Department of Chemical Engineering

NON-IDEAL VLE CALCULATIONS

CHE 3105 THERMODYNAMIC ANALYSIS AND MODELING OF MIXTURES

Submitted by:

Branzuela, James Darel M.

Candar, John Reil
Lasola, Nico

November 24, 2020

Annex:
10.2-4

Given:

Azeotropic mixtures of Benzene and Ethanol

Experimental data:

‫ݔ‬ா ஺ ‫ݕ‬ா ஺ ܲሺܾܽ ‫ݎ‬ሻ

0.0000 0.0000 0.2939

0.0374 0.1965 0.3613
0.0972 0.2895 0.3953
0.2183 0.3370 0.4088
0.3141 0.3625 0.4124
0.4150 0.3842 0.4128
0.5199 0.4065 0.4100
0.5284 0.4101 0.4093
0.6155 0.4343 0.4028
0.7087 0.4751 0.3891
0.8102 0.5456 0.3615
0.9193 0.7078 0.3036
0.9591 0.8201 0.2711
1.0000 1.0000 0.2321

Required:

Prepare an x-y and a P-x diagram for the benzene-ethanol system at 45⁰C assuming,

a.) The mixture is ideal.

b.) The mixture is regular.

c.) The mixture is described by the UNIFAC model.

d.) The activity coefficients for this system obey the van Laar equation and the datum point at
x EA =0.6155 is used to obtain the van Laar parameters

Compare the results obtained from (a)-(d) with the experimental data given.

Solution:

Equilibrium criterion:

f Li ( T , P , x )=f vi ( T , P , y )

a.) The mixture is ideal.

At low-pressure, VLE equation:

 x i γ i Pvap
i = yi P (1)

Obtain value of P from Raoult’s law (for ideal liquid mixture + ideal vapor phase)

P=∑ xi Pvap vap vap

i =x EA PEA + x B PB (2)

Pvap vap
EA and PB were obtained using Antoine Equation

B
A−
P=10 C+T (3)

Where,

P is the vapor pressure

A, B and C are parameters for specific compound at a given temperature T

At 45⁰C, the vapor pressure of each specie was calculated using the following parameters

Parameters
A C B P(mmHg) P(bar)
Benzene 6.87987 1196.76 219.161 223.5893178 0.298094
Ethanol 8.20417 1642.89 230.3 172.3989804 0.229846

Pvap vap
EA = 0.229846, PB = 0.298094

Substituting Pvap vap

EA and PB to equation 2 and assuming values for x EA , P was calculated.

‫ݔ‬ாூீெ஺ ‫ݔ‬஻ூீெ ܲሺܾܽ ‫ݎ‬ሻ

0.0000 1.0000 0.2981

0.0374 0.9626 0.2955
0.0972 0.9028 0.2915
0.2183 0.7817 0.2832
0.3141 0.6859 0.2767
0.4150 0.5850 0.2698
0.5199 0.4801 0.2626
0.5284 0.4716 0.2620
0.6155 0.3845 0.2561
0.7087 0.2913 0.2497
0.8102 0.1898 0.2428
0.9193 0.0807 0.2354
0.9591 0.0409 0.2326
1.0000 0.0000 0.2298

Since γ i=1, for ideal mixtures, equation 1 simplifies to:

x i Pvap
i
y i=
P

x EA Pvap
EA
y EA= (3)
P
Using equation 3 and P (bar) values obtained from equation 2, y EA was calculated.

‫ݔ‬ாூீெ஺ ‫ݕ‬ாூீெ஺ ܲሺܾܽ ‫ݎ‬ሻ

0.0000 0.0000 0.2981

0.0374 0.0291 0.2955
0.0972 0.0767 0.2915
0.2183 0.1772 0.2832
0.3141 0.2610 0.2767
0.4150 0.3536 0.2698
0.5199 0.4550 0.2626
0.5284 0.4635 0.2620
0.6155 0.5524 0.2561
0.7087 0.6523 0.2497
0.8102 0.7670 0.2428
0.9193 0.8978 0.2354
0.9591 0.9476 0.2326
1.0000 1.0000 0.2298
, Mole fraction of ethanol in vapor phase

T = 45⁰C

x-y diagram of ethanol assuming ideal mixture

 T = 45⁰C

P-x diagram of ethanol assuming ideal mixture

b.) The mixture is regular.

