10.

2-1
a) Given: ethyl bromide (1) n-heptane (2) ideal mixture at T = 30 oC
P1vap=0.7569 bar
P2vap=0.0773 bar
x1=47.23 mol %
P=0.4537 bar
Required: y1, y2 at T= 30 oC
Solution: Basis: 1 mol of mixture, x1=0.4723

)(

)(

Answer: y1=0.7879; y2=0.0899

b) Given: ethyl bromide (1) n-heptane (2) mixture (regular solution) at T = 30 oC
P1vap=0.7569 bar
P2vap=0.0773 bar
x1=47.23 mol %
P=0.4537 bar
VL(cc/mol)
(cal/cc)1/2
(J/cc)1/2
Ethyl bromide(1)
75
8.9
37.2376
n-heptane(2)
148
7.4
30.9616
Required: y1, y2 at T= 30 oC
Solution: Basis: 1 mol of mixture, x1=0.4723, x2=0.5277
The regular solution model is employed,

(
(

)(

)(

)(

)(

R=1.986 cal/mol K
T=30+273.15=303.15 K
) (

)(
(

) (

)(

)(
(

)(

)(

)(

)(

)(

Answer: y1=0.8998, y2=0.0949

c) Given: ethyl bromide (1) n-heptane (2) mixture at T = 30 oC

P1vap=0.7569 bar
P2vap=0.0773 bar
x1=47.23 mol %
P=0.4537 bar
Required: y1, y2 at T= 30 oC
Solution: Basis: 1 mol of mixture, x1=0.4723, x2=0.5277
Using The Modified UNIFAC Program, and inputting necessary data as depicted below,

The activity coefficients from both species can be calculated,

)(

)(

)(

)(

Answer: y1=0.8681, y2=0.0982

d) Given: ethyl bromide (1) n-heptane (2) mixture at T = 30 oC
P1vap=0.7569 bar
P2vap=0.0773 bar
x1=47.23 mol %
P=0.4537 bar
It is also known that.
x1=28.43 mol %
y1=81.5 mol%
P=0.3197 bar
Required: y1, y2 at T= 30 oC
Solution: Basis: 1 mol of mixture, x1=0.2843, x2=0.7157
y1=0.815, y2=0.185

(
(

)(
)(

)
)

Using the One constant Margules Model,

)(
(

)
)

Hence, the activity coefficients of the 47.23 mol % mixture can now be calculated,
x1=0.4723, x2=0.5277

(
(
(

)(
)(
)(

)(

)(

)(

)(

Answer: y1=0.8667, y2=0.0977

)
)

)(

10.2-4
Given: Ethanol(1) Benzene(2) mixture at T=45 oC
Experimental Data:
x1
0.0000
0.0374
0.0972
0.2183
0.3141
0.4150
0.5199
0.5284
0.6155
0.7087
0.8102
0.9193
0.9591
1.0000

y1
0.0000
0.1965
0.2895
0.3370
0.3625
0.3842
0.4065
0.4101
0.4343
0.4751
0.5456
0.7078
0.8201
1.0000

x2
1.0000
0.9626
0.9028
0.7817
0.6859
0.5850
0.4801
0.4716
0.3845
0.2913
0.1898
0.0807
0.0409
0.0000

y2
1.0000
0.8035
0.7105
0.6630
0.6375
0.6158
0.5935
0.5899
0.5657
0.5249
0.4544
0.2922
0.1799
0.0000

P(bar)
0.2939
0.3613
0.3953
0.4088
0.4124
0.4128
0.4100
0.4093
0.4028
0.3891
0.3615
0.3036
0.2711
0.2321

a) Given: Ethanol(1) Benzene(2) mixture at T=45 oC

Required: P-x and x-y diagram with the assumption that the solution is ideal
Solution:
From the Experimental Data, it can be determined that,
P1vap = 0.2321 bar at x1=1.00
P2vap = 0.2939 bar at x2 = 1.00

For ideal mixtures, the Raoults Law is assumed to be valid,

With Equations 1,2 and 3, the following Data table and consequently the P-x and
x-y diagrams can be determined,
Table 4.1. P-x-y Data for Ethanol(1)- Benzene(2) Ideal Mixture

x1

x2

P(bar)

y1

y2

0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00

0.2939
0.2877
0.2815
0.2754
0.2692
0.2630
0.2568
0.2506
0.2445
0.2383
0.2321

0.0000
0.0807
0.1649
0.2529
0.3449
0.4413
0.5422
0.6482
0.7596
0.8767
1.0000

1.0000
0.9193
0.8351
0.7471
0.6551
0.5587
0.4578
0.3518
0.2404
0.1233
0.0000

0.4500

0.4000

P(bar)

