Advanced Thermodynamis for Engineers 170 equenons oF stare mn de Waal equation FIGURE 56 (Citcalisotiems for argon. for the gas. The general shape is correct, but the van der Waals isotherm exhibits a critical volume greater than the true value, The reason is that Z. for a van der ‘Waals (vdW) gas is too large. With reference to Fig. 5-6. it may be shown that Pena Zens Powe Zot For argon, for example, with a Z, value of 0.291, the critical volume ratio in the above equation is 1.29. Thus the critical state in Fig. 5-6 for the van der Waals isotherm is moved roughly 30 percent 0 the right from the true position if the gas were argon. Although the van der Waals equation is not very good in predicting real-gas bbchavior except at low pressures, the preceding discussion demonstrates one im portant point: The two constants in any cubic equation of state may be determined more accurately by using experimental PeT data to fit the constants, However, in the absence of such data the criteria of PeT behavior at the eriteal state as expressed by Eqs. (5-3) and (5-4) is commonly used to evaluate a and b. For given values of P and T the van der Waals equation will yield three volume roots. two of which may be complex. A root is physically significant only if itis real, positive, and greater than 6. Three specific situations exist: When 7 > 7, tere are two Imaginary roots and one real positive TOOt for ©. The pressure has a monotonically decreasing value as v increases, as shown by the curve marked 7 > 7, on Fig. 5-7.Advanced Thermals ‘rwo.ranawerer cunic equarions or stare 7H FIGURE 5-7 Isotbems as given by a cuble equation of sae 2. For the critical isotherm, where T = T-, again only one real positive root exists, except at the critical pressure, At P, the equation has three real and coqual roots, all equal to ve. The isotherm also has a horizontal inflection at P., as shown in Fig, 5-7. 3. When 7’ < 7-, one real positive root occurs at high pressures. Over a range of lower pressures, however, the chee roots are real and unequal. The isotherm exhibits both a’ minimum and a maximum, as shown by the curve marked T 7. When experimental PoT data are not available for cvaluating @ and b, the criteria ofthe critical state are used. Setting (/Je)r, = (@P/ac®)r, = 0, and also employing Eq. (5-20), one finds that P- (5-20) Zonk. 392 Pog Peli g Pz #2 Bz +[o3s uF azz 9.07 Values of a and b are listed in Table A-23 in the Appendix for a few substances. Note that the critical compressibility factor based on the critical state eriteria is 1/3. This value is better than the van der Waals value of 3/8, but itis still somewhat higher than the typical range of experimental values. Similar to the discussion of the van der Waals equation, the RK equation prodicts liquid and vapor specific volumes when the temperiture is below the Critical value. The van der Waals and RK equations are easily solved when the independent variables are either © and T, or and P. However, when P andAduanced Thermesiyamics ‘ie coneEsPonowNG STATES mancioLe 73 T are known, a cubic equation in © must be solved. As noted earlier, either programmable electronic caleulators or computer software should be used to find the roots of the cubic equation. 5-5 THE CORRESPONDING STATES PRINCIPLE 5-19) and (5-24), both the van der Waals and RK equations in the form Z= Sth) (5-25) ‘This functional eolationship was first mengnized hy van der Waals in 1873. Thus the prediction of a unique relationship among Z, T;, and P, is known as the van der Waals two-parameter theorem of corresponding states. I states that any pure {gt at the same reduced temperature and presture should have the same compress ibility factor Exprocsions such a Eq, (5-25) are known ar generalized equations because of their general applicability to all substances. Since the van der Waals and RK equations apply to both the liquid and gas phases, the theorem expressed by Eq. (5-25) should also apply to both single phases, up to and including the satrated-vapor and saturated-liquid states. The theorem of corresponding states has been tested by evaluating Z versus TT, and P, from experimental PoT data for a sizable number of substances. Figure 5-8 shows Z plotted as a function of 7; and P, for 10 common substances [3]. ‘The overall average deviation from the mean isotherm lines is on the order of 1 pervent. However, for many oiler substanves the weary sometines proves to be less than desirable for engineering calculations. The well-known Nelson-Obert (4) ccharts for Z as a function of (T,, P,), based on the average PeT’ behavior of 30 fluids, predict Z within 