100 PETROLEUM FLUIDS We have arrived at the equation pV = oRT (3-14) both empirically and theoretically. Mixtures of Ideal Gases Since the petroleum engineer primarily is concerned with gas mix- tures, the laws governing the behavior of mixtures of ideal gases will now be introduced. This will fater lead to an understanding of the behavior of mixtures of real gases. Dalton’s Law of Partial Pressures The total pressure exerted by a mixture of gases is equal to the sum of the pressures exerted by its components. The pressure exerted by each of the component gases is known as its partial pressure. Dalton postulated that the partial pressure of each component in a mixture of gases is equal to the pressure the component would exert if it alone were present in the volume occupied by the gas mixture. This is valid only when the mixture and each component of the mixture act as ideal gases. Dalton’s law sometimes is called the law of additive pressures. The partial pressure exerted by each component of a gas mixture can be calculated using the ideal gas equation. Consider a mixture containing n, moles of component A, ng moles of component B, ng moles of component C, and so on. The partial pressure exerted by each component of the gas mixture may be determined as RT Sa. According to Dalton, the total pressure is the sum of the partial pressures pa =a, 57, pp = mp SE pe = 1c @-27) P= Pat Ppt Pet... (3-28) Thus, = RE 4 my RE a a RT _ pam tm tty t.-- (3-29) and = RT — RT p= VFS = R (3-14)Equations of State 101 The ratio of the partial pressure of component j, p;, to the total pressure of the mixture p is B= = ="y, 3-30) ? yi ) where y; is defined as the mole fraction of the jth component in the gas mixture. Therefore, the partial pressure of a component of a mixture of ideal gases is the product of its mole fraction times the total pressure. B= YP. GB-30) Remember that this is valid only for ideal mixtures of ideal gases. EXAMPLE 3-3: Calculate the partial pressure exerted by methane in the following gas when the gas is at a pressure of 750 psia. Assume that the gas is a mixture of ideal gases. Component Composition, ___ mole fraction _ Methane 0.85 Ethane 0.10 Propane 0.08 1,00 Solution Por = P¥cr (3-30) Pa = (750 psia)(0.85) Por = 638 psia Amagat’s Law of Partial Volumes Amagat postulated that the total volume occupied by a gas mixture is equal to the sui of the volumes that the pure components would occupy at the same pressure and temperature. This is sometimes called the law of additive volumes. Amagat’s law of partial volumes is analogous to Dalton’s law of partial pressures. The volumes occupied by the individual components are known as partial volumes. This equation is correct only if the mixture and cach of the components obey the ideal gas equation.102 PETROLEUM FLUIDS Again consider a gas mixture consisting of ng moles of component A, ng moles of component B, and so on. The partial volume occupied by each component can be calculated using the ideal gas equation. RT RT RT Va = ty, Vp = np =, Ve = no ~,... (3-31 ‘A a Ve Bo? Ve an GB-31) According to Amagat the total volume is Vi= Va + Ve + Vo +t... (3-32) Thus, RT RT RT Vem + np +n +... 3-33 AF BD oF (3-33) and RT. RT v= §S, = Ea. G-14 pr ’p » ‘The ratio of the partial volume of component j to the total volume of the mixture is RT YL LP Lm — Vv Torr Tao O39) nT P Equation 3—34 states that for an ideal gas the volume fraction of a component is equal to the mole fraction of that component. Apparent Molecular Weight of a Gas Mixture Since a gas mixture is composed of molecules of various sizes, saying that a gas mixture has a molecular weight is not strictly correct. However, a gas mixture behaves as if it has a definite molecular weight. This molecular weight is known as the apparent molecular weight and is defined as M, =2yiM, . (3-35)Equations of State 103 EXAMPLE 3-4: Dry air is a gas mixture consisting essentially of nitrogen, oxygen, and small amounts of other gases. Compute the apparent molecular weight of air given its approximate composition. ‘Component Composition, mole fraction Nitrogen 