Using equation 1 and 2:

x i γ i Pvap
i = yi P

∑ x i γ i Pvap
i = ∑ Pi=P

Using regular solution model activity coefficients,

RT ln γ 1=V 1 Φ22 [δ 1−δ 2 ]2 (4)

RT ln γ 2=V 2 Φ21 [δ 1−δ 2] 2 (5)

Where component 1 is ethanol and component 2 is benzene

Component VL ߜ
Ethanol 58.24 12.92
Benzene 89 9.2

V Lfor benzene is taken from 9.6-1 of Chemical, Biochemical, and Engineering Thermodynamics 4th
Edition by Stanley Sandler
V L for ethanol is calculated given that:

kg
ρ E A at 45 ℃=791.1 =0.7911 g/cc
m3

Taken from https://www.engineeringtoolbox.com/ethanol-ethyl-alcohol-density-specific-weight-

temperature-pressure-d_2028.html

46.07 g
MM E=
mol

Taken from https://pubchem.ncbi.nlm.nih.gov/compound/ethanol

MM E 46.07 g /mol
V L E A= = =58.24 cc /mol
ρ E at 45℃ 0.7911 g /cc

Solubility parameters, δ, for ethanol and benzene are taken from

https://cool.culturalheritage.org/byauth/burke/solpar/solpar2.html

Φ j can be expressed as:

xjV j x jV j
Φ j= =
∑ xk V k ∑ xk V k
k k

For Regular Solution, activity coefficient is expressed as:

2
x B V LB
RT ln γ E A=V L
EA
( x B V + x EA V L
B
L
EA
) (δ E A −δ B )2

2
x E A V LE A
RT ln γ B =V L
B
( x B V + x EA V L
B
L
EA
) (δ E −δ B )2

2
x B V BL
V EA
L
( L
x B V B + x EA V EA
L
) 2
(δ E A −δ B )

RT
γ E A=e
2
x EA V LE A
VB
L
( L
x B V + x EA V
B
L
EA
) (δ EA −δ B )
2

RT
γ B =e

Where,

cal
R=1.987046
K mol

T =318.15 K
Calculating activity coefficients, y EA, and P:

‫ݔ‬ாோ஺ ‫ݔ‬஻ோ ߛாோ஺ ߛ஻ோ ܲሺܾܽ ‫ݎ‬ሻ ‫ݕ‬ாோ஺

0.0000 1.0000 3.5783 1.0000 0.2981 0.0000

0.0374
0.0972 0.9626
0.9028 3.3617
3.0422 1.0012
1.0085 0.3162
0.3394 0.0914
0.2003
0.2183 0.7817 2.4877 1.0476 0.3689 0.3383
0.3141 0.6859 2.1271 1.1091 0.3803 0.4038
𝑦_ 𝐸 ,𝐴M ^ o 𝑅l e f r a c t i o n o f e t h a n o l i n v a p o r p h a s e

0.4150 0.5850 1.8124 1.2163 0.3850 0.4490

0.5199 0.4801 1.5476 1.3981 0.3850 0.4803
0.5284 0.4716 1.5287 1.4171 0.3849 0.4824
0.6155 0.3845 1.3554 1.6652 0.3826 0.5012
0.7087 0.2913 1.2089 2.0854 0.3780 0.5210
0.8102 0.1898 1.0926 2.8761 0.3662 0.5556
0.9193 0.0807 1.0180 4.5476 0.3245 0.6629
0.9591 0.0409 1.0048 5.5685 0.2894 0.7654
1.0000 0.0000 1.0000 7.0161 0.2298 1.0000

T = 45⁰C

𝑥_ 𝐸𝐴^𝑅 , Mole fraction of ethanol in vapor phase

x-y diagram assuming regular solution

 P, bar

T = 45⁰C

𝑥_𝐸𝐴^𝑅 , Mole fraction o f ethanol in vapor phase

P-x diagram assuming regular solution

c.) The mixture is described by the UNIFAC model.

A computer program called “Modified UNIFAC” was used to generate values of activity coefficients.

‫ݔ‬ா௎஺ ‫ݔ‬஻௎ ߛா௎஺ ߛ஻௎ ܲሺܾܽ ‫ݎ‬ሻ ‫ݕ‬ா௎஺

0.0000 1.0000 12.0387 1.0000 0.2981 0.0000

0.0374 0.9626 7.8071 1.0078 0.3563 0.1884
0.0972 0.9028 4.9093 1.0411 0.3899 0.2813
0.2183 0.7817 2.7934 1.1531 0.4089 0.3428
0.3141 0.6859 2.1017 1.2773 0.4129 0.3675
0.4150 0.5850 1.6857 1.4488 0.4134 0.3889
0.5199 0.4801 1.4164 1.6873 0.4107 0.4121
0.5284 0.4716 1.3993 1.7101 0.4104 0.4141
0.6155 0.3845 1.2527 1.9824 0.4044 0.4382
0.7087 0.2913 1.1415 2.3786 0.3925 0.4738
0.8102 0.1898 1.0602 3.0045 0.3674 0.5373
0.9193 0.0807 1.0113 4.0723 0.3116 0.6857
0.9591 0.0409 1.0030 4.6288 0.2775 0.7967
1.0000 0.0000 1.0000 5.3405 0.2298 1.0000
 𝑦_ 𝐸 ,𝐴M ^ o 𝑈l e f r a c t i o n o f e t h a n o l

