Fugacity and Fugacity Coefficient (Multicomponent) Edward McLaughlin and Jaime Wisniak Department of Chemical Engineering Loui ina State University Baton Rouge, Louisiana 70803 OBJECTIVES Upon completion of this module, the student should be able to: 1. Extend the concept of the fugacity of a pure substance to a component of a mixture. 2. Caleulate the fugacity of a component of multicomponent mixture. 3. Appreciate the significance of the various degrees of sophistication with which the fugacity of a component of a mixture can be calculated. 4. Understand the mixing law for fugacities, PREREQUISITE MATHEMATICAL SKILLS. 1. Elementary Calculus. PREREQUISITE ENGINEERING AND SCIENCE SKILLS, 1, Elementary Thermodynamics, including fur gacity of a pure substance, partial molar properties, equations of state and free en- ergy funetions. ‘The concepts of fugacity and fugacity coefficient can be extended without difficulty to deseribe the overall behavior of a multicomponent mixture and of each one of its components. We will obtain expressions that correlate the overall fugacity and fugacity coefficient with the composition of the mixture and the fugacity of its components. Expressions will be derived to deter- imine the effect of pressure and temperature on these variables, as well as methods for their calculation from basic P-V-T data. FUGACITY ‘The fugacity of a pure component has already been defined as an intensive state property simply related to the Gibbs function, G, by Modular Instruction Series dG = nRTd Inf 0 jim Ee £ =i @ where the symbol (*) is used to indicate a pressure sufficiently low to assume ideal gas behavior and nis, the total number of moles in the system. “There is nothing in Equations | and 2 to prevent their application to describe the overall behavior of a mult component mixture of constant composition. Never- theless, we will proceed one step further and attempt to describe the fugacity of the mixture in terms of its ‘components and composition. Inspecting Equation |, we sce that the fugacity of pure component is defined in terms of its chemical potential, Using this idea as our model, we define the fugacity of a component in the mixture f,, as dG, = du, = RTdin f, 8) ‘The symbol (") has been added to indicate that fis not ‘a partial property, that is to say, SFE @ ‘The definition of fs in differential form; soin order to complete it, one has to provide one boundary condi- tion, A first impulse might be to try to extend Equation Zand say that tends to the partial pressure p, a8 P; tends to zero. Unfortunately, this is not general enough; may tend toward 2er0 by either dilution of component or by letting the fotal pressure P approach zero. The gas mixture will behave ideally only in the second case, hence: BL PRP 1 co) where y,P represents the partial pressure at very low values of P. Equation 5 completes the definition of f,Proceed now to determine the relationship between the overall fugacity of a mixture and that of its com- ponents. To do this, first integrate Equations I and 3 at constant temperature and composition, from a low pressure P* to any pressure P: G = ot = nrTint, 6 7 a fi G,- Gr = arin: 0 But at constant temperature G = 0G, ® G* = 3nG? 9) so that G-Gt=3,G,- Gh) (10) ‘Substitution of Equation 6 and 7 into Equation 10 yields eels f ART In = = En, In Fa ORT In Fe ay or fi fi In= = 2y, Ins fen Blo Fe (2) Finally, replacing f* and f* with the expressions given by Equation 2 and Equation 5, fi Inf = 2m f= Bytn5! a3) Inspection of Equation 13 shows that In (/,/y,) is equivalent to the partial property of In f. FUGACITY COEFFICIENT Although the definition of fugacity has the advantage of retaining the simplicity of the Maxwell equation for 4G, its logarithmic form makes it cumbersome for caleulations at low pressures. For this reason, itis convenient to define the auxiliary variable A Sai) (4) called the fugacity coefficient of component j in solution. One sees immediately that for low pressures 5 f Hg &> By sip as jim Ing, = 0 (16) ‘As seen later, the fugacity coefficient will et us get around the problem of calculating fugacities at very low pressures, The relation between , and g, the fugacity coef- ficient of the mixture, is easily found as follows. By definition 2 f ont ay therefore, substitution of Equation 13 and rearrange- ment gives sy ind! In(+ P) = Sy, Int In (@ + P) = Ey, In! or P| Ino) = By, ta( 2) = By In -P) Hence, Ing = 3y,In 6, (as) EFFECT OF PRESSURE AND TEMPERATURE Effect of Pressure The effect of pressure on f, and g, can be found by direct differentiation of Equation 13 with respect to P, at constant composition: (Ge), -2armf),, -»(? inf y «9 From the definition of f (Equation 1) aims) _ (26 or). G2" ‘Im (CP), RT 20) where v is the molar volume. Now v= Ly;y, so that comparing Equations 19 and 20, one gets ‘ain fy i ( wP ., RT en Equation 21 can be written in terms of 4, as follows. By definition, ¥ Inf = ing + InP Hence, from Equations 13 and 18: By, In = By, Ing, + InP x Therefore, Eom), =a 32 (2) % ae b= fv Amer te of Chemical Engineers Combining with Equation 21, gets: RT” \ P P so that ang) _1(-_R ),,7 ar) @ Equation 22 can be written in a more compact form using the residual volume of component i in solution, a, By definition, -# 3) Effect of Temperature ‘To obtain the effect of temperature on f,, differen- tiate Equation 6 at constant composition. aG/T) _ (G*/T) AT Joy, VT oy, (Gr..