5-6 percent except near the critical state (Z less than 0.5), ‘or near the saturation line, Figure A-36 in the Appendix shows a modified form ‘of a Nelson-Obert chart for the low-pressure range (P, = 1), where the saturation line is shown for both the vapor and liguid regions. Reasonable estimates of Z for either the saturated-vapor or saturated-liguid states can be made from this ‘chart. Figures A-37 and A-38 in the Appendix are Nelson-Obert charts for the imidpressure range, where P, varies from 0 to 10, and for the high-pressure range, ‘where P, varies from 10 to 40, The two-parameter corresponding states correlation ‘may be Considerably in error for strongly polar substances. (A polar substance is ‘one for which the centers of positive and negative charge do mot coincide.) In such cases the estimate for Z may be off by as much as 1520 percent. When used {or hydrogen, helium, and neon (quantum gases), one suggestion for improving the correlation is to redefine the reduced pressure and temperature for these three gases in the following manner: (5-26)Advanced Thermodynamis for Engineers 174 eouanos oF sxe — a Legend x Mate eo-pemane a rim O Biilene © mbapane Suman Nien (© Pupane 9 Caton donde i Gnbuave © War a Average ce ton da on hyd 0 a5 10 15 20 25 30 35 40 45 sO ss 60 45 70 Redced presse FIGURE 58 Experimental data corelaion fra generalized Z char. (K. Wa, Thermadmamics, Sth ed ‘McGraw-Hil Ine. Nw York, 1988. Sources Gur-Jen Su: "Mode Law of Conesponding Sty" Finds Cg Chern ete), 38.808, 1940.] Reprimed win Permiion Oy the AENCaR (Chemical Sos. IP is expressed in atmospheres and 7 in kelvins, then the value of C in both equations is 8 A generalized Z chart is a graphical representation of the relation Z = SMT, Pr). The variable © is introduced into generalized Z charts in the following ‘munnet. Substitution of the definitions of P,, 7;, and e, given by Eq. (5-2) into Eq, (5-8) which defines Z yields 627) Where the critical compressibility factor Z: = Prtc/RT. appears. Recall that Z: ranges from 0.22 (0 0.30 for most substances. Hence the above equation predicts that o- will not correlate very weil with 7, and P,: however, the parameter eZ should. Consequently, the variable v is introduced on the Nelson-Obert chart in the format ofthe pseudoreduced volume, w, where i wPe aa (5-28)Advanced Thermals re conmcesromone stares amare 175 Equation (5-28) shows that although isometric lines of the form ¢, = v/v. cannot be added to @ Nelson-Obert-lype chart, a redefined reduced volume line in the form of e; can be added. Lines of constant v; are also shown in Figs. A-36, ‘A-37, and A-38 in the Appendix. S-8-1 Three-Purameter Corresponding States Principle Statistical theory of panicle behavior shows that the two-parameter principle of corresponding states is fulfilled only if the intermolecular potentials of various types of particles are identical, except for the specific energy scale € and the di tance & factors which are characteristic of each substance. Thus any to macro- scopic parameters, such as T; and Pe, could be used to correlate PeT data However, the failure of the two-parameter corresponding states principle to pre- dict Z accurately except for a small number of substances indicates one or more additional parameters are required if better aceuracy is desired for a larger nu ber of substances, When actual experimental Z data for a number of faids are compared, they tend to fall into three rough classes: 1, Molecules which are spherical with respect to geometry and force field agree quite closely ‘Molecules with nonsphericity and/or a weak to moderate dipole moment show similar behavior, but Variations are more pronounced within the group and in ‘comparison to those in class (1) above. 3. Molecules with extreme nonsphericity andor strong dipole moments vary most ‘widely from the norm ‘This qualitative classification indicates that the degree of “sphericity” of a molecule might be used to account for the wide range of PeT behavior observed. ‘Thus many more substances might conform more closely to the corresponding states principle if a third parameter, characteristic of molecular structure, were included in the correlation. 5-5-2. The Critical Compressibility asa Third Parameter (One approach is to group Muids into several classes, where the critical compress ‘bility isthe third parameter. This method, first proposed by Lydersen, Greenkorn, and Hougen [5] presents separate Z-T,-P, charts or tables for particular values ‘of Z-. That is, the charts represent the relation Z = f(U-, Pr, Z<)- This approach does provide a significant improvement in accuracy. 