T = 45⁰C

𝑥_ 𝐸𝐴^𝑈, Mole fraction of ethanol in vapor phase

x-y diagram for UNIFAC model

P, bar

T = 45⁰C

𝑥_ 𝐸𝐴^𝑈, Mole fraction of ethanol in vapor phase

P-x diagram for UNIFAC model

d) Use van Laar model to calculate for vapor compositions

x EA =0.6155

y 1=0.4343

P=0.4028 ¯¿
 initial y EA P
γ EA =
x EA Pvap
EA

0.4343(0.4028)
γ EAinitial= =1.224 6
0.6155(0.2321)

initial yBP
γB =
x B P vap
B

γ Binitial =2.016 4

Calculating van Laar parameters:

2
x B ln γ Binitial
(
α = 1+
x EA ln γ EA initial ) ln γ EAinitial=2.026 3

2
x EA ln γ EAinitial
(
β= 1+
x B ln γ B initial ) ln γ B initial=1.499 8

Calculating final activity coefficients :

α
2
αx EA

γ EA final
=e
( 1+
βx B )
β
2
βx B

γ B final =e
( 1+
αx EA )

Find vapor compositions

x EA γ EA final P vap
EA
y EA=
P

where P=∑ x i γ ifinal Pivap

Calculating activity coefficients, y EA, and P:

௙௜௡௔௟ ௙௜௡௔௟
‫ݔ‬ா௩௅஺ ‫ݔ‬஻௩௅ ߛா ஺ ߛ஻ ܲሺܾܽ ‫ݎ‬ሻ ‫ݕ‬ா௩஺௅

0.0001 0.9999 7.5818 1.0000 0.2982 0.0006

0.0374 0.9626 6.2290 1.0037 0.3416 0.1568
0.0972 0.9028 4.6849 1.0245 0.3804 0.2752
0.2183 0.7817 2.9101 1.1191 0.4068 0.3589
𝑦_ 𝐸 𝐴, M ^ o𝑣 l 𝐿e f r a c t i o n o f e t h a n o l i n v a p o r p h a s e

0.3141 0.6859 2.1670 1.2450 0.4110 0.3807

0.4150 0.5850 1.6961 1.4322 0.4115 0.3931
0.5199 0.4801 1.3966 1.6975 0.4098 0.4072
0.5284 0.4716 1.3780 1.7227 0.4095 0.4087
0.6155 0.3845 1.2245 2.0164 0.4044 0.4284
0.7087 0.2913 1.1166 2.4150 0.3916 0.4645
0.8102 0.1898 1.0452 2.9722 0.3628 0.5365
0.9193 0.0807 1.0076 3.7523 0.3032 0.7023
0.9591 0.0409 1.0019 4.0936 0.2708 0.8157
0.9999 0.0001 1.0000 4.4798 0.2300 0.9994

T = 45⁰C

𝑥_ 𝐸𝐴^𝑣𝐿, Mole fraction of ethanol in vapor phase

x-y diagram using van Laar model

 P, bar

T = 45⁰C

𝑥_ 𝐸𝐴^𝑣𝐿, Mole fraction of ethanol in vapor phase

P-x diagram using van Laar model

Comparing the results from a-d to the experimental data:

Mole Fraction of ethanol in vapor phase

T = 45⁰C

Mole Fraction of ethanol in liquid phase

Figure 1. x-y diagrams generated from various models including the experimental data
 Expe
rime
P,b a r

ntal
Data

,
Mole fraction of ethanol in liquid phase

Figure 2. x-y diagrams generated from various models including the experimental data

It was observed when all the data were compared that the UNIFAC and van Laar models were
the models that generated values closest to the experimental data. It was also be observed that the
experimental data had a large deviation from the data generated assuming ideal mixtures. This implies
that the mixture was not close to ideality and can be considered non-ideal which required further
corrections in order to make predictions on the data. For this case, the UNIFAC and van Laar models
made the closest predictions to the experimental data.
10.2-8

Given:

bar
‫ݔ‬௉ ‫ݕ‬௉ ௩௔௣
ܶ,⁰C ܲ௉ ௩௔௣
ܲ஺
0.021 0.108 49.15 1.560 0.803
0.061 0.307 45.76 1.397 0.703
0.134 0.475 39.58 1.146 0.551
0.210 0.550 36.67 1.036 0.493
0.292 0.614 34.35 0.960 0.453
0.405 0.664 32.85 0.913 0.425
0.503 0.678 32.35 0.903 0.421
0.611 0.711 31.97 0.887 0.413
0.728 0.739 31.93 0.880 0.41
0.869 0.810 32.27 0.896 0.419
0.953 0.906 33.89 0.954 0.445

Required:

a.) Are these data thermodynamically consistent?