0.3500
Ideal Mixture
0.3000

Experimental Data

0.2500

0.2000
0.00

0.20

0.40

0.60

0.80

1.00

Ethanol mole fraction

Figure 4.1. P-x diagram for Ethanol(1) Benzene(2) ideal Mixture

1.0000

Ethanol vapor mole fraction

0.9000
0.8000
0.7000
0.6000
0.5000

Ideal Mixture

0.4000

Experimental Data

0.3000

x=y

0.2000
0.1000
0.0000
0.00

0.20

0.40

0.60

0.80

1.00

Ethanol Liquid Mole Fraction

Figure 4.2. x-y diagram for Ethanol(1) Benzene(2) ideal Mixture

b)
Given: Ethanol(1) Benzene(2) regular mixture at T=45 oC

Ethanol(1)*
benzene(2)**

VL(cc/mol)
58.5
89

(cal/cc)1/2
12.7
9.2

(J/cc)1/2
37.2376
30.9616

*Data from J. Appl. Polym. Sci., 5(15), 339 (1961)

**Data from Sandler, S.I.(2006). Chemical, Biochemical and
Thermodynamics (4th edition).Asia: John Wiley and Sons, p 447 Table 9.6-1

Engineering

Required: P-x and x-y diagrams at T=45 oC

Solution:
Using the regular solution Model, the following equations will be used to determine the
activity coefficient and consequently the P and vapor composition,

R=1.986 cal/mol K
T=45+273.15=318.15 K
(


With Equations
diagrams can be determined,

, the following Data table and consequently the P-x and x-y

Table 4.2. P-x-y Data for Ethanol(1)- Benzene(2) Regular Mixture

x1

x2

Vmix(cm/mol)

P(bar)

y1

y2

0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00

89.00
85.95
82.90
79.85
76.80
73.75
70.70
67.65
64.60
61.55
58.50

0.0000
0.0681
0.1411
0.2198
0.3047
0.3966
0.4965
0.6053
0.7245
0.8554
1.0000

1.0000
0.9319
0.8589
0.7802
0.6953
0.6034
0.5035
0.3947
0.2755
0.1446
0.0000

3.1086
2.6779
2.3086
1.9945
1.7304
1.5112
1.3332
1.1932
1.0899
1.0240
1.0000

1.0000
1.0080
1.0350
1.0869
1.1737
1.3118
1.5300
1.8818
2.4734
3.5345
5.6153

0.2939
0.328787
0.350505
0.362492
0.367622
0.368152
0.365531
0.359787
0.347767
0.317782
0.2321

0.0000
0.1890
0.3057
0.3831
0.4370
0.4764
0.5079
0.5388
0.5819
0.6731
1.0000

1.0000
0.8110
0.6943
0.6169
0.5630
0.5236
0.4921
0.4612
0.4181
0.3269
0.0000

0.45

0.4

P(bar)

0.35
Regular Mixture
0.3

Experimental Data

0.25

0.2
0.00

0.20

0.40

0.60

0.80

1.00

Ethanol mole fraction

Figure 4.3. P-x diagram for Ethanol(1) Benzene(2) Regular Mixture

1.0000

Ethanol vapor mole fraction

0.9000
0.8000
0.7000
0.6000
0.5000

Regular Mixture

0.4000

Experimental Data

0.3000

x=y

0.2000
0.1000
0.0000
0.00

0.20

0.40

0.60

0.80

1.00

Ethanol Liquid Mole Fraction

Figure 4.4. x-y diagram for Ethanol(1) Benzene(2) Regular Mixture

c) Given: Ethanol(1) Benzene(2) mixture at T=45 oC

Required: P-x and x-y diagram if the mixture is described by UNIFAC Model
Solution:
Using the Modified UNIFAC program, the vapor compositions and the total
Pressure values was generated, as tabulated below,

Table 4.3. P-x-y Data for Ethanol(1)- Benzene(2) using UNIFAC MODEL
x1

x2

y1

y2

P(bar)

0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00

0.0000
0.2854
0.3386
0.3661
0.3876
0.4093
0.4353
0.4717
0.5309
0.6494
1.0000

1.0000
0.7147
0.6614
0.6339
0.6124
0.5907
0.5647
0.5283
0.4691
0.3506
0.0000

0.297
0.391
0.408
0.413
0.414
0.412
0.406
0.394
0.371
0.326
0.231

Figure 4.5. P-x diagram for Ethanol(1) Benzene(2) using UNIFAC Model

0.45

0.4

P(bar)

0.35
UNIFAC MODEL
0.3

Experimental Data

0.25

0.2
0.00

0.20

0.40

0.60

Ethanol mole fraction

0.80

1.00

Figure 4.6. x-y diagram for Ethanol(1) Benzene(2) using UNIFAC Model
1.0000

Ethanol vapor mole fraction

0.9000
0.8000
0.7000
0.6000
0.5000

UNIFAC MODEL

0.4000

Experimental Data

0.3000

x=y

0.2000
0.1000
0.0000
0.00

0.20

0.40

0.60

0.80

Ethanol Liquid Mole Fraction

1.00

d) Required: x-y and P-x diagrams Using van Laar model

Solution:
x1 = 0.6155
x2 = 1-0.6155 = 0.3845
y1 = 0.4343
y2 = 1-0.4343 = 0.5657
P=0.4028 bar

