5th Semester B. Tech., Tutorial - 7, Monsoon Semester, 2024-25
CH3001D CHEMICAL ENGINEERING THERMODYNAMICS-II
Instructions Use Appendices from Introduction to Chemical Engineering Thermodynamics (8th ed.) by Smith and Van Ness
Q. No. Question
1 a) Assuming that carbonated water contains only CO 2 (1) and H2O (2), determine the compositions of the vapor and liquid phases in a sealed can of “soda” at 25°C if the pressure inside the can is 5 bar. Assume H1 = 1670 bar at 25°C.
b) A concentrated binary solution containing mostly species 2 (but x2 ≠ 1) is in equilibrium
with a vapor phase containing both species 1 and 2. The pressure of this two-phase sat system is 1 bar; the temperature is 25°C. At this temperature, H1 = 200 bar and P 2 = 0.10 bar. Determine good estimates of x1 and y1. State and justify all assumptions.
2 The following is a set of VLE data for the system methanol(1)/water(2) at 333.15 K:
P (kPa) x1 y1 P (kPa) x1 y1
19.950 0.0000 0.0000 60.614 0.5282 0.8085
39.223 0.1686 0.5714 63.998 0.6044 0.8383
42.984 0.2200 0.6268 67.924 0.6804 0.8733
48.852 0.3039 0.6943 70.229 0.7255 0.8922
52.784 0.3681 0.7345 72.832 0.7800 0.9141
56.652 0.4461 0.7742 84.562 1.0000 1.0000
a) Find parameter values for the Margules equation that provide the best fit of G E / RT to the data, and prepare a Pxy diagram that compares the experimental points with curves determined from the correlation.
GE =( A 21 x 1 + A 12 x 2 ) x 1 x 2 RT
ln γ 1=x 22 [ A 12 +2( A 21− A 12 ) x 1 ] ln γ 2=x 12 [ A 21 +2( A 12− A 21 ) x 2 ]
b) Repeat part (a) for the van Laar equation.
GE A ' 12 A ' 21 x 1 x 2 = RT A ' 12 x 1 + A ' 21 x 2 A ' 12 A ' 21 ln γ 1= ln γ 2=
( ) ( ) 2 2 A ' 12 x 1 A ' 21 x 2 1+ 1+ A ' 21 x 2 A ' 12 x 1
3 The excess Gibbs energy for the system chloroform(1)/ethanol(2) at 55°C is well E represented by the Margules equation, G / RT = ( 1.42 x 1 +0.59 x 2 ) x 1 x 2. The vapor sat sat pressures of chloroform and ethanol at 55°C are P 1 =82.37 and P 2 =37.31 kPa respectively.
Assuming the validity of Modified Raoult’s law, make BUBL P calculations at 55°C for a) a liquid-phase mole fraction of 0.50.
For comparison, repeat the calculations using gamma/phi formulation of VLE with virial b) coefficients: B11 = -963, B22 = -1523, and B12 = 52 cm3.mol−1. Assume the Poynting factor as one for both the species.
4 A liquid mixture of 25 mol% n-pentane, 45 mol% n-hexane, and 30 mol% n-heptane,
initially at 69°C and a high pressure, is partially vaporized by isothermally lowering the pressure to 1.01325 bar. Find the relative amounts of vapor and liquid in equilibrium and their compositions.