Solution:
1
γ
∫ ln γ 1 d x1 =0
0 2

bar
ߛ஺
‫ݔ‬௉ ‫ݕ‬௉ ܶ,⁰C
௩௔௣
ܲ௉ ௩௔௣
ߛ௉ ߛ஺ ݈݊
ܲ஺ ߛ௉
0.021 0.108 49.15 1.560 0.803 0.3396 1.1494 -1.0666
0.061 0.307 45.76 1.397 0.703 0.3649 1.0635 -1.2330
0.134 0.475 39.58 1.146 0.551 0.3133 1.1145 -1.0337
0.210 0.550 36.67 1.036 0.493 0.2561 1.1704 -0.7830
0.292 0.614 34.35 0.960 0.453 0.2188 1.2191 -0.5988
0.405 0.664 32.85 0.913 0.425 1.8191 1.3460 -0.3012
0.503 0.678 32.35 0.903 0.421 1.5121 1.5589 0.3049
0.611 0.711 31.97 0.887 0.413 1.3290 1.8222 0.3157
0.728 0.739 31.93 0.880 0.41 1.1685 2.3708 0.7075
0.869 0.810 32.27 0.896 0.419 1.0538 3.5065 0.1022
0.953 0.906 33.89 0.954 0.445 1.0095 4.5528 1.5063

γ1
Plottingln vs mole fraction
γ2
 2.0000

1.5000

1.0000

0.5000

0.0000
0.000 0.200 0.400 0.600 0.800 1.000 1.200

-0.5000

-1.0000

-1.5000

The consistency relation can still be considered satisfied for the given VLE data of n-pentane-acetone
system at 1.013 bar. Although x = 0.021 could be a potential outlier, majority of the values are
consistent yet opposite in sign. Therefor to answer the question, it would be a yes.
10.1-9

Given:

Stream molar compositions  55% n-pentane ( x ¿¿ pent )¿, 25% n-hexane ( x ¿¿ hex)¿ and 20% n-heptane
( x ¿¿ hept ) ¿

Given vapor pressures: Required:

1
Pvap ¯
pent =2.755 ¿ a) Find Ptotal, x pent , x hex , x hept , y pent , y hex , y hept given that n= n
10 basis

9
Pvap ¯
hex =1.021 ¿ b) Find Ptotal, x pent , x hex, x hept , y pent , y hex , y hept given that ṅ= ṅ
10 basis

Pvap ¯
hept =0.390 ¿

Solution:

a)

 Selecting basis for the stream at 100 moles (n basis=100 moles ¿

1 1
n= nbasis= (100 moles )=10 moles
10 10

 Calculating molar fractions x pent , x hex, x hept at n = 10 moles

 However, molar fractions do not change with whatever flow rate given, then,

x pent =0.55 x hex =0.25 x hept =0.20

 Assuming that the liquid and vapor in the mixture behave ideally, we can use Raoult’s Law.

y i P total=x i Pvap
i

 Manipulating Raoult’s Law in terms of Ptotal given that ∑ yi =0 and solving for Ptotal

Ptotal =x pent Pvap vap vap

pent + x hex Phex + xhept Phept

Ptotal=0.55 ¿
Ptotal=1.8485 ¯¿

 Calculating vapor compositions at equilibrium y pent , y hex , y hept

x pent Pvap
pent
y pent = =0.55 ¿ ¿
P total

x hex Pvap
hex
y hex = =0.25¿ ¿
Ptotal
 x hept Pvap
hept
y hept = =0.20 ¿ ¿
Ptotal

b)

9 9
n= nbasis= (100 moles )=90 moles
10 10

 Calculating molar fractions x pent , x hex, x hept at n = 90 moles

 However, molar fractions do not change with whatever flow rate given, then,

x pent =0.55 x hex =0.25 x hept =0.20

 Assuming that the liquid and vapor in the mixture behave ideally, we can use Raoult’s Law.

y i P total=x i Pvap
i

 Manipulating Raoult’s Law in terms of Ptotal given that ∑ yi =0 and solving for Ptotal

Ptotal =x pent Pvap vap vap

pent + x hex Phex + xhept Phept

Ptotal=0.55 ¿
Ptotal=1.8485 ¯¿

 Calculating vapor compositions at equilibrium y pent , y hex , y hept

x Pvap
y pent = pent pent =0.55 ¿ ¿
P total

x hex Pvap
hex
y hex = =0.25¿ ¿
Ptotal

x hept Pvap
hept
y hept = =0.20 ¿ ¿
Ptotal
Conclusion: The equilibrium vapor and liquid compositions does not change with the number of moles in the
stream.
10.2-14

