32° VAPOR-LIQUID EQUILIBRIA Solve for the mole fractions in the liquid: a Se (3. “STE De eo ” Put that expression into Eq. (3.3) to obtain the final equation: cs (Ki — De ea 1+ (K; — Dv! ~ ia This is called the Rachford-Rice equation. Notice that if the K-values and inlet composi- ms {z;} are known, this is a nonlinear equation to solve for v’. Thus, you can apply here the same methods used with Excel and MATLAB in Chapter 2. Once the value of »' is known, you can calculate the value of the liquid compositions, {x)}, and vapor compositions, {y;}, using Eqs. (3.1) and (3.8). The mole balance is then complete. Example Using Excel ‘Suppose you have a mixture of hydrocarbons in the inlet stream. You want to find the fraction of the stream that is vapor and find the mole fraction of each chemical in the vapor and liquid streams. Table 3.1 shows the flow rates and K-values at 180°F and 70 psia, using a basis of one mole per unit of time, To solve this problem, prepare the spreadsheet as shown, ‘Step I “Term 1” js the numerator in Eq. (3.9) and “Term 2” is the denominator. and these are calculated in columns D and E. Step 2 The ratios of “Term 1” over “Term 2” are calculated and put into column F; this column is summed in cell F9, which represents Eq. (3.9). Step 3 You can then use “Goal Seek” to make the Rachford-Rice equation (cell F9) zero by changing the fraction of the feed that is vapor (cell E1), giving the result shown, Once you find the fraction vapor, the mole fractions in the two phases are easy to calculate using Eq. (3.8) and (3.1), and these are included in columns G and H. TABLE 3.1 Spreadsheet for Flash Example A BC D E F G H 1 v = 0.425837 2 Phase 3 Equil. Terml= Term2= —_Ratio= 4 &_KNalue (Ky (Ki—Dot] Termiferm2 x, y 5 Propane 0.1 6.8 0.58 3.4699 0.1672 0.0288 6 n-Butane 03 © 22 036 1.5110 0.2383 0.1985 7 nPentane 04 08 -0.08 0.9148 — -0.0874 0.4372 0.3498. 8 mOctane 02 0.052 ~0.1896 0.5963 1 So) 3180 0.3354 0.0174 8.2719E-07 0,9999996 1.00000534° VAPOR-LIQUID EQUILIBRIA just one K-value that you can use in the calculations. Instead, one option is to choose the liquid mole fractions, determine the activity coefficients, then the K-values and see if the liquid mole fractions changed significantly. If so, you might use the new values and repeat the process. If this procedure did not work, you would have to use more sophisticated ‘methods to solve the Rachford-Rice equation using process simulators such as Aspen Plus or other iterative algorithms. There is one special case that is easy, however. If the liquid is an ideal liquid mixture, the activity coefficients are 1.0. If the pressure is low enough (say less than 10 atm.) the vapor phase is essentially an ideal gas and the fugacity coefficient of the vapor is 1.0, too. The fugacity of the liquid in the standard state is the vapor pressure, too, at low pressures. With those assumptions, the K-value becomes Pi P K, 3.12) ‘where vp; is the vapor pressure at a given temperature, In this special case, you can find the ‘K-values knowing the vapor pressure as a function of temperature and the total pressure of the system. Clearly, light components (lower boiling points) have a higher vapor pressure than heavy components, and thus their K-value will be larger. If two phases coexist at equilibrium, at least one of the components needs a K-value greater than | and at least one of the other components needs a K-value less than one. Even then two phases are not ‘guaranteed, and the result depends upon the composition as well as the K-values, Example Using MATLAB ‘You can solve the same problem (Table 3.1) using MATLAB. First, you define a function that represents the problem you wish to solve (Eq. (3.9)]. Then, you check the function to make sure it is correct. Finally, you use the “fzero” function to find the solution. The function defining the problem is % vapor-liguid equilibrium function y = vpequil(v) z= (0.1 0.3 0.4 0.2) K = [6.8 2.2 0.8 0.052} (3.43) suml = 0,; for isi:4 num = (K(i)-1)*z(i) (Kea) tz, denom = 1 + (K(i)-1)"v 1+ (e1)v sum = suml + num/denom end y = sum. sum1 = sum(num. /denom) ‘Step 1 Program the function and save it in your working directory as vpequil.m. ‘Step 2 Issue the command “vpequil(0.2)” in the command window; the output should be z= 0.1000 0.3000 0.4000 0.2000 K = 6.8000 2.2000 0.8000 0.0520 num = 0.5800 (3.14)