208 Chapter 5 Single-Phase Systems 1s eneralized comoresibiltyYactors (= 0.27) Or 02 030405 10 20 304080 10 2030, Reduced pressure, P, Figure 5.4-1 (Reprinted with permission from Chemical Process Principles Charts, 2nd Edition, by O. A. Hougen, K. M. Watson, and R. A. Ragatz, John Wiley & Sons, New York, 1960.) The procedure for using the generalized compressibility chart for PVT calculations is as follows: 1. Look up or estimate the critical temperature, T., and pressure, P., of the substance of interest (Table B.1). 2. If the gas is either hydrogen or helium, determine adjusted critical constants from the empirical formulas T; =Te+8K 4-4) Ph = Pe+8atm (54-5) ‘These equations are known as Newton's corrections. 3. Calculate reduced values of the two known variables (temperature and pressure, temper- ature and volume, or pressure and volume) using the definitions (4-6) P, (64-7) videat _ Pe? (54-8)54 The Compressibility Factor Equation of State 209 compressibility factor, = PPIRT Reduced pressure, P, Figure 5.4-2 Generalized compressibility chart, low pressures. (From D. M. Himmelblau, Basic Principles and Calculations in Chemical Engineering, 3rd Edition. copyright © 1974, p. 175. Reprinted by permission of Prentice Hall, Inc., Englewood Cliffs, NJ.) Don't forget to perform whatever unit conversions may be necessary to make the calcu- lated reduced variables dimensionless. If the gas is Hy or He, substitute for 7. and Pe the adjusted values of these quantities calculated in Step 2. All temperatures and pressures used in these calculations must be absolute. 4, Use the compressibility charts to determine the compressibility factor, and then solve for the unknown variable from the compressibility-factor equation of state (Equation 5.4. ‘The compressibility-factor equation of state used in conjunction with the generalized com- pressibility chart is not generally as accurate as a multiple-constant equation of state for PVT. calculations under highly nonideal conditions. Furthermore, it lacks precision and cannot read- ily be adapted to computer calculations. Its advantages include relative computational simplic- ity and (as will be shown) adaptability to multicomponent gas mixtures. The Generalized Compressibility Chart One hundred gram-moles of nitrogen is contained in a S-liter vessel at ~20.6°C. Estimate the pres- sure in the cylinder. SOLUTION From Table B.1, the critical temperature and pressure of nitrogen are Te = 1262K, — P; = 335 atm ‘The reduced temperature and volume are calculated from Equations 5.4-6 and 5.4-7 as T _ (-206 +2732) K tT 126.2K SL_| 335 am mol-K 100 mot [126.2 [0.08206 L! 2.00 qT im210 Chapter Single-Phase Systems z & 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Recuced pressure, P, Figure 5.43 Generalized compressibility chart, medium pressures. (From D. M. Himmelblau, Ba- sic Principles and Calculations in Chemical Engineering, 3rd Edition, copyright © 1974, p. 176. Reprinted by permission of Prentice Hall, Inc., Englewood Cliffs, NJ) TEST YOURSELF (Answers, p. 658) From Figure 5.4-4, the intersection of 7, = 2 and Vi! = 0.161 occurs at approximately z = 1.77. From Equation 5.4-2a, we can now calculate 2RT _ 1,77 | 0.08206 L-atm | 252.4 K P =| 733 atm v mol-K 5 Limol Note: You could also read the value of P, at the intersection and calculate P = P,P:; however, it is generally more accurate to calculate unknown variables by first determining z and then using the equation of state, as was done above. 1. Suppose you need to know the volume that would be occupied by 10 kmol of Hp at 190°C and 300 atm. Would you consider it reasonable to use a value calculated from the ideal gas equation of state? How would you use the generalized compressibility chart for this calculation? 2. Why would a chart such as that in Figure 5.4-1 be useless if T and P were the chart pa- rameters? 3. What isthe law of corresponding states, and how does it provide a basis for the generalized compressibility chart? 5.4c Nonideal Gas Mixtures ‘Whether an analytical or graphical correlation is used to describe nonideal gas behavior, dif- ficulties arise when the gas contains more than one species. Consider, for example, the SRK40 5.4 The Compressibility Factor Equation of State 211 1 TT T Le Li bs i CO Coot Cot COO { CP cris a T Trt T Tt T ae oe Coo oH cor rs Cho mn ! Z, 10 is 20 25 Reduced pressure, P, Figure 4-4 Generalized compressibility chart, high pressures (From D. M. Himmelblau, Basic Principles and Calculations in Chemical Engineering, 3rd Edition. copyright © 1974, p.177. Reprinted by permission of Prentice Hall, Inc., Englewood Cliffs, NJ.) equation of state (Equation 5.3-7): How would you estimate the parameters a, b, and a if the gas consisted of methane, carbon dioxide, and nitrogen? Mixture rules developed for such cir- cumstances are summarized by Reid. Prausnitz, and Poling (see footnote 1). We will illustrate PVT calculations for mixtures with a simple rule developed by Kay" that utilizes the general- ized compressibility charts. Kay's rule estimates pseudocritical properties of mixtures as simple averages of pure- component critical constants:!! Pseudocritical Temperature: T! = yaTea + yoTea + yeTec + * (54-9) Pseudocritical Pressure: PL = yaPca + yaPep + yoPec + (84-10) where ya,yp,... are mole fractions of species A, B,... in the mixture. Assuming that the system temperature 7 and pressure P are known, the pseudocritical properties can be used to estimate the pseudoreduced temperature and pressure of the mixture: Pseudoreduced Temperature: T= 1/7; (64-11) Pseudoreduced Pressure: PL = P/PL (5.412) ‘The compressibility factor for a gas mixture, zm, can now be estimated from the compressibility charts and the pseudoreduced properties, and V for the mixture can be calculated as SmRT =_= (84-13) "WB Kay, Ind. Eng. Chem, 28, 1014(1936) "The pseudocritcal constants are simply empirical parameters that have been found useful for correlating the physical properties ofa mixture. Unlike T_ and P. for asingle component, T; and P; have no physical significance.