Given: Ethanol-Water Solution at 78.15 degrees Celsius

Molar Composition: Vapor Pressure: Activity coefficients at infinite

dilution:

x eth=0.20 Pvap ¯
eth =1.006 ¿ y ∞eth=1.6931

x H 2 O=0.80 Pvap ¯
H2 O =0.439 ¿ y ∞H 2 O =1.9523

Required:

Ptotal, y eth, y H 2 O

Solution:

 Using the van Laar model to calculate for Ptotal

Ptotal y i=x i γ i P vap
i

 Manipulating equation in terms of Ptotal given that ∑ yi =0

Ptotal=x eth γ eth Pvap vap

eth + x H 2O γ H 2 O P H 2 O missing values: γ eth and γ H 2 O
 Solving for γ eth and γ H 2 O
ln γ eth=x H 2O [( A ¿ ¿ 21 x eth + A12 x H 2O ) ( 1−2 x eth ) + A 21 x eth ] ¿

ln γ H 2 O =x 2eth [ A ¿ ¿21+2 ( A21− A 12) x H 2 O ]¿ missing values: A21∧ A 12

 Solving for A21∧ A 12 at infinite dilution
A12=ln y ∞eth=ln ( 1.6931 )=0.5266

A21=ln y ∞H 2 O=ln ( 1.9523 ) =0.6990

 Substituting values of A21∧ A 12 and solving for γ eth and γ H 2 O
ln γ eth=x H 2O [( A ¿ ¿ 21 x eth + A12 x H 2O ) ( 1−2 x eth ) + A 21 x eth ] ¿

¿ 0.80[((0.6990)(0.20)+(0.5266)(0.80)) ( 1−2(0.20) ) +(0.6990)(0.20)]

γ eth=e0.3811584

γ eth=1.4640
 ln γ H 2 O =x 2eth [ A ¿ ¿21+2 ( A21− A 12) x H 2 O ]¿

¿ 0.22 [0.6990+2 ( 0.6990−0.5266 ) 0.8 ]

γ H 2 O =e 0.0389936

γ H 2 O =1.0398

 Substituting values of γ eth and γ H 2 O and solving for Ptotal

Ptotal=x eth γ eth Pvap vap
eth + x H 2O γ H 2 O P H 2 O

¿ 0.20 ( 1.4640 ) ¿
Ptotal=0.6597 ¯¿

 Manipulating van Laar model in terms of y and substitute value of Ptotal to solve for y eth and y H 2 O

x eth γ eth Pvap

eth
y eth= =0.20 (1.4640) ¿ ¿
Ptotal

x H 2 O γ H 2 O P vap
H 2O
y eth= =0.80(1.0398) ¿ ¿
P total

Conclusion:

A 20 mol % ethanol (1) solution in water (2) at 78.15⁰C has a total pressure of 0.6597 bar and a vapor
composition of 44.65% ethanol and 55.35% water in equilibrium.
10.2-16

Given: benzene (1)–cyclohexane (2) mixture

Description of Mixture:

G ex= A x 1 x2 where: A=3750−8 T

Required:

a) Expressions for activity coefficients γ 1∧γ 2

b) Entropy and enthalpy changes on mixing ∆ H mix ∧∆ S mix at constant pressure

Given: n1 =1mole T =300 K

n2 =2moles

ntot =3 moles

c) Bubble point pressure Ptotal and vapor compositions y 1 and y 2

Given: Pvap ¯
1 =0.3203 ¿ T =320 K

Pvap ¯
2 =0.3218 ¿

Solution:

a)
ex
 The mixture is described by the equation G = A x 1 x2

ex GE
where: A=3750−8 T and G =
RT
 Using Equations 9.3-9 and 9.3-12 from Sandler (2017) for expressions for γ 1∧γ 2
∂ ntot (GE /RT ) ∂ ntot (GE /RT )
RT ln γ 1= RT ln γ 2= Eq. 1
∂ n1 ∂ n2
ex
 Substituting G = A x 1 x2 into Equation 1
 ∂ ntot ( A x1 x 2) ∂ ntot ( A x 1 x 2)
RT ln γ 1= RT ln γ 2= Eq. 2
∂n 1 ∂n 2
n1 n2
Where: x 1= x 2=
ntot ntot
 Substituting values of x 1∧x 2 Equation 2
n1 n2

