BINARY VAPOR-LIQUID

EQUILIBRIUM
 Nonideal Liquid Solutions
 If a molecule contains a hydrogen atom attached
to a donor atom (O, N, F, and in certain cases C),
the active hydrogen atom can form a bond with
another molecule containing a donor atom. two water molecules
coming close together

 Table 2.7 shows qualitative estimates of deviations from Raoult’s law for binary
pairs when used in conjunction with Table 2.8.

 Positive deviations correspond to values of iL > 1. Nonideality results in a

variety of variations of (iL) with composition, as shown in Figure 2.15
(Seader & Henely) for several binary systems, where the Roman numerals
refer to classification groups in Tables 2.7 and 2.8.

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 BINARY VAPOR-LIQUID
EQUILIBRIUM

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EQUILIBRIUM

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 BINARY VAPOR-LIQUID
EQUILIBRIUM
 Figure 2.15a: Normal heptane (V) breaks ethanol (II) hydrogen
bonds, causing strong positive deviations.

n-heptane(v)-Ethanol
(II) system
(Semi-log paper)

Note: Ethanol molecules form H-bonds between each other and n-heptane
breaks these bond causing strong (+) deviation.
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 BINARY VAPOR-LIQUID
EQUILIBRIUM
 In Figure 2.15b, iL>1

Similar Figure 2.15a but less positive

deviations occur when acetone (III) is added
to formamide (I).

 In Figure 2.15c,

Hydrogen bonds are broken and formed with

chloroform (IV) and methanol (II) resulting in

an unusual positive deviation curve for

chloroform that passes through a maximum.

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 BINARY VAPOR-LIQUID
EQUILIBRIUM
In Figure 2.15d,

Chloroform (IV) provides active hydrogen

atoms that can form hydrogen bonds with
oxygen atoms of acetone (III), thus causing
negative deviations

 Non-ideal solution effects can be incorporate into K-value formation

into different ways.

1. Non-ideal liquid solution at near ambient

pressure

2. Non-ideal liquid solution at moderate

pressure and TC.

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 BINARY VAPOR-LIQUID
EQUILIBRIUM
1. Repulsion Component(1)
Molecules that are dissimilar enough from each x1

other will exert repulsive forces

e. g: polar H2O molecules – organic hydrocarbon +

molecules.
i > 1 Component(2)
x2 

When dissimilar molecules are mixed together

due to the repulsion effects, a greater partial
pressure is exerted, resulting in positive
+
deviation from ideality.

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 BINARY VAPOR-LIQUID
EQUILIBRIUM

 Fore the last two figures, as the mole fraction x1 increases its 1 →1, as

its mole fraction x1 decreases 1 increases till it reaches to 1 (activity

coefficient at infinite dilution)

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 Attraction
When dissimilar molecules are mixed together, due to the attraction
effects, a lower partial pressure is exerted, resulting in negative
deviation from ideality.

i < 1 are called negative deviation from ideality.

Component(1) Component(2)
x1 x2

- -

 1  2

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 BINARY VAPOR-LIQUID
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 Example:

calculate ij of methanol – water system for the following data 760 mmHg

Vapor phase Liquid phase

ym = 0.665 xm = 0.3
yw = 0.33 xw = 0.7 Vapor phase
ym = 0.665
Vapor Pressure Data at 78 oC (172.1°F) yw = 0.33

Methanol: Pmsat = 1.64 atm Liquid phase

xm = 0.3
Water: Pwsat = 0.43 atm xw = 0.7

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solution
For methanol
Py m  Pmsat x m  mL

1 0.665  1.64  0.3  mL

γ mL  1.35 atm 1.0 ( Repulsion)
(increase in partial pressure P)
For water
Pyw  Pwsat xw wL
1 0.335  0.43  0.7  mL
γ wL  1.11 atm  1.0 ( Repulsion)
(increase in partial pressure P)
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 BINARY VAPOR-LIQUID
EQUILIBRIUM
 How to calculate iL of Binary Pairs

Many empirical and semi-theoritical equations exists for estimating

activity coefficients of binary mixtures containing polar and/ or non-

polar species.

These equations contain binary interaction parameters, which are

back calculated from experimental data.

Table (2.9) show the different equations used to calculate iL.

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 THERMODYNAMICS OF
SEPARATION OPERATIONS
Table (2.10) shows the equations used to calculate excess volume,
excess enthalpy and excess energy.

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Example. (problem 2.23 (
Benzene can be used to break the ethanol/water azeotrope so as to
produce nearly pure ethanol. The Wilson constants for the
ethanol(1)/benzene(2) system at 45°C are A12 = 0.124 and A21 = 0.523.
Use these constants with the Wilson equation to predict the liquid-phase
activity coefficients for this system over the entire range of composition
and compare them, in a plot like Figure 2.16, with the following
experimental results [Austral. J. Chem., 7, 264 (1954)]:

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 THERMODYNAMICS OF
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Let: 1 = ethanol and 2 = benzene
The Wilson constants are A12 = 0.124 and A21 = 0.523 From Eqs. (4),
Table 2.9,

Using a spreadsheet and noting that  = exp(ln ), the following values
are obtained,

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 Activity coefficient at infinite dilution
Modern experimental techniques are available for accurately and rapidly
determining activity coefficient at infinite dilution (iL )
Appling equaion(3) in table (2.9) (van Laar (two-constant)) to conditions:

Xi = 0 and then xj = 0

Aij
lin  i  , xi  0
[1  ( xi Aij ) /( x j A ji )] 2

lin   Aij or   e
  Aij
i i

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 THERMODYNAMICS OF
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A ji
lin  j  , xj  0
[1  ( x j A ji ) /( xi Aij )] 2

lin  j  A ji or  j  e
A ji

Component(1) Component(2)
x1 x2 

+
+
Repulsive  > 1.0
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