Chemical Thermodynamics: Chapter 6. Equilibrium Applications

Chemical Thermodynamics
Chapter 6. Equilibrium Applications
Jorge Omar Gil Posada
Jorge Omar Gil Posada Chemical Thermodynamics 1 / 138

Abstract
This modules covers applications of phase equilibrium mixtures, and it

corresponds to chapter 13 of our textbook Kevin Dahm.

Aims and Objectives
Aims
This lecture is intended to:
explain why liquid-liquid equilibrium occurs
explain how calculate the compositions where LL, VLL, and SL
equilibrium occur
Objectives
At the end of this lecture you should be able to:
identify di↵erent types of equilibrium situations of interest to chemical

engineering
conduct calculations in LL, VLL, and SL equilibrium situations

Table of contents
1 Review
2 Henry’s Law Revisited
3 LLL Equilibrium
4 Solid Liquid Equilibrium (SLE)
5 LLL Equilibrium
6 References

Review
µ↵i = µi
fî ↵ = fî
method
fî V = fî L
yi ˆV ˆL
i P = xi i P
yi ˆV ˆL
i = xi i

Review
Van Deer Waals EOS
RT a RT am
P= ! P =
V b V2 V bm V2
27 R 2 Tc2 RTc
ai = ^ bi =
64 Pc 8 Pc
XX p X
a= xi xj (1 ij ) ai aj ^ b = b i xi
i j i
" #
P(V b) b 2a
Ln( ) = Ln +
RT V b RT V
" # Pm
P(V b) bi yk aik
Ln( î ) = Ln + 2 k=1
RT V b RT V

Review
Calculation of ˆV
i , three levels of rigour:
1 ˆV = ˆV ! fˆV = yi ˆV P: Most rigorous solution. i-j interactions
i i i i
2 ˆV = V ! fˆV = yi V P : Lewis fugacity rule. i-i interactions
i i i i
3 ˆV = 1 ! fˆV = yi P: Less rigorous solution (ideal gas). No
i i
interactions
method
fî V = fî L
yi ˆV
i P = xi i f i
o

Review
fî V = fî L
yi ˆV
i P = xi i f i
o
Henry 0 s Law Ref . State : yi ˆV

i P = xi
H
i Hi
" #
V i (P Pisat )
Lewis/Randall Ref . State : yi ˆV
i P = xi
L sat sat
i Pi i exp
RT
ˆV
yi iP = xi iL Pisat where i = h i
V i (P Pisat )
i
sat exp
i RT
At low to mid P values: i ⇡ ˆV

i

Review
GE
Redlich/Kister Expansion : = B + C (x1 x2 ) + D(x1 x2 )2 + ...
x1 x2 RT
x1 x2 RT I I
Inverse Expansion : = B + C (x1 x2 ) + D I (x1 x2 )2 + ...
GE
" #
E
@(nG /RT )
Ln( i ) =
@ni
T ,P,nj
Ideal solution (Redlich Kister with B = C = D = ... = 0)
GE
=0! i = 1.0
x1 x2 RT

Henry’s Law Revisited
Henrys Law Constants for Various Gases in Water at 25o C
Gas Hi [bar]
Ar 35987.9
Br2 74686.8
H2 70381.1
N2 87365.0
O2 44253.9
H2 S 54991.8
CO 58487.0
CO2 1651.9
CH4 41675.8
C2 H2 1342.2
C2 H4 11522.0
C2 H6 30525.9

Henrys Constants in [bar] of H2 , N2 , O2 , CO, and CO2 in Four Di↵erent

Liquids at 25o C
Substance H2 N2 O2 CO CO2
C6 H6 3657.4 2386.6 1554.9 1620.6 114.1
CS2 10865.9 6961.9 - 4907.3 469.0
CH3 OH 6425.0 4293.2 3179.4 3106.7 158.3
C3 H6 O 4373.4 2288.0 1478.9 1502.1 53.1
For multicomponents (solute i and solvent j):

X
Ln(Hi ) = xj Ln(Hi,j )
j

" # 1
@Ln(Hi ) V
= i
@P RT
T
" # 1
@Ln(Hi ) HV Hi
= i
@T RT 2
P
" # 1
@Ln(Hi ) Hi HV
i
=
@(1/T ) R Figure. (a) Henrys law constants for
P
N2 and O2 in H2 O vs. temperature.
(b) Natural logarithm of H vs. T 1 .
To solve for equilibrium composition of the solute using Henrys law, we
again set the fugacity of the vapor equal to the fugacity of the liquid:
fî V = fî L
yi ˆV
i P = xi
H
i Hi
Consider a binary system of dissolved gas (solute) a in liquid (solvent) b.

Assume that the gas mixture is well represented by the ideal gas law.
fâV = fâL ! ya ˆV
a P = xa
H
a Ha ! ya P = xa Ha
" #
V b (P Pbsat )
fˆbV = fˆbL ! yb ˆV
b P = xb
L sat sat
b Pb b exp ! yb P = xb Pbsat
RT

ya P = xa Ha
yb P = xb Pbsat
P = xa Ha + xb Pbsat
xa Ha xa Ha
ya = =
P xa Ha + xb Pbsat
xb Pbsat xb Pbsat
yb = =
P xa Ha + xb Pbsat

For high pressure and ideal liquid:
a P = xa
H P
a Ha ! ya ˆV P
a P = xa Ha
But we have seen:

"Z 1
#
P
ref Vi
HiP = HiP exp dP
P ref RT
"Z 1
#
P
P ref Va
a P = x H
a a exp dP
P ref RT
Where normally P ref = 1 bar

" #
V b (P Pbsat )
b P = xb
L sat sat
b Pb b exp
RT
Since the vapor is mostly solute, we can apply the Lewis fugacity rule to
get: ˆV V
b = b = b so,
" #
sat
V b (P Pb )
yb b P = xb Pbsat sat
b exp
RT
And
"Z 1
#
P
ref Va
ya ˆV P
a P = xa Ha exp dP
P ref RT

For high pressure and non ideal liquid:
a P = xa
H P
a Ha
But we have seen:

"Z 1
#
P
ref Vi
HiP = HiP exp dP
P ref RT
"Z 1
#
P
H P ref Vi
a P = xa a Hi exp dP
P ref RT

" #
V b (P Pbsat )
b P = xb
L sat sat
b Pb b exp
RT
Since the vapor is mostly solute, we can apply the Lewis fugacity rule to
get: ˆV V
b = b = b so,
" #
sat
V b (P Pb )
yb b P = xb bL Pbsat sat
b exp
RT
And
"Z 1
#
P
H P ref Vi
ya ˆV
a P = xa a Hi exp dP
P ref RT

Example 1
Find compositions in the liquid and vapor

phases at 25o C and 1 bar. Start with H2 O:
fˆwV = fˆwL
" #
V w (P Pwsat )
yw ˆV
w P