5-8-3 The Acentric Factor as the Third Parameter Im the class structure described above molecules with a spherical geometry and force field and negligible quantum effects were called simple fluids by Pitzer [6]Advanced Thermodynamis for Engineers 176 ovanons or siare ‘The heavier permanent gases argon, Krypton, and xenon fulfil these characteris- tics, (In addition, the structure of gases such as methane, nitrogen, carbon monox- ide, and hydrogen sulfide is close to the permanent gases.) Fluids which fit class (Q) described in Sec. 5-5-1 are termed normal fluids, Because simple fluid be- havior is easily measured, a third parameter might be developed which measures the deviation from simple fluid behavior. That is, it measures nonsphericity or acentricity. Whatever characteristic is used, it should be easily measured. A prop: ‘erty which fits this nicely is the vapor pressure. Recall Fig. 5-3, which presemted vapor-pressure data on a reduced (generalized) basis. These curves are approxi: ‘ately Linear, and thus ean be represented by 2 single slope. Ifthe two-parameter corresponding states principle were generally valid, then the slope of the lines in the figure would be the same for all substances. This obviously is not true, except for the simple uids (Ar, Kr, Xe), The vaporpressure data for these ds do lic oon the same curve on this plot. Thus the position of the reduced vapor-pressure curve of a uid relative to the position for a simple fluid is a sensitive property ‘upon which a third parauetes uiay be bused Pitzer et al. [6] altibuied his difference in vapor-pressure variation 10 the degree of the sphericity of the molecular forve field of a substance. They defined ‘third parameter w, the acentric factor for a fluid, as the difference between the value of logy P& for the fluid and that for a simple fluid at a fixed value of 7 It was noted that logo P™* = ~1 at T#* = 0.7 for simple fluids. (In terms of Fig. 5-3, m = 5.4 for simple fluids.) With this data point as a convenient reference, the definition of w becomes 10 logo (PPj.-07 6-29) “The evaluation of e only requues fey Fe, and the vapor pressure at 1; = 0.7 This choice for definition of makes « = 0 for a simple fuid and positive for nearly all other Guids. In a general sense, «increases with polarity and with hydrocarbons it increases with molecular weight. Values of «for a number of substances are listed in Table A-2 in the Appendix. Several references [7,8] provide an extensive list of acensic values for substances, Example 5.2. Determine the value of for water based om Eq. (5-29), Solution. The critical data for water are 647.3 K and 220.9 bars. At a reduced temperature of 0.7 the actual temperature is T = T)Te = 0.1647.3) = 453.1 K = 180°C From the saturation table for water the vapor pressure at 180°C is 10.02 bars. Hence on the basis of Eq. (5-29) 10.02 © = =1.00— logy 92 = 0.343 ‘This value isin substantial agreement with that found in Table A-2. ‘The three-parameter corresponding states principle of Pitzer states that Z = fl,Prw)Advanced Thermals "kee RAMETER cusie HuATIONS UF siate 177 Ulike the method used by Lydersen etal. when Z. is the third parameter, Pitzer and coworkers developed linear coelation for Z, which has the form Z= +02" 60) where 2 and 2° ae both functions of T; and P,. In the case of simple fluids where w = 0, Eq, (5-30) reduces to Z = Z®. Thus the correlation for Z° as 4 function of T, and P, is based solely on data for argon, krypton, and xenon. ‘Analytical expressions for Z® and Z” are not practical. Hence the data are presented in graphical and tabular format. Data for Zand Z°? appear in Tables ‘A-24 and A-25 in the Appendix as generated by Lee and Kesler [9], who revised and extended the data of Pitzer. ‘The Lee and Kesler correlation is not particularly successful for polar com- pounds. ‘The method has been extend (10) 10 polar compounds by the addition Of a third term YZ® to Eq, (5-30), where Y is a parameter unique to each polar compound, In addition, water was used as a reference fuid to establish values of 21'aa a function of Ty and P,. [Example 5-3. Estimate the compressibility factor for nitrogen at 50 bars and 200 K by means of (a) Lee-Kessler data and (6) the superbeat table. Solution (@) The critical temperature and pressure of nitrogen are 126.2 K and 33.9 bars, respectively. Therefore, 200 = 1363 rom lables A-24 and 9-23 the values of 2 and 2.0 ae close to 0.895 and (0.130, respectively. On the basis of «= 0.039 from Table A-2, Eq. (5-30) yields Z = 0.895 + 0.039(0.130) ~ 0.900 (@) From the superhest able for nitrogen at 200 K and SO bars, » = 10.7 