RT ln γ 1=
∂ ntot A
( )( )
ntot ntot RT ln γ 2=∂ ntot A
n1
( )( )
ntot
n2
¿ ¿
ntot ∂ n2
∂ n1

n1 n 2 n1 n 2

RT ln γ 1=
∂A
( n1 +n2 ) RT ln γ 2=
∂A
(n1 +n2 )
∂ n1 ∂ n2

 Partial integration in terms of n1 for the left equation and n2 for the right equation
(n1 + n2)( n2)−n1 n2 (n1 + n2)(1)−n1 n 2
RT ln γ 1= A
( (n 1+ n2) 2
) RT ln γ 2= A
( (n1 +n2 )2 )
n 1 n2 +n22−n 1 n2 n 1 n2 +n12−n 1 n2
RT ln γ 1= A
( ( n1 +n2 )2 ) RT ln γ 2= A
( (n1 +n2 )2 )
n22 n12
RT ln γ 1= A
( (n1 +n2 )2 ) RT ln γ 2= A
( (n1 +n2 )2 ) Eq. 3

n1 n2
 Since x 1= and x 2= where ntot =n1 +n2, we can simplify Equation 3.
ntot ntot

RT ln γ 1= A x 22 RT ln γ 2= A x 12
 Substituting values for A and expressing in terms of γ 1∧γ 2
2 2
(3750−8T ) x2 (3750−8 T) x1
RT RT
γ 1=e γ 2=e
b)

 If we directly assume ideal mixing of the binary solution, then ∆ H mix =0 .

 Given in a binary system, entropy change of mixing is calculated as,
∆ S mix=−R ∑ x i ln x i
∆ S mix=−R ( x1 ln x 1+ x 2 ln x2 )
J
Where: R=8.314
mol K
 n1
x 1=
ntot
n2
x 2=
ntot
 Substituting values to solve for ∆ S mix

n1 n n n
∆ S mix=−R
( ( )
ntot
ln 1 + 2 ln 2
ntot ntot ntot ( ))
J 1 mol 1 mol 2 mol 2 mol
∆ S mix=−8.314
(
mol K 3 mol
ln + (
3 mol 3 mol
ln
3 mol ) ( ))
J
∆ S mix=5.291978795
mol K

J
∆ S mix ≈ 5.2920
mol K

c)

 Using the van Laar’s Law to calculate for Ptotal

Ptotal y i=x i γ i P vap
i

 Manipulating equation in terms of Ptotal given that ∑ yi =0

Ptotal =x 1 γ 1 Pvap vap

1 + x 2 γ 2 P2 Eq. 4
1 2
Where: x 1= x 2=
3 3

Pvap ¯
1 =0.3203 ¿ Pvap ¯
2 =0.3218 ¿

2 2
(3750−8T ) x2 (3750−8 T) x1
RT RT
γ 1=e γ 2=e

 Solving for γ 1∧γ 2

2 2
2 1
(3750−8(320)) (3750−8(320))
3 3
γ 1=e (8.314)(320) γ 2=e (8.314)(320)
γ 1=1.2199 γ 2=1.0510
  Substituting values and solving for Ptotal
1
Ptotal = (1.2199)¿
3

Ptotal=0.3557 ¯¿

 Solving for y 1∧ y 2

x 1 γ 1 P1vap 1
y 1= = (1.2199) ¿¿
Ptotal 3

x 2 γ 2 P vap
2 2
y 2= = (1.0510) ¿ ¿
Ptotal 3

Conclusion: The benzene (1)–cyclohexane (2) binary mixture at 320 K has a total pressure of 0.3557 bar and a
vapor composition of 36.62% ethanol and 63.38% water in equilibrium.
Annex:
10.2-35

Given:

T =90 ℃
P=1.8505 y 1=0.3767 x 1=0.4
vap Bi
log 10 Pi = A i−
T
For pressure in bar and T in K, where, A1=4.125 , B1 =1500 , A2 =5.000 , B2=1750

Data: The vapor pressure of the components are given by

vap Bi
log 10 Pi = A i−
T
For pressure in bar and T in K, where, A1=4.125 , B1 =1500 , A2 =5.000 , B2=1750
Required:

a. Determine the van Laar parameters for this mixture.

b. Determine whether the mixture has an azeotrope at 90°C, and if so, determine its composition and
whether it is a maximum-pressure or minimum-pressure azeotrope.
c. Obtain the P-x-y and x-y diagrams for this system at 90°C.
d. An equimolar mixture of species 1 and 2 at initially very low pressure is compressed at a constant
temperature of 90°C. At what pressure does the first drop of liquid form, and what is its composition?
At what pressure does the last bubble of vapor appear, and what is its composition?
Solution:

a. Determine the van Laar parameters for this mixture.

