Tutorial I- LMPVLE (Answers are in parenthesis)

1. For the system ethyl ethanoate(1)/n-heptane(2) at 70oC, ln 1 = 0.95 x 22 ;ln 2 = 0.95 x12 ; P1sat =

79.80 kPa; P2sat = 40.50 kPa, (a) Make a BUBL P calculation for T = 70oC, x1 = 0.05.
[P=47.97kPa, y1 = 0.196] (b) Make a DEW P calculation for T = 70oC, y1 = 0.05. [P=42.19kPa,
x1 = 0.0104], (c) What is the azeotrope composition and pressure at T = 70oC? [Paz =47.97kPa,
x1 az = y1az = 0.857]
2. For a binary liquid solution: (GE/RT) = Ax1x2. For a wide range of temperatures it is found that
ln (P1S/ P2S) ~ 0.5. Find the range of values of A for which azeotropic behavior may occur for
the system at low pressure (< 1bar) VLE. [A>0.5 and A< – 0.5]
3. A liquid mixture of cyclohexanone(1)/phenol(2) for which x1 = 0.6 is in equilibrium with its
vapor at 144oC. Determine the equilibrium pressure P and vapor composition y1 from the
following information: ln 1 = A x 22 ; ln 2 = A x12 . At 417.15 K (144oC), P1sat= 75.20 and P2sat =
31.66 kPa. The system forms an azeotrope at 417.15 K (144oC) for which x1az = y1az = 0.294.
[P=38.19kPa, y1 = 0.844]
4. For the acetone (1)/methanol (2) system a vapor mixture for which z1 = 0.25 is cooled to
temperature T in the two-phase region and flows into a separation chamber at a pressure of 1
bar. If the composition of the liquid product is to be x1 = 0.175, what is the required value of T,
and what is the value of y1? For liquid mixtures of this system to a good approximation: ln 1 =
0.64 x 22 ; ln 2 = 0.64 x 12 [T =59.4C, y1 = 0.307]
5. The following is a rule of thumb: For a binary system in VLE at low pressure, the equilibrium
vapor-phase mole fraction y1 corresponding to an equimolar liquid mixture is approximately y1
= P1sat /( P1sat  P2sat ) ; where P isat is a pure-species vapor pressure. Clearly, this equation is valid
if Raoult’s law applies. Prove that it is also valid for VLE described by with: ln 1 = A x 22 and ln

2 = A x 12
6. The liquid phase activity coefficients at infinite dilution are 2.5 and 7.2 respectively for
chloroform (1) – methanol (2) system at 500C, and P1 sat = 0.67atm, and P2sat = 0.18atm. (i) Show
that the system forms an azeotrope, (ii) What type of azeotrope is it (maximum or minimum
boiling? Why? (iii) Assuming that van Laar activity coefficient model is valid for the liquid
phase compute the azeotropic composition and pressure. [x1az = 0.91; Paz = 0.69atm]
7. For a distillation column separating ethyl-ether(1)/ ethanol(2) into essentially pure components
at 1atm, find the range of values of 12 (relative volatility).
s s
Data: ln P1 = 9.25-2420.72 /(T-45.72), lnP2 = 12.17 - 3737.60 / (T-44.17), where P (bar),
T(K), For the liquid phase, GE/x1x2 RT = A21 x1 + A12 x2 ,
A12= 0.1665+233.74/T;A21 = 0.5908+197.55/T.
[12( x1  1 ) = 2.2, 12( x2  1 ) = 8.64]
8. Find if Benzene(1)/Cyclohexane(2) forms an azeotrope at 77.6oC. The following data are
available for use of Regular Solution theory. At 77.6oC, P1s = 745 mm Hg, P2s = 735 mm Hg.
[(x1)az = 0.525]

Species(i) Vi (cc/mole) i(cal/cc)1/2

Benzene 89 9.2
Cyclohexane 109 8.2

9. A liquid hydrocarbon ‘H’ of molecular weight 160 and specific gravity 0.8 has a saturation
vapour pressure of 13.3 kPa at 100C. An equimolar liquid phase mixture of H and CS2 at 100C
gives an equilibrium partial pressure of 8 kPa for ‘H’ in the vapour phase mixture. Assuming
ideal gas behaviour and using the data in the table below, estimate the composition of the vapour
1
 phase in equilibrium with an equimolar liquid mixture of ‘H’ and toluene. The solubility
parameters for hydrocarbons are  20 (J.cm–3)1/2. (All data in table are at 100C). [yH = 0.31]

Parameter Unit CS2 Toluene

Solubility Parameter ( δ) (J.cm–3)1/2 20.5 18.2
Liquid Molar Volume (VL) cm3/ mol 61 107
Saturation Vapour Pressure kPa 1.73 25.5

10. Low pressure, isothermal VLE data is generated experimentally for a certain binary system and
the activity coefficients computed (at suitable intervals of compositions) for the entire range of
liquid phase composition (0  x1  1.0). Further in order to obtain the expression for the molar
excess Gibbs free energy as a function of the liquid phase composition at the given temperature
 xx 
the function  E 1 2  is plotted against x1.
 G / RT 
a) If the resultant plot yields a straight line, show that the Van Laar type expressions for
the activity coefficients satisfy the above linear relationship.
 xx 
b) For the system both the slope and intercepts of the plot of  E 1 2  vs. x1 are
 G / RT 
found to be 0.5. Does the system have an azeotrope at the given temperature?
P1sat  0.8bar; P2sat  0.6bar. [x1az = 0.55]
11. Prove that for a non-ideal gas mixture: ln f mix   y ln  fˆ / y 
i
i i i

12. Prove that for a non-ideal gas mixture ln ˆi is a partial property of ln mix
13. The fugacity fmix of a binary gas mixture at 250C and 70bar pressure is:
ln f mix  4.2485  0.235 y1 . For equimolar mixture, calculate the species fugacities. [ fˆ1 = 27.7
bar, fˆ = 35.0bar]
2
14. For a binary mixture at 400C: ln  1  x22  x23 ; if the corresponding vapour pressures for
components 1 and 2 are 0.5 and 0.8 bar respectively, find the bubble point for an equimolar
liquid solution. [1.0234bar]
15. Consider a binary system of propanol (1) / water (2) the liquid phase for which is described by
the Wilson activity model. Compute the following: (i) P, y1, given T = 80C, x1 = 0.25 [91.5kPa,
0.54]; (ii) P, x1 , given T = 80C, y1 = 0.6 [96.72kPa, 0.45]. Data: The Wilson parameters are:
a12  437.98, a21  1238.00cal / mol; V1l  76.92, V2l  76.92cm3 / mol
P1sat  92.59kPa; P2sat  47.38kPa.
16. A certain binary mixture of two species (1 & 2) behaves as an ideal solution in the liquid phase.
A vapour mixture containing 75mol% of component ‘1’ at 3000K is in equilibrium with a liquid
phase. Find the liquid phase composition using the following information.
a. The 2nd virial coefficients are: B11  B22  B12  –500cm3 / mole.
b. The liquid phase molar volumes V1L and V2L are negligibly small.
At 3000K: P1sat  4.0bar; P2sat  2.0bar. [x1 = 0.6]