emg = 0.0107 mg. Therefore 7 Pe _ Sars x 0.0107 mg, _ 28 kg Rr 20K TORST bae “The value from the thee-paraineter principle of corresponding states. which depends fom the accuracy of reading Z© and Z\) from the figures, is very close to the tabulated value. Note thatthe third perameter correction is very sual in this case Nitrogen behaves nearly as a simple fluid, as indicated by its small value of « relative to other substances. T and Pp = = 18 0.901 5.6 THREE-PARAMETER CUBIC EQUATIONS OF STATE [As discussed in the preceding section, the addition of a third parameter greatly improves the accuracy of compressibility factor data, The use of the acentric factor @ has also been extended to cubic equations of state. Two widely used ‘equations in this format are the Redlich-Kwong-Soave (RKS) equation and theAdvanced Thermodynamis for Engineers 178 quarios or state Peng-Robinson (PR) equation. The primary use of these two equations is in the prediction of vapor-pressure and vapor-liquid equilibria data, Although similar in format, the RKS equation has an advantage in that it is somewhat easier to solve. 5-6-1 Redlich-Kwong-Soave Equation ‘The modification of the Redlich-Kwong equation made by Soave [11] in 1972 involves the cohesive energy term, or last term, in Eq. (5-20). The temperature ‘quantity 7"? was altered to include both the temperature and the aeentric factor «@, The RKS equation is Rr ea o-b were esh wine ag SABRE gy 52 @=[1+50-TY)F (5:33) 5 = 0480 + 1.574 ~0.17 639 where $ js a correlation against the Pitzer acentrc factor. The value of bis the ‘same as for the RK equation, while the factor @ requires 7? rather than T2*. The factor ais an empirical function determined from the vapor-pressure data of pure hydrocarbons. The value of in the RK equation is simply T~'/2, A refit of the ‘original correlation for $ has been done by Graboski and Daubert (12), and theit equation is = 0.48808 1 1.55176 0.156130? (538) ‘The RKS equation was developed to predict reasonable vapor pressures for pore fluids. Thus, there is no reason to suspect it is more accurate than the RK equation in predicting PoT behavior in the superheat region. One use of the RKS equation or its modification has been the prediction of the thermodynamic properties of refrigerants [13] 5-6-2 Peng-Robinson Equation This equation of state was developed primarily for vapor-liquid equilibrium pre- dictions and uses the same format for a as appears in the RKS equation. The Peng-Robinson (PR) equation [14] is a D+ oe 29. where the equation for $ in Bq, (5-33) is given by 5 = 0.37464 + 1.542260 — 0.269920 637) ‘The equation for « was again developed so as to reproduce hydrocarbon vapor pressures data. Since the denominator of the last term in Eq. (5-36) differs from theAdvanced Thermals “THRBEPARAMEFER CURIE EQUATIONS OF STATE 179) RKS equation, the relations for a and b determined from the critical state criteria, are altered. These become AAT? yy, . O.07780RT. > = (5-38) ‘The PR equation has about the same accuracy as the RKS equation in predicting compressibility factors or specific volumes, 5-6-3 General Comments on Cubic Equations of State ‘The van der Waals, Redllich-Kwong, Soave. and Peng-Robinson cubic equations of state discussed earlier are very similar in their analytical format. They are called ‘cubic equations of state, because, if expanded, each would contain volume terms rived to the first, second, and third powers “These eyations, and many other ceubie equations of state, can be expressed by a general lain in the format [151 y - 5-39) (w+ eo td) cm where b, ¢, and d are constants, and 1 is a function of temperature and has dimensions of Po®. The quantities © and & may be expressed on either a mass or ‘molar basis. As we have seen, the constants in cubic PeT equations are invariably evaluated in terms of critical data by employing Eqs. (5-3) and (5-4). Table 5-1 summarizes the values of-y, b ©, and d in Bq, (5-0) for the four eubic equations previously discussed. ‘AS a result of the data in Table 5-1, these four equations can be converted 10 a dimensionless format in terms of the reduced parameters P, and T,, and the pseudoreduced volume v= Po/ RT... Substitution of these reduced parameters into Eq. (5-39) gives the general reduced equation, r, at i = 5-40) as aCe CT oa where we have introduced the dimensionless parameters Le Per Pb Pee Pad ahh wath cake pak ean Finally, as we have seen already for the van der Waals and RK relations, cubic PoT equations can also be expressed as cubic equations for Z as a function of P, and T,..On the basis of the definition Po _ Prot ar” T, (5-42)