Computing for the Pvap
1 ∧P2
vap
@ T =90 ℃=363.15 K
Bi
Ai −
vap
P =10 T (1)
i

Where,
T =363.15 K A1=4.125B1=1500
A2=5.000
B2=175 0

Therefore, Pvap vap

1 =0.9874 ¿ and P2 =1.5172 ¿ .
¯ ¯
Recall:
x i γ i Pvap
i = yi P (2)

Using equation 2 to compute for γ 1∧γ 2:

yi P
γ i=
x i Pvap
i
Where,
Pvap
1 =0.9874 ¿
¯
Pvap
2 =1.5172 ¿
¯
P=1.8505 y 1=0.3767 x 1=0.4

γ 1=1.764 9
 γ 2=1.267 0

Recall:
2
x 2 ln γ 2
[
α = 1+
x 1 ln γ 1 ]
ln γ 1 (3)

2
x 1 ln γ 1
[
β= 1+
x 2 ln γ 2
ln γ 2
] (4)

Using equations 3 & 4 to compute for the van Laar parameters, α ∧β:

Where,

x 1=0. 4

γ 1=1.764 9

γ 2=1.267 0

Therefore, α =1.499 9 and β=1.600 2

b. Determine whether the mixture has an azeotrope at 90°C, and if so, determine its composition and
whether it is a maximum-pressure or minimum-pressure azeotrope.

xi
An azeotrope point of a mixture is the point at which x i= y i. Using equation 2 to find P at which =1 .
yi
xi
P= γ P vap
yi i i

P=γ i Pvap
i (5)

Where,

α
ln γ 1= 2
αx (6)
( 1+ 1
β x2 )
β
ln γ 2= 2
βx (7)
( 1+ 2
α x1 )
Pvap ¯ vap
1 =0.9874 ¿ P2 =1.5172 ¿α =1.4999β=1.6002
¯

Substituting the equations 5, 6, and 7, we get:

Pvap
1 ∙ exp ⁡¿

Therefore, x 1=0.367 5.
 Using equation 5 to compute for P at x 1=0.3675:

P=1.8513 ¯¿

The mixture has an azeotrope point at 90°C at a pressure of 1.8513 bar. From that, we can infer
that the azeotrope is a maximum-pressure given that it is greater than the boiling point pressure of both
components of the system. Additionally, at such conditions the mole fractions of the component 1 in
liquid and vapor phase are both equal to 0.3675.

c. Obtain the P-x-y and x-y diagrams for this system at 90°C.

Σ x i γ i Pivap=P (7)

Computing P and y 1 at different x 1 using equations 2 and 7:

0.0000 4.4812 1.0000 1.5172 0.0000

0.1000 3.4222 1.0143 1.7230 0.1961
0.2000 2.6764 1.0594 1.8143 0.2913
0.3000 2.1455 1.1405 1.8468 0.3441
0.4000 1.7649 1.2670 1.8504 0.3767
0.5000 1.4913 1.4544 1.8395 0.4002
0.6000 1.2958 1.7271 1.8158 0.4228
0.7000 1.1591 2.1246 1.7682 0.4531
0.8000 1.0688 2.7109 1.6668 0.5065
0.9000 1.0170 3.5930 1.4489 0.6238
1.0000 1.0000 4.9540 0.9874 1.0000
2
T= 90°C
1.8
1.6
1.4
1.2
P, bar

1
0.8
0.6
0.4
0.2
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of component 1

x y

Figure 1. P-xy diagram of the system at T= 90°C

 1.2
T = 90°C
1

0.8

0.6

y1
0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x1

y x=y line

Figure 2. x-y diagram of the specie 1 at T= 90°C

d. An equimolar mixture of species 1 and 2 at initially very low pressure is compressed at a constant
temperature of 90°C. At what pressure does the first drop of liquid form, and what is its composition? At
what pressure does the last bubble of vapor appear, and what is its composition?

Using the same method as that found in part c, we can obtain the bubble point pressure and dew point
pressure of an equimolar mixture. To get the bubble point pressure, we must obtain the equilibrium
pressure of the mixture at x 1=0.5. Meanwhile, to get the dew point pressure, we must obtain the
equilibrium pressure of the mixture at y 1=0.5 . In this case, we must combine equations 2 and 7 to get x 1
at y 1=0.5 . And finally get P using the obtained x 1.
Bubble point pressure:
P=1.8395 ¯¿
x 1=0.5

Dew point pressure:

Combining equations 2 and 7, we get:

x i γ i Pivap
vap
Σ xi γ i P = i
yi

Where,

α β
ln γ 1= 2
ln γ 2= 2
αx βx
( 1+ 1
β x2 ) 1+ 2 (
α x1 )
 α

α β
[( ) ]
x1 exp ⁡
αx
1+ 1
β x2
2
P1vap

[( ) ]
x 1 exp ⁡
αx
1+ 1
β x2
2
Pvap
1 +(1−x ¿¿ 1)exp

[( ) ]
βx
1+ 2
α x1
2
P2vap=
y1
¿

at y 1=0.5 , x 1=0.7909∧P=1.6795 ¯¿

Therefore, an equimolar mixture compressed at 90°C will show its first drop of liquid at 1.6795 bar and
its last bubble of vapor will appear until at 1.8395 bar.