(
(

)(
)(

)
)

(
(

)(
)(

)
)

Using van Laar Equation Model,

(

) (

(
(

)(
)(

)
) (
)

) (

(
(

)(
)(

)
) (
)


With Equations
diagrams can be determined,

, the following Data table and consequently the x-y and P-x

Table 4.4. P-x-y Data for Ethanol(1)- Benzene(2) using van Laar Equation Model
x1

x2

P(bar)

y1

y2

0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00

7.5867
4.6268
3.1025
2.2538
1.7521
1.4427
1.2475
1.1247
1.0506
1.0118
1.0000

1.0000
1.0259
1.1003
1.2235
1.4005
1.6410
1.9590
2.3735
2.9093
3.5980
4.4799

0.2939
0.3787
0.4027
0.4086
0.4096
0.4086
0.4040
0.3920
0.3661
0.3171
0.2321

0.0000
0.2835
0.3576
0.3840
0.3971
0.4098
0.4300
0.4661
0.5329
0.6665
1.0000

1.0000
0.7165
0.6424
0.6160
0.6029
0.5902
0.5700
0.5339
0.4671
0.3335
0.0000

0.4500

0.4000

P(bar)

0.3500
van Laar Model
0.3000

Experimental Data

0.2500

0.2000
0.00

0.20

0.40

0.60

0.80

1.00

Ethanol mole fraction

Figure 4.7. P-x diagram for Ethanol(1) Benzene(2) using van Laar equation Model

1.0000

Ethanol vapor mole fraction

0.9000
0.8000
0.7000
0.6000
0.5000

van Laar Model

0.4000

Experimental Data
x=y

0.3000
0.2000
0.1000
0.0000
0.00

0.20

0.40

0.60

0.80

1.00

Ethanol Liquid Mole Fraction

Figure 4.8. x-y diagram for Ethanol(1) Benzene(2) using van Laar Model

From Figure 4.1 and 4.2, it is apparent that the mixture does not exhibit ideality,
the experimental results clearly shows the azeotropic nature, and hence non-ideality, of EthanolBenzene. The regular solution model was not able to coincide with the experimental data, as
shown in Figures 4.3 and 4.4, but it was able to depict the azeotropic behavior of the mixture.
The UNIFAC and van Laar Models proved to be sufficient in describing the equilibrium
properties of Ethanol-Benzene Mixture as depicted in Figures 4.5-4.8 since it coincides closely
with the P-x and x-y diagrams of the Experimental Data.

10.2-35
c) Given: 1 and 2 mixture at 90 oC
Required: P-x-y and x-y diagram
Solution:
Using van Laar Equation model,
From item a:
1.4999

Where P1vap = 0.9874 bar and P2vap=1.5172 bar (From item a)

Using Equations

, the P-x-y and x-y diagrams can be illustrated,

Table 35.1. P-x-y Data

x1

x2

P(bar)

y1

y2

0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00

4.4812
3.4222
2.6764
2.1455
1.7649
1.4913
1.2958
1.1591
1.0688
1.0170
1.0000

1.0000
1.0143
1.0594
1.1405
1.2670
1.4544
1.7271
2.1245
2.7109
3.5930
4.9540

1.5172
1.7230
1.8143
1.8468
1.8504
1.8395
1.8158
1.7682
1.6668
1.4489
0.9874

0.0000
0.1961
0.2913
0.3441
0.3767
0.4002
0.4228
0.4531
0.5065
0.6238
1.0000

1.0000
0.8039
0.7087
0.6559
0.6233
0.5998
0.5772
0.5469
0.4935
0.3762
0.0000

Figure 35.1. P-x-y diagram

1.9874
1.8874
1.7874
1.6874

P(bar)

1.5874
1.4874

LIQUID

1.3874

VAPOR

1.2874
1.1874
1.0874
0.9874
0.00

0.20

0.40

0.60

Component 1 mole fraction

0.80

1.00

Figure 35.1. x-y diagram

1.0000

Component 1 vapor mole fraction

0.9000
0.8000
0.7000
0.6000
0.5000

xy

0.4000

y=x

0.3000
0.2000
0.1000
0.0000
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
Component 1 liquid mole fraction

10.2-8
Given: n-pentane (1) acetone(2) mixture at P=1.013, with the following experimental data,

x1

y1

T(oC)