0.78 Oxygen 021 Argon 0.01 Solution M, = ywaMyz + YooMo2 + yaMa (3-35) M, = (0.78)(28.01) + (0.21)(82.00) + (0.01)39.94) = 28.97 Ib/lb mole A value of 29.0 Ib/Ib mole usually is considered sufficiently accurate for engineering calculations. Specific Gravity of a Gas The specific gravity of a gas is defined as the ratio of the density of the gas to the density of dry air with both measured at the same temperature and pressure. Symbolically Pair” where +, is the specific gravity of the gas. On. the assumption that the behavior of both the gas and air may be represented by the ideal gas equation, specific gravity may be given as y, = 2 (3-36) (3-37) where M,i, is the apparent molecular weight of air and M, is the molecular weight of the gas. If the gas is a mixture, this equation becomes104 PETROLEUM FLUIDS w= w=, (3-38) a where M, is the apparent molecular weight of the gas mixture. Note that this equation is strictly true only if both the gas and air act like ideal gases. Often, specific gravity is called gravity or gas gravity; however, specific gravity is the correct term. EXAMPLE 3-5: Calculate the specific gravity of a gas of the following composition. Component Composition, mole fraction ‘ on Methane 0.850 Ethane 0.090 Propane 0.040 n-Butane 0.020 1,000 ~ Solution First, calculate apparent molecular weight, Equation 3-35. Mole fraction, Molecular weight, M, Component vw yM Cc, 0.850 16.04 13.63 Ce 0.090 30.07 271 cs 0.040 44.10 1.76 nC, 0.020 58.12 1.16 1.000 19.26 = Ma Second, calculate specific gravity. M, 19.26 = Ma = 1.260 = 9, 38) Ye = 39 = “a9 = 0.664 G-38) Behavior of Real Gases Researchers have proposed hundreds of equations of state for real gases. We will consider first the compressibility equation of state. This equation of state is the one used most commonly in the petroleum industry. This equation does have some limitations; therefore, we will examine later several other equations of state which are used to a lesser extent by petroleum engineers.Vu Equations of State 105 The Compressibility Equation of State We have shown from kinetic theory that the ideal gas equation has the correct form. The behavior of most real gases does not deviate drastically from the behavior predicted by this equation. So the best way of writing an equation of state for a real gas is to insert a correction factor into the jdeal gas equation.' This results in RE mM M zRT’ where the correction factor, z, is known as the compressibility factor and the equation is known as the compressibility equation of state. The equation has various names, such as the compressibility equation or the real gas equation. Compressibility factor is also known as gas deviation factor, super- compressibility, or z-factor. Sometimes the reciprocal of compressibility factor is called supercompressibility. ‘The z-factor is the ratio of the volume actually occupied by a gas at given pressure and temperature to the volume the gas would occupy at the same pressure and temperature if it behaved like an ideal gas. pV = 2nRT, pVy = 2RT, pv = , and py = (3-39) z = Yona (3-40) Vidcat In low pressure range, actual At higher pressures, V less than ideal V ‘actual V greater than Ideal V Pressure, p Fig. 3-1. Typical shape of z-factor as a function of pressure at constant temperature.106 PETROLEUM FLUIDS The z-factor is not a constant. It varies with changes in gas composition, temperature, and pressure. It must be determined experimentally. The results of experimental determinations of z-factors usually take the form shown in Figure 3-1. The shape of the curve is consistent with our knowledge of the behavior of gases. At very low pressure the molecules are relatively far apart, and the conditions of ideal gas behavior are more likely to be met. Experiments show that at very low pressures the z-factor approaches a value of 1.0. This indicates that ideal gas behavior does in fact occur at very low pressures. At moderate pressures, the molecules are close enough to exert some attraction between molecules. This attraction causes the actual volume to be somewhat less than the volume predicted by the ideal gas equation, that is, the z-factor will be less than 1.0. At higher pressures the molecules are forced close together, repulsive forces come into play, the actual volume is greater than ideal volume, and z-factor is greater than 1.0. 