CL 253 Tutorial -5, September 2009

(For Antoine Constants see table before Problem Set in Ch 10)

1. 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 system is 1 bar; the temperature is
298.15 K (25oC). Determine from the following data good estimates of x1 and y1. H1 = 200 bar; P sat =
2
0.10 bar. [x1 = 0.0045, y1 =0.9].

2. A binary system of species 1 and 2 consists of vapor and liquid phases in equilibrium at temperature T.
The overall mole fraction of species 1 in the system is z1 = 0.65. At temperature T, ln γ1 = 0.67 x 2 ; ln γ2 =
2
2 sat sat
0.67 x ; P = 32.27 kPa; P = 73.14 kPa (a) Over what range of pressures can this system exist as
1 1 2
two phases at given T and z1? [43.86 – 56.75kPa] (b) For a liquid-phase mole fraction x1 = 0.75, what is
the pressure P and what molar fraction V of the system is vapor? [V= 0.379, P=51.9kPa], (c) Show
whether or not the system exhibits an azeotrope.[No]

3. For the system ethyl ethanoate(1)/n-heptane(2) at 70oC, ln γ1 = 0.95 x 2 ;ln γ2 = 0.95 x 2 ; P sat = 79.80
2 1 1
sat o
kPa; P = 40.50 kPa, (a) Make a BUBL P calculation for T = 70 C, x1 = 0.05. [P=47.97kPa, y1 = 0.196]
2
(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, x1az = y1az = 0.857]

4. 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
γ1 = A x 2 ; ln γ2 = A x 2 At 417.15 K (144oC), P1sat= 75.20 and P2sat= 31.66 kPa. The system forms an
2 1
azeotrope at 417.15 K (144oC) for which x1az = y1az = 0.294. [P=38.19kPa, y1 = 0.844]

5. A binary system of species 1 and 2 consists of vapor and liquid phases in equilibrium at temperature T,
for which ln γ1 = 1.8 x 2 ; ln γ2 = 1.8 x 2 ; P sat = 1.24bar; P sat = 0.89 bar. (a) What is the pressure P and
2 1 1 2
vapor mole fraction y1 within this range? [P=1.671bar, y1 = 0.6013] (b) For what range of values of the
overall mole fraction z1 can this two-phase system exist with a liquid mole fraction x1 = 0.65? [0.6013<
z1< 0.65] (c) What are the pressure and composition of the azeotrope at temperature T? [Paz =1.673bar,
x1az = y1az = 0.592]

6. 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 γ1 = 0.64 x 2 ; ln γ2 = 0.64 x 2 [T =59.4C, y1 = 0.307]
2 1

7. 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 Pisat 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 γ1 = A x 2 and ln γ2 = A x 2
2 1

8. A process stream contains light species 1 and heavy species 2. A relatively pure liquid stream containing
mostly 2 is desired, obtained by a single-stage liquid/vapor separation. Specifications on the equilibrium
composition are: x1 = 0.002 and y1 = 0.950. Use data given below to determine T(K) and P(bar) for the
B
separator. Data: For the liquid phase, ln γ1 = 0.93 x 2; ln γ2 = 0.93 x 2 ; lnPisat (bar) = Ai - i
; A1
2 1 0
T( K)
= 10.08, B1 = 2572.0, A2 = 11.63, B2 = 6254.0. [T=376.45K, P=0.137bar].
CL 253 Tutorial Set 5 1/2
9. A cooking gas cylinder is filled with LPG (a mixture of propane and butane) at 250C and 4 bar. Assume
that the mixture behaves ideally in both phases, and that the cylinder contains a large amount of liquid
phase and a small amount of gas phase. (a) Determine the composition of the mixture when the cylinder is
filled (b) When the cylinder is used for some time the pressure drops to 2.5 bar. What is the liquid
composition at this pressure (c) Estimate the cylinder pressure when it contains 95 mole% butane. The
Antoine constants are:
Substance A B C
Propane 6.82972 813.20 248
Butane 6.83029 945.9 240
Where P is in torr, t is in 0C; 1 bar = 750 torr [0.2233, 0.009844, 2.78bar]

10. For Propanol (1) / Water (2) system compute the following using Wilson equation for the liquid phase
activity coefficients. (a) P, y1, for T=60C, x1=0.3 [31.27 kPa, 0.414] (b) P, x1, for T=60C,
y1=0.3[27.69kPa, 0.042] (c) T=60C, P= 0.5 (Pb+Pd), z1=0.3, find x1, y1, V [0.08, 0.92, 0.811] (d) If an
azeotrope exists at T=60C, find Paz, and x1az = y1az [31.45kPa, 0.4403]. The Wilson parameters are: V1 =
75.14x10-3 m3/mol, V2 = 18.07x10-3 m3/mol, a12 = 3246.8kJ/kmol, a21 = 5660.1kJ/kmol

11. For the Propanol (1) / Water (2) find the following with NRTL model for the liquid phase. (a) P=101.3
kPa, x1=0.3, find y1, T [360.8K, 0.416] (b) P=101.3 kPa, y1=0.3, find x1, T [364.3K, 0.041] (c)
P=101.3kPa, T= 0.5 (Tb+Td), z1=0.3, find x1, y1, V [0.069, 0.353, 0.814] (d) If an azeotrope exists at
P=101.3kPa, find Taz, and x1az = y1az [360.64K, 0.4477]. The NRTL parameters are: b12 = 2095.1kJ/kmol,
b21 = 6852.0kJ/kmol, α=0.5081.

12. For a distillation column separating ethyl-ether(1)/ ethanol(2) into essentially pure components at 1atm,
find the range of values of α12 (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. [α12( x1 → 1 ) = 2.2, α12( x2 → 1 ) = 8.64]

13. 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) δi(cal/cc)1/2
Benzene 89 9.2
Cyclohexane 109 8.2

14. A vapour mixture contains 20mol% methane, 30mol% ethane, and rest propane, at 300C. Determine the
dew composition. [x1 = 0.0247, x2 = 0.1648]

15. The overhead product of from a distillation column is to have the following mole fraction composition
{zi}: propane (0.23), isobutane (0.67), and n-butane (0.10). Calculate the temperature at which the
overhead condenser must operate in order to completely condense the overhead product; (ii) if the
overhead product is in equilibrium with the liquid on the top plate of the column, calculate the
temperature of the overhead vapours and the composition of the top plate liquid at 8 bar; (iii) If the vapour
product is taken to a partial condenser at 8 bar and 320K, what faction of vapour condenses and the
corresponding composition of the two phases? [317K; 324.8K; L/F=0.75; x1 = 0.1829, x2 = 0.7053; y1 =
0.3713, y2 = 0.5642]

x2 ln γ 2 2 x ln γ 1 2
16. For Van Laar Model show that: A = ln γ 1 (1 + ) ; B = ln γ 2 (1 + 1 )
x1 ln γ 1 x2 ln γ 2

CL 253 Tutorial Set 5 2/2