-PaA),] 2 But /* = P* (Equation 2) so that the last term is zero. According to the Gibbs-Helmholtz equation, aG/T) Hn 5 =n a fp, RT cD oor(t) HY OT dry, RT? 26) so that on a molar basis ain fy ata Ot), RE en At the very low pressure (*) the solution may be assumed to behave like an ideal gas so that We = By fit = Syke 08) h= 3yh, 9) where hj# represents the molar enthalpy of pure com- ponent i at P* and T. Substitution of Equations 28 and 29 in Equation 27 yields finally with Equation 13, ‘ain f, Heh, (a), - “ae Using the definition of ¢ in Equation 30: ),- Pe, Modular instruction Series Bn ‘Comparing Equations 30 and 31, one sees that the effect of temperature on f, and 4,is identical. EVALUATION OF /, and $, Equation 23 provides a powerful tool for evaluating 6, from experimental P-V-T data. Integration at con- stant temperature and composition, from a low pressure P* to any pressure P gives §-mngre- fe Ing, - ng? ad are? ‘And from Equation 5, In 6* = 0 at low or zero pressure, sothat ; Pa rod In = Bear = S (an - 3) 0? (32) ‘There are no problems in evaluating the RAS integral because the residual partial volume is bounded for all pressures. Thus one can calculate ¢, at any pressure and temperature, provided that the appropriate P-V-T data are available. The value of f, then follows from Equa- tion 14. Equation 32 demonstrates the importance of the auxiliary variable g. Had f; been calculated instead by direct integration of Equation 21, then Inf, - Inf? jar? 33) ‘The second term in the LHS is equal to in y,P* and it can only be obtained experimentally EVALUATION OF FUGACITY AND FUGACITY COEFFICIENTS IN GAS MIXTURES Various degrees of sophistication can be used to estimate the numerical values of fugacities and fugacity coefficients of components in gas mixtures. One meth- ‘od, the zero approximation, assumes that the fugacity js equal to the partial pressure: Si = yP G4) This may be used to fix the order of magnitude of f,. From a physical viewpoint, Equation 34 simply means that the mixture behaves like an ideal gas for all values of P. The fugacity coefficient 4, becomes 1.0 every- where, since it measures the departure from ideality. The Lewis Fugacity Rule ‘A second method assumes that the fugacity of a ‘component in a mixture is the mole fraction of the component, y, times the fugacity of species i in theTable 1. Thermodynamic Properties(1) of Ethylene (1) at 0.2 ‘mol fraction in mixtures with Argon (2) at 24.95 °C. Praim wNen/emod Frat yyfilata fy/atm—¢ r 0992 98 0.198 0990 5 481T 09630964 0964 10 9318 1864 18760938 15 13552 2710-247 0916 20 Ws 350235800395 25 21189 4238 ©4383 0877 30 84 el «4925 S.153 0.59 35 coz 276853 = S89 08a 40 5123 30761 6182 660s 0826, 4s ur9 3347366957283 0.809 50 30186 35867 2.173, 7938. 0.794 55 3515 3807609856509 0 3162 39958 19919162 0.763, 65 2852 416108329736 0749 70 2598 42964 859310282 0.735. 18 236.1 44066 8813 oT O72 %0 2159 45113 902311380 0.709, a 2002 46035 920711839 0.696, 30 848 46979 9396-12308 0.684 95 m7 41863 © 9357312773 0672 100 1610 48753 975113213661 10s 49.6 991 9918 13643 0.650 110 M03 S043 1008614038 0.638, us 1310 51286 10257 4aas 0.628 120 4a 52168 104344180617 ps 189 53052 Ia610 15.199 0.608, pure state, which can be obtained by any of the methods outlined in the module on fugacity of pure substances. One may therefore write Fi WL ous 35) This second method is often used, because if experi- mental P-V-T data on mixtures are not available, the RHS of Equation 32 cannot be evaluated in the absence of knowledge of the equation of state of mixtures. P-V-T-y, Data ‘There is very little experimental information available on P-V-T-y, data for multicomponent dense gas mix- tures for the obvious reason of the monumental ex- perimental task involved. Let us examine the data given in Table | for the partial molar volumes of ethylene ina ture with argon as a function of pressure(/). The fourth column gives the fugacity of ethylene in the mix- ture determined from the Lewis fugacity rule (Equation 35) and the fifth column the fugacity found from the Partial molar volume data using Equation 32. This shows that as the pressure increases the difference between the two sets of values increases so that the Lewis rule is only applicable at modest pressures. Known Equation of State Ifthe P-V-T-y, behavior of a system can be repre- sented by an equation of state in analytical form, then an expression for v, can be obtained and Equation 32 integrated analytically. It may be more convenient to use an equivalent alternative equation to Equation 