2 Factors for several hydrocarbon gases are given in Figures 3-2, 3-3, and 3-4. METHANE 09) 4 3,000 on 07 vm =-BM8 os] os | as u lo o. ao 10 o eT Tope goo,” 3-000 6,000 7,000 8,000 9,000 10,000 Preteute, pio Fig. 3-2. z-Factors for methane. (Brown, et al., Natural Gasoline and the Volatile Hydrocarbons, NGAA, 1947, 24, with permission.)pen Alle i 10.9 8 $00 1,000 1,500! 5,002 6,000 7,000 8,000 9,000 10,000 Pressure, pia Fig. 3-3. z-Factors for ethane. (Brown, et al., Natural Gasoline and the Volatile Hydrocarbons, NGAA, 1947, 26, with permission.) ‘0 007,000 $00 Prevsre, ple Fig. 3-4. z-Factors for propane. (Brown, et al., Natural Gasoline and the Volatile Hydrocarbons, NGAA, 1947, 27, with permission.)108 , PETROLEUM FLUIDS EXAMPLE 3-6: Calculate the mass of methane gas contained at 1,000 psia and 68°F in a cylinder with volume of 3.20 cu ft. Do not assume that methane is an ideal gas. Solution m= ey (3-39) Zz = 0.890, Figure 3~2 . Ib (1,000 psia) (ise pos) (3.20 cu ft) m= psia cu ft 30) (0.89) (10 732 b acl (528°R) m 10,2 Ib Note that the assumption that methane acts as an ideal gas in Example 3~1 resulted in an error in mass of about 11%. The Law of Corresponding States? Notice that the shapes of the isotherms of compressibility factors for the three gases given in Figures 3-2, 3-3, and 3-4 are very similar. The realization that this is true for nearly all real gases led to the development of the Law of Corresponding States and the definition of the terms reduced temperature and reduced pressure. Reduced temperature and reduced pressure are defined as a - ?P T, = qo and p, eS (3-41) The Law of Corresponding States says that all pure gases have the same z-factor at the same values of reduced pressure and reduced temperature. Figure 3-5 gives a test of this theory for compressibility data of methane, propane, n-pentane, and n-hexane.‘ Some of the deviation between lines at constant reduced temperatures may be due to experimental error and some due to inexactness of the theory. Data for pure hydrocarbon gases such as those presented in Figures 3-2, 3-3, and 3-4 have been put on a reduced basis and are given as Figure 3-6,* EXAMPLE 3-7: Determine the specific volume of ethane at 918 psia and 117°F, Use Figure 3-6 to determine the com- pressibility factor.Equations of State 109 Fig. 3-5. z-Factors at reduced pressure and reduced temperature for ethane, propane, n-pentane, and n-hexane. (From the Handbook of Natural Gas Engineering by Katz et al. Copyright 1959 by McGraw-Hill Book Co. Used with permission of McGraw-Hill Book Co.) Solution First, calculate reduced temperature and reduced pressure and deter- mine z. = T= STR _ —- T= = shine = 1085 @-41) p, = Pi = D8 psia_ = 139 (3-41) P —-706.5 psia z = 0.390, Figure 3-6 Second, calculate specific volume. 2RT pM y= (3-39)10 PETROLEUM FLUIDS ao No 120 30 14.0 15.0 Ractuced pressure, pe Fig. 3-6. z-Factors for pure hydrocarbon gases. (Brown, et al., Natural Gasoline and the Volatile Hydrocarbons, NGAA, 1947, 32, with permis- sion.) psia cu ft 0 (0.390) (10.730 7b moe | aoe (S77°R) ys aot lb (918 psia) (5007 wai = cu ft v = 0.0875 aa — Note the error that would occur if ethane was assumed to be an ideal gas at this pressure and temperature. The Law of Corresponding States is more accurate if the gases have similar molecular characteristics. Fortunately most of the gases the petroleum engineer deals with are composed primarily of molecules of the same class of organic compounds known as paraffin hydrocarbons.Equations of State il The Compressibility Equation of State for Gas Mixtures* The Law of Corresponding States has been extended to cover mixtures of gases which are closely related. As was brought out in Chapter 2, obtaining the critical point for multicomponent mixtures is somewhat difficult; therefore, pseudocritical temperature and