Leiden form (pressure explicit virial equation) by the relations ‘hat it can be used for iterative calculation of vapor ios it can be used for iterati culation of vap' B c-8* B= 3BC+2B3 RT o> Try —RTy B Express the van der Waals equation of state as a generalized equa Z=Z (Tr Pe) of state, that isammics nde See pam on ility chart of Nelson ees essibility cl ang eneralized COM Tn and Obert determine bey em 3.7 using the genet art of © sn 3.23 Rework Problem ized compressibility CON tpg. As a result of contys, “ci = gencralized 32.5 ification. As a res I Ae mse af armmonia at $66.8 K and 22.55 Mf a pressure Of 13.7 MPa Men ey Soe raers are| calor coded with © hylene eal conditions it holds 34 oki a as eylinders are color coder | emical conditions it 8 kg ng te $25 The ges ciltviens 8 exlindr i filed under sere the generalized compress * code, a ad wi viinder. US BG Sane the mass of ethene in the i Jene at 37°C. Determine tye termine the mass of ethy ylene at 3 , te Det 250 kg cthy ed compressibility chart of Nelson te ine generaliz of Nelson and Obert. 4 from the relation § c is filled with lank of 1 m* volume is pet aes developed by the gas in the tank. Obert. stimate ance can be ¢ fa substance The vapor pressure of 3.27 A B ogi P = . logy t+E constants A, B, C for the Substance ‘The values of the P is in Torr and ¢ is in * ie tre given below, Calculate heir centre fa c A B n-Pentane 6,876 32 1075.780 ae Ethanol 8,112 20 _1592.864 ma6.184 Benzene 6.879 87 1196.760 219. Pretest, ‘ter compressibil . 3.28 Rework Problem 3.7 using the two parame! <2 ee ide at 10.0 MPa and 3 Be tank, ic oxi it tio three parameter compressibility factor correla! | jk the two parameter and three parameter compressibitiy, size of the tank using 3.29 It is required to store 1000 kg nit Determine the factor correlations with Lee-Kesler eae me 0.1 m? be filled to store 12 kg ethylene ay ure should a cylinder of volume 0. 3.30 To what press . developed when a tank of 1 m® filled with 100 kg methane is lef, pressure develo 25°C: 3.31 Calculate the is 40°C. in the surroundings where the temperature * ity of propa: 3.32 Using the generalized Redlich-Kwong equation calculate the ieee Roane Rewind 10 MPa, Use the iterative method of ealeulation 10 ecg . '33 Rework Problem 3.32 using the Cardan's method to determine the mola aan store 100 kg methane in a tank at 25°C and 2.0 MPa. Estima’ pacity 4 It is required to ase é the generalized SRK equation of state. | | eerste a tank of volume 50 mé is to be filled if the tank is to Of the tank usin, 35 Calculate the pressure to which i C. Use the generalized SRK equation of state. 1 of state, estimate the contain 750 ky of methane at 25° 6 Using the Peng—Robinson equatio (plume is to be filled with ethane at 400 K. se thar it contains 25 kg ethane. 7 Using the PR cquation of state, determing the size of a tank which can hold 1000 kg plane at 400 K, when filled to a pressure of 4 MPa. hen aneitions, calculate the capacity of a tank which > Using the generalized virial cool can hold 500 kg ethylene at 25°C, when filled ts Pressure of 10 bar,