32, ‘hich involves the pressure derivative and is given by RTIng, = S|) ~ Par - arin am, 6) instead of the equation already derived which involves the volume derivative, RTIng= ff fi. - lar The derivation of Equation 36 may be found in an article by Beattie(2). NOMENCLATURE second virial coefficient of mixture second viral coefficient of species cross-term second virial coefficient fugacity of a mixture or of a pure component fugacity of a species iin a mixture Gibbs free energy of the system partial molar Gibbs free energy of species jin the mixture enthalpy of the system molar or mean molar enthalpy partial molar enthalpy of species jin the mi ture molar enthalpy of pure component at low pressure total number of moles pressure partial pressure of species / gas constant absolute temperature volume of system molar or mean molar volume partial molar volume of species iin the mix- ture OOS SEE ar = " x mole fraction of species 7 x mole fraction of species / in the vapor phase Zon = compressibility factor for the mixture property at a pressure sufficiently low that the ideal gas law is obeyed am residual volume of component /in the mixture 4 = chemical potential of species i fugacity coefficient of species /in the mixture s " LITERATURE CITED 1. Gibson, G.. and B, Sosnick, J. Amer. Chem. Soe, 49,2172 (sz, 2. Beattie, J.A., Chom. Rev. 44, 141 (1948). 3. MeGlashan, M. Land D. J.B. Potter, Proc. R. Soe, A267, 478 (1962), 4, Hou ples,” 1:0. Ax and K. M. Watson, ‘Chemical Provess Prin "IT Thermodynamics, 601, Wiley, New York (1959), STUDY PROBLEMS 1, a) What are the dimensions of the fugacity of a component / in a multicomponent mixture? b) If the fugacity of a component i in a mixture is 4 bar in S.I, units, what is it in British Engineering Units? ©) Is the fugacity of a component in a mixture always less than the fugacity of the whole mix- ture? American Institute of Chemical Engineers [ 4d) What is the fugacity of nitrogen in a mixture containing 0.2 mol % nitrogen, 0.3 mol % carbon monoxide and 0.5 mol % oxygen at 90 °C and 0.1 at total pressure if the Lewis fugacity rule is valid? ©) What is the residual volume of species I ina binary ideal gas mixture? 2. If the fugacity of each component in a multicom- ponent gas mixture was adequately represented by the Lewis fugacity rule obtain an expression for the Fugacity of the mixture. 3. If there is no volume change on mixing, i.e. ve San where v, is the molar volume of pure species i at the temperature and pressure of the mixture then show the Lewis fugacity rule holds for such a mixture. HOMEWORK PROBLEMS 1. The partial molar volume of argon in ethylene at 25 °C as a function of pressure is given in Table 2 for a mole fraction of argon of 0.8. Evaluate the fugacity of argon in the mixture at 125 atm using graphical integration of the residual volume. ‘Table 2. Partial motar volume of Argon In Ethylene at 25 °C and ‘mole traction Argon 0 Prat Wem?mol" plat WenPmal! aT 24478 70 391 0 2481 30 2962 20 1208 50 2028 30 ‘sons 100 2356 0 600s 10 242 30 4788 120 1964 © 3970 ns 188.1 2, If the equation of state of a multicomponent mixture ‘of m species can be represented by the virial series, Py Ba Py oy 4 Bay Cue 7 RET te Se. 67) where v = mean molar volume of the mixture, show that ¢, is given by Py ye In = By, - ino (38) n= 5 3 9B, — Inge Modular Instruction Series if the virial series is truncated after the'second term, and Boa = 3 3 27By oo) (f you encounter problems, you may find it con- venient to start with a binary mixture and then generalize your result by inspection.) 3. The second virial coefficients of simple molecules obey the principle of corresponding states. This can bbe demonstrated by looking at the reduced second Virial coefficient B/», which is, as expected, a unique function of the reduced temperature T/T, where » is the ertical volume and 7. the critical temperature. This was done by McGlashan and Potter(3) for methane, argon, kypton and xenon who fitted the results to the equation: B ty Ty Boss osu (2) -oou(P ao so that if critical volumes and critical temperatures of simple molecules are known, their second virial coefficients can be estimated using Equation 40. In addition, the curve may be used to evaluate the B,, terms in Equation 39, as well as the B,, and B,, terms, if appropriate critical volumes and temper- atures are defined by Equations 41 and 42(3): 1 | ua gw ‘at gone +m) an TT.) (a2) Using the appropriate equations given, estimate the fugacity of a ternary mixture of 80 mol % methane, 10, mol % nitrogen, and 10 mol % argon, at 75 °C and 10, atm pressure. 4, Using the Lewis fugacity rule and the generalized fugacity coefficient tables in Hougen and Watson(4) calculate the fugacity of ethylene in a mixture of 0.2 ‘mol fraction ethylene and 0.8 mole fraction argon at 50 atm and 25 °C and compare your result with the experimental values given in Table |. Acknowledgements Thanks are due to Mr. David Caillet and Mr. Ken Reibert for checking the problems.