pseudocritical pres- sure have been invented. These quantities are defined as Tye =SyjTy and Pye = BYiPy - G-42) These pseudocritical properties were devised simply for use in correlating physical properties. Pseudocritical properties are not equal to the actual critical properties of a gas mixture. Equations 3— 42 are often called Kay’s mixture rules. A somewhat more accurate method of calculating pseudocritical properties is given in Appendix B. EXAMPLE 3-1 8: Calculate the pseudocritical temperature and pseudo- critical pressure of the gas given in Example 3-5. Use the critical constants given in Appendix A. Solution 2 =ZyiTy and Pye = EPs (3-42) Critical Critical Mole temperature, pressure, fraction, °R psia Component w Ta YiTor Pay YiPot C 0.850 343.3 (281.8 666.4” 566.4 Ce 0.080 549.9 49.5 706.5 63.6 Cy 0.040 666.1 26.6 616.0 24.6 nC, 0.020 765.6 18.3 550.8 11.0 1.000 Tre = 383.2°R Bp: = 665.6 psia = 389°R, Pp = 686 psia Physical properties of gas mixtures are correlated with pseudoreduced temperature and pseudoreduced pressure in the same manner that properties of pure gases are correlated with reduced temperature and reduced pressure. Tr = te and py = (3-43)112 PETROLEUM FLUIDS Psoudoreduced pressure Pr Pseudoreduced pressure, Pp: Fig. 3-7. Compressibility factors of natural gases. (Standing and Katz, Trans., AIME, 146, 140. Copyright 1942 SPE-AIME).Equations of State 113 7 Peaudereduced pressure, por Fig. 3-8. Compressibility factors of natural gases at high pressures. (From the Handbook of Natural Gas Engineering by Katz et al. Copyright 1959 by: McGraw-Hill Book Co. Used with permission of McGraw-Hill Book Co.) The compressibility factors for, natural gases have been correlated using pseudoreduced properties.° The correlations are presented in Figures 3-7, 3-8, and 3-9. Remember that z-factors are a function of the type of gas as well as of temperature and pressure. Fortunately, most of the components of natural gases are hydrocarbons of the same family. Therefore, a correlation of this type is possible. The correlation is also successful because the components of most natural gases appear in approximately the same ratio to one another.14 PETROLEUM FLUIDS 05 10 as Prevdoreduced presures py Fig. 3-9. Compressibility factors of natural gases at low pressure. (Brown, et al., Natural Gasoline and the Volatile Hydrocarbons, NGAA, 1947, 33, with permission.) EXAMPLE 3-9: Calculate the mass in ib moles of the gas of Example 3-8 which is contained in 43,560 cu ft at 9,300 psia and 290°F. Solution First, calculate the pseudoreduced temperature, pseudoreduced pressure, and determine z, = 1 _ 70R | - Tr = To = —gaggg” = 1.96 G-43) Pe = P= 2300 pola _ yg (3-43) ~ Dee 666 psia 2% = 1,346, Figure 3-7Equations of State 115 Second, calculate mass in Ib moles. pv a= oe (3-39) ne (9300 psia)(43,560 cu ft) (1.346) {10.732 = cu fl lb mole °R, (750°R) n = 37,400 Jb moles Pseudocritical Properties of Heptanes Plus ‘We wil] see in Chapter 10 that the composition of a petroleum fluid is often given with all components heavier than hexane lumped together as heptanes plus. Pseudocritical pressures and pseudocritical temperatures for heptanes plus for use in Equations 3-42 can be obtained from Figure 3-10." EXAMPLE 3-10: Determine a value of z-factor for the dry gas given below for use at 3810 psia and 194°F, Component Composition, —__ mole percent__ Methane 97.12 Ethane 2.42 Propane 0.31 i- Butane 0.05 n-Butane 0.02 i- Pentane trace n-Pentane trace Hexanies 0.02 Heptanes plus 0.06 100.00 Properties of heptanes plus Specific gravity 0.758 Molecular weight 128 Ibfb mole Solution First, calculate pseudocritical properties, Equations 3-42.116 PETROLEUM FLUIDS woo 1600 1500 ‘Specitic gravity of heptancs plus =1,0" 7 1400 1300 1200 Peoudocritical temperature, ° R 1100 1000 300 100 150 200 250 300 Molecular weight of heptanes plus 500 450 400 <.0 = Sgecitic gravity of heptanes plus 350 s zi 300 Fas 30 250 73) Psoudocritical pressure, psia 200 a 150 190 100 150 200 250 300 Molocular wolght of hoptanes plus Fig. 3-10. Pseudocritical properties of heptanes plus.