P1vap

P2vap

0.021
0.061
0.134
0.210
0.292
0.405
0.503
0.611
0.728
0.869
0.953

0.108
0.307
0.475
0.550
0.614
0.664
0.678
0.711
0.739
0.810
0.906

49.150
45.760
39.580
36.670
34.350
32.850
32.350
31.970
31.930
32.270
33.890

1.560
1.397
1.146
1.036
0.960
0.913
0.903
0.887
0.880
0.896
0.954

0.803
0.703
0.551
0.493
0.453
0.425
0.421
0.413
0.410
0.419
0.445

Required: Thermodynamic consistency of the experimental data

Solution:
Since the mixture is at constant P, the thermodynamic consistency relation
consistent with this system is,
(

Since the temperature range is not large we need to determine the value of the
excess enthalpy in order to deem the right term negligible. Using the Maxwell relation,
( )
For excess properties,
(

Hence to determine the relationship for Hex/T2, we need to graph the excess Gibbs
energy over temperature with respect to the whole temperature range and determine the slope of
such graph, the excess Gibbs energy can be determined from,

Where R= 8.314 J/mol K

The activity coefficients can be determined by,

Tabulating the results,

x1
0.021
0.061
0.134
0.210
0.292
0.405
0.503
0.611
0.728
0.869
0.953

y1
0.108
0.307
0.475
0.550
0.614
0.664
0.678
0.711
0.739
0.810
0.906

x2
0.979
0.939
0.866
0.790
0.708
0.595
0.497
0.389
0.272
0.131
0.047

y2
0.892
0.693
0.525
0.450
0.386
0.336
0.322
0.289
0.261
0.190
0.094

T(oC)
49.150
45.760
39.580
36.670
34.350
32.850
32.350
31.970
31.930
32.270
33.890

T (K)
322.300
318.910
312.730
309.820
307.500
306.000
305.500
305.120
305.080
305.420
307.040

P1vap
1.560
1.397
1.146
1.036
0.960
0.913
0.903
0.887
0.880
0.896
0.954

P2vap
0.803
0.703
0.551
0.493
0.453
0.425
0.421
0.413
0.410
0.419
0.445

1
3.340
3.649
3.133
2.561
2.219
1.819
1.512
1.329
1.169
1.054
1.009

2
1.149
1.063
1.115
1.170
1.219
1.346
1.559
1.822
2.371
3.507
4.553

ln2/1

ln1

ln2

G1ex

G2ex

Gex

Gex/T

-1.0666
-1.2330
-1.0337
-0.7830
-0.5988
-0.3012
0.0305
0.3157
0.7075
1.2022
1.5063

1.2058
1.2946
1.1421
0.9404
0.7970
0.5983
0.4135
0.2844
0.1557
0.0524
0.0094

0.1393
0.0615
0.1085
0.1574
0.1982
0.2971
0.4440
0.6001
0.8632
1.2546
1.5157

3231.169
3432.427
2969.538
2422.22
2037.522
1522.204
1050.275
721.4618
395.0408
133.1137
24.07796

373.138
163.1394
281.9742
405.3784
506.6393
755.929
1127.728
1522.241
2189.534
3185.827
3869.287

433.1567
362.566
642.1077
828.9151
953.6569
1066.27
1088.769
1032.965
883.1429
533.0192
204.8028

1.343955
1.136891
2.053233
2.675473
3.101323
3.484543
3.563893
3.385439
2.894791
1.745201
0.667023

Graphing the excess Gibbs energy over Temperature with the temperature range results
into,

G excess/T vs T
4.00
3.50
3.00

Gex/T

2.50
2.00
1.50
1.00
0.50
0.00
304.000

309.000

314.000

319.000

T(K)

J
A portion of the graph is almost linear, from 305.12 K to 318.91 K, hence we shall
concentrate our analysis on this area and determine the equation of the line,

4.00
3.50
y = -0.1778x + 57.789
R = 0.987

3.00

Gex/T

2.50
2.00
1.50
1.00
0.50
0.00
304.000 306.000 308.000 310.000 312.000 314.000 316.000 318.000 320.000
T(K)

From the add trendline function in EXCEL the equation of the line is,

Hence,

Since the value for the excess enthalpy is rather small in magnitude it is assumed to be
negligible, hence the thermodynamic consistency relation becomes,

The graph of

with respect to x1 is illustrated below,

2.0000
1.5000
y = 1.0105x2 + 1.9388x - 1.2457
R = 0.9958

ln2/1

1.0000
0.5000
0.0000
0.000

0.100

0.200

0.300

0.400

0.500

0.600

0.700

0.800

0.900

1.000

-0.5000
-1.0000
-1.5000

x1 n-pentane mole fraction

Using the ADD TRENDLINE function in EXCEL, a best fit equation is a second order
polynomial,

Substituting this equation to the thermodynamic consistency relation,

Since the integral is approximately equal to zero, the experimental data is thermodynamically
consistent.