10.2-39

Given: at T =323.15 K
Required:

a) activity coefficients γ 1 at all compositions

x 1=1
γ2
b) determining if the data is thermodynamically consistent, if −0.02 ≤ ∫ ln d x ≤ 0.02
x 1=0
γ1 1

c) Plot the excess Gibbs energy for this system as a function of composition

Solution:

a)

 Using the van Laar model to calculate for γ i

Ptotal y i
γ i=
x i Pivap

 Using Antoine Equation to calculate vapor pressure

  The equation is used to correlate vapor pressures accurately over the range from 1 to 200
kPa which fits the given data for pressure.
 Using Antoine Equation Parameters for water at 323.15 K

Source: https://webbook.nist.gov/cgi/cbook.cgi?
ID=C7732185&Mask=4&Type=ANTOINE&Plot=on#ANTOINE
 Choosing the constants on the row with temperatures at 304-333 K
 Calculating γ i

P (mm Hg) ‫ݔ‬ଵ ‫ݕ‬ଵ ‫ݔ‬ଶ ‫ݕ‬ଶ ߛଵ ߛଶ ௩௔௣

ܲଵ
௩௔௣
ܲଶ
120.49 0 0 1 1 0 35.69356 3.023128 3.375679
140.85 0.056 0.192 0.944 0.808 159.73992 35.71372 3.023128 3.375679
151.16 0.097 0.268 0.903 0.732 138.1476 36.29937 3.023128 3.375679
159.17 0.17 0.345 0.83 0.655 106.85007 37.21031 3.023128 3.375679
164.57 0.216 0.383 0.784 0.617 96.524843 38.36707 3.023128 3.375679
165.65 0.298 0.403 0.702 0.597 74.100926 41.73184 3.023128 3.375679
167.89 0.366 0.425 0.634 0.575 64.487581 45.10682 3.023128 3.375679
167.74 0.44 0.443 0.56 0.557 55.86388 49.42454 3.023128 3.375679
167.79 0.446 0.446 0.554 0.554 55.502109 49.70555 3.023128 3.375679
167.95 0.484 0.451 0.516 0.549 51.767191 52.93482 3.023128 3.375679
166.84 0.539 0.455 0.461 0.545 46.587159 58.42982 3.023128 3.375679
165.48 0.629 0.466 0.371 0.534 40.553113 70.55888 3.023128 3.375679
160.82 0.749 0.495 0.251 0.505 35.156599 95.85098 3.023128 3.375679
155.14 0.811 0.543 0.189 0.457 34.359448 111.1263 3.023128 3.375679
142.64 0.89 0.604 0.11 0.396 32.020763 152.1187 3.023128 3.375679
114.76 0.967 0.795 0.033 0.205 31.208623 211.188 3.023128 3.375679
92.51 1 1 0 0 30.600752 0 3.023128 3.375679
 x 1=1
γ2
b) To check if the data is thermodynamically consistent, if −0.02 ≤ ∫ ln d x ≤ 0.02
x 1=0
γ1 1

Using data γ 2=35.71371605 and γ 1=159.7399207 ,

x1=1
γ2
∫ ln d x =−1.498
x1=0
γ1 1

Using data γ 2=211.1880228 and γ 1=31.2086229 ,

x1=1
γ2
∫ ln d x =1.91
x1=0
γ1 1

Conclusion: The data is not thermodynamically consistent.

c)

 Calculating excess Gibb’s free energy

Gex
1 =RTln γ 1

G ex
2 =RTln γ 2

 Graphing calculated excess Gibb’s free energy vs liquid and vapour compositions of water and 1,4-
dioxane

error 9604.762
13630.94 9606.279
13240.77 9649.979
12550.58 9716.569
12277.54 9798.818
11567.26 10024.67
11193.93 10233.61
10808.25 10479.21
10790.79 10494.44
10603.63 10663.55
10320.37 10928.9
9947.695 11435.67
9564.038 12258.72
9502.418 12656.01
9313.028 13499.6
9244.007 14381.06
9191.161 error
 16000

14000

12000
Excess Gibb's free energy

10000

8000 x-water
x-1,4-dioxane
6000 y-water
y-1,4-dioxane
4000

2000

0
0 0.2 0.4 0.6 0.8 1 1.2

vapor and liquid compositions

Fig. 1. Vapor and liquid compositions vs excess Gibb’s free energy graph for a water-1,4-dioxane binary
system at 323.15 K.