Alba, Tristan Joshua B.

Ch46 AA Experiment #9: Liquid-Vapor Equilibrium in an Azeotropic Mixture Results and Discussion: In the experiment, the liquid-vapor equilibrium of the acetone-cyclohexane solution is observed. As with most real solutions, the acetone-cyclohexane binary system behaves nonideally; but, also treated as if it behaves ideally, in the experiment. Three boiling point curves were generated: (1) Experimental, (2) Ideal; and, (3) Ideal curves. Two solutions initially acetone-rich and cyclohexane-rich were prepared. Using a reflux set-up, the boiling points of the pure components were determined. Samples were obtained from the reflux flask and from the sample tube for refractive index analysis. 2, 4, 6, 8 and 12 mL addition of the acetone were added to the cyclohexane-rich solution. Likewise, same amounts of addition of cyclohexane were added to the acetone-rich solution. Boiling points in every addition were determined. Samples from both reflux flask and sample tube were also obtained for analysis.
Cyclohexane Acetone Exp. BP 81.2 58.5 Lit BP 80.7 57 % Error 0.005 0.015

In order to determine quantitatively the concentration of the components of the binary system in each addition of a component, a calibration curve of the refractive index and mole fraction of cyclohexane must be constructed. Since the polynomial trend line y = -0.0055x2 + 0.0718x + 1.355; R2=0.992 [1] gives rise to a higher linearity compared to the linear trend line y = 0.0664x + 1.3557; R = 0.9985 [2] The polynomial trend line was used to solve the mole fractions of cyclohexane in each sample run. Both mole fractions of the liquid phase, X Cyc, obtained from the reflux flask and of the gas phase, Y Cyc, obtained from the sample tube were condensed vapor were caught, were calculated. With that, mole fraction of the corresponding component, acetone could also be computed. X Ac = (1- X Cyc)

Mole fractions of cyclohexane were graphed against the experimental onsets of boiling points of the solution. The experimental boiling curve of the acetone-cyclohexane binary system is as follows:

Subsequently, the boiling curve assuming ideal behavior of the binary system solution was plotted. For a solution to be ideal, the vapor pressure of a particular component of the solution should be proportional to the mole fraction of that component in the liquid phase over the entire range of mole fractions. This definition of an ideal solution is given by the Raoults Law: [3] where is the partial pressure of the ith component, is the mole fraction of the ith component and is the proportionality constant, the vapor pressure of the pure ith component. For a system containing gaseous components, the Daltons Law of Partial Pressures can also be applied. It states that: [4] where is the total pressure and are partial pressures of the components If P1, X1 refers to that of the Acetone and P2, X2 refers to that of Cyclohexane, combining Daltons Law of Partial Pressures and Raoults Law can determine the value of X2 to be equal to

[5] Y2, the mole fraction of cyclohexanes gas phase could similarly be derived as The values in Torr are made available through the Antoine equation:

[6] where A, B, and C are Antoine constants. The ideal boiling point curve was constructed by dividing into parts the temperature starting from the experimental boiling point of pure acetone to the that of pure cyclohexane. At the corresponding temperatures at the selected points, were determined. With that X1, Y1, X2, Y2, where 1 refer to that of Acetone and 2 to that of cyclohexane, were obtained. Boiling points versus mole fractions of cyclohexane plot was graphed.
P1 824.29 956.47 1104.87 1270.82 1455.68 1670.51 P2 369.620348 431.612756 501.58844 580.244439 668.304402 771.129913 X1 0.84321407 0.61232864 0.41673843 0.25016342 0.10756675 -0.0201583 X2 0.156785934 0.387671358 0.583261574 0.749836581 0.892433249 1.020158273 Y1 0.92303948 0.7777903 0.61147774 0.42219322 0.20794546 -0.0447205 Y2 0.07696052 0.222209699 0.388522262 0.577806782 0.79205454 1.044720531 T 58.5 63.0 67.5 72.0 76.5 81.2

The boiling point curve considering a non-ideal solution behavior was also constructed. Since activity coefficients are considered in such, equation 3 is rewritten: [7] where are activity coefficients Substituting the literature azeotropic point (50oC) in the Antoine equation gives the at the azeotropic point. By definition, the azeotropic point is the temperature at which the composition of the liquid and gas phase are equal. It follows that the activity coefficient at the azeotropic point:

[8] From the literature values of the exact composition of cyclohexane and acetone in solution at the azeotropic point (0.235 Cyclohexane: 0.765 acetone) and using the derived the Van Laar Constants which will be used in the computation of activity coefficients other than the .
Po
Acetone Cyclohexane
(REF-AZ)

(REF-AZ)

614.316147 1.22575323 271.780006 2.77062324

X (REF) 0.764565372 0.235434628

Inputing the values in the following equation for the Van Laar Constants: ( )
Van Laar Constants A 0.57106957 B 1.20297198

) [9], [10]

The Van Laar equations are as follows: ( ) ( ) [11], [12] With these, the activity coefficients other than that of the azeotropic point were calculated The composition of cyclohexane was divided into parts from 0 to 1 mole fraction at 0.05 mole fraction increments. Corresponding activity coefficients were determined. Using Daltons Law, the temperature is varied until the calculated P equals the experimental P = 753 Torr. [13] Values for the obtained vapor pressure values of each component at the determined temperatures are tabulated below:
X2 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Y2 NA 0.023 0.045 0.067 0.088 0.109 0.130 0.152 0.176 0.201 0.230 0.262 0.299 0.342 0.391 0.449 0.519 0.602 0.705 0.834 1.000

P1 824.29 764.57 761.88 750.33 733.85 715.12 695.96 677.54 660.68 645.90 633.62 624.20 617.94 615.21 616.50 622.39 633.76 651.80 678.30 715.97 769.02

P2 369.62 341.73 340.48 335.10 327.42 318.71 309.80 301.25 293.43 286.58 280.89 276.53 273.64 272.38 272.97 275.70 280.96 289.31 301.60 319.10 343.81

P NA 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00 753.00

T 58.5 56.276899 56.1735 55.72649 55.079 54.3291 53.5456 52.776 52.0564 51.414 50.871 50.4486 50.165 50.041 50.0997 50.367 50.877 51.6716 52.808 54.3635 56.4475

NA 1.013 1.048 1.101 1.169 1.251 1.344 1.450 1.566 1.693 1.831 1.978 2.136 2.303 2.479 2.665 2.860 3.063 3.276 3.496 3.725

NA 1.000 1.001 1.006 1.015 1.031 1.055 1.086 1.126 1.175 1.232 1.298 1.371 1.453 1.541 1.636 1.737 1.844 1.956 2.071 2.190

The boiling points and mole fractions of cyclohexane values were graphed.

As expected from a real solution, it could be noticed that the graph of the experimental boiling point curve is much similar to that of the non-ideal with a positive deviation from the Raoults Law, compared to that of ideal boiling curve. Azeotropic point was also determined at approximately 50.5oC (1% error) and 49.0 oC (2% error) in the non-ideal and experimental respectively. In the experimental, the composition of cyclohexane at the azeotropic point was at 0.32 (33% error). Errors in the experiment would greatly be attributed to the inaccuracy in the measurement of the refractive index of the solutions. Since acetone and cyclohexane are volatile substances, these might have vaporized if not measured immediately, altering the concentration of the components. Moreover, there is a need to equilibriate the sample to the room temperature at which the indices were obtained. Perhaps, lack of time of equilibriation might have also gave errors. Loss of sample during the determination of the boiling point, due to the components volatile nature, could also produce errors. The understanding of the Liquid-vapor equilibrium is vital to many chemical engineering processes such as in the determination of the amounts of the components of not only the liquid but also the gas phase at certain temperature at certain bulk composition. Conclusion: The liquid-vapor equilibrium of cyclohexane-acetone binary system was observed. The experimental, ideal and non-ideal boiling point curves were constructed and interpreted. As expected, the experimental had a distorted but sort of similar shape like that of the non-ideal. Azeotropic point was determined at 50.5oC and 49.0 oC in the non-ideal and experimental respectively.

Sample Calculation: Given: X Cyc = 0.25 X Ac = (1- X Cyc) = (1 0.25) = 0.75 More Calculations found in excel file References: Atkins, P. Physical Chemistry, 9th ed.