Appendices D: Problems

1). From the data given in the following table, construct a complete temperature-composition

diagram for the system ethanol-ethyl acetate for 1.013 bar. A solution containing 0.80 mole

fraction ethanol is distilled completely at 1.013 bar. (a) What type of a curve is the mixture? (b)

What is the composition of the first vapour to come off? (c) What is the composition of the last

drop of liquid to evaporate?

Given:

BP,°C 77.15 76.7 75.0 72.6 71.8 71.6 72.0 72.8 74.2 76.4 77.7 78.3

XEtOH, 0 0.025 0.1 0.24 0.36 0.462 0.563 0.71 0.833 0.942 0.982 1.0

(L)

YEtOH, 0 0.07 0.164 0.295 0.398 0.462 0.507 0.6 0.735 0.88 0.965 1.0

(V)

Required: a) Type of Curve of the mixture

b) Composition of the first vapor to come off

c) Composition of the last drop of liquid to evaporate

Solution

80

78

76
BOILING POINT (°C)

74
Liquid
Vapor
72

70

68
0 0.2 0.4 0.6 0.8 1 1.2
Mole Fraction Ethanol
 a) The Temperature-composition diagram of the mixture is parabolic in shape.

b) The liquid phase of with 0.8 mole fraction will start boiling at the temperature 73.966°C

and equilibrium vapor to that temperature has a mole fraction of 0.7562.

c) Since all of the ethyl acetate will be separated eventually from the mixture as the

temperature increases, the composition of the last drop will be pure ethanol.

2) The vapor pressures of toluene and benzene have the following values in the temperature

range between their boiling points at 1 bar. (a) Calculate the compositions of the vapor and liquid

phases at each temperature and plot the boiling point diagram. (b) What type of a curve is the

mixture? (c) If a solution containing 0.5 mole fraction benzene and 0.5 mole fraction of toluene is

heated, at hat temperature will the first bubble of vapor appear and what will be its composition?

Given:

BP, °C 79.4 88 94 100 110

P°benzene, bar 1.00 1.285 1.526 1.801

P°toluene, bar 0.508 0.616 0.742 1.00

Required: a) Compositions of the vapor and liquid phases at each temperature and plot the

boiling point diagram.

b) Type of curve of the mixture

 c) The temperature and composition in which the first bubble of vapour appears after

a solution containing 0.5 mole fraction benzene and 0.5 mole fraction toluene is heated.

Solution:

a)

Let X B=mole fraction of Benzene X T =mole fraction of Benzene

X B + X T =1 X T =1−X B

At 79.4°C At 88°C

X B ( P° B ) + X T ( P ° T )=PT X B ( P° B ) + X T ( P ° T )=Patm

X B ( P° B ) +(1−X B) ( P ° T ) =P T X B ( P° B ) +(1−X B) ( P ° T ) =P atm

XB¿ XB¿

X B=1 1.285 ( X¯B ) +0.508 −0.508

¯ ( X¯B ) =1 ¯¿

X B (P ° B) 1.285 ( X¯B )−0.508 ( X¯B )=1 −0.508

¯ ¯¿
Y B= =1 ¿ ¿ Y B =1
PT
¯¿
0.777 ¯¿ ¿
0.777 ¯¿ (X B )=0.492 ¿¿
0.777 ¯¿ ¿

X B=0.6332

X B (P ° B)
Y B= =0.6332 ¿ ¿ Y B =0.8127
PT

At 94°C At 100°C

X B ( P° B ) + X T ( P ° T )=Patm X B ( P° B ) + X T ( P ° T )=Patm

X B ( P° B ) +(1−X B) ( P ° T ) =P atm X B ( P° B ) +(1−X B) ( P ° T ) =P atm

XB¿ XB¿

1.526 ( X¯B ) +0. 616 −0.

¯ 616 ( X¯B )=1 ¯¿ 1. 801 ( X¯B ) + 0.742 −0.
¯ 742 ( X¯B ) =1 ¯¿

1. 526 (X¯B )−0. 616 (X¯B )=1 −0

¯ .616 ¯
¿ 1. 801 (X¯B)−0.742 ( X¯B )=1 −0.
¯ 742 ¯¿

¯¿
1.059 ¯¿ ¿
1.059 ¯¿ ( X B )=0.258 ¿¿
1.059 ¯¿ ¿
 ¯¿ X B=0.2436
0 .91 ¯¿ ¿
¯
0. 91 ¿ ( X B)=0. 384 ¿¿
0. .91 ¯¿ ¿ X B (P ° B)
Y B= =0. 2436 ¿ ¿ Y B =0. 4387
PT
X B=0.4220

X B (P ° B)
Y B= =0. 4420 ¿ ¿ Y B =0. 6745
PT

At 79.4°C
TEMPERATURE-COMPOSITION DIAGRAM
X B ( P° B ) + X T ( P ° T )=PT 120
Temperate,°C

100
X B ( P° B ) +(1−X B) ( P ° T ) =P T 80
60 Liquid
40 Vapor
X B ( 0 ) + ( 1− X B ) ¿
20
0
X B=0 0 0.2 0.4 0.6 0.8 1 1.2

Mole Fraction Benzene

0( P ° B )
Y B= =1¿ ¿ Y B =0
PT

b) The temperature-composition diagram is biconvex in shape

c)

The temperature will be 92.091°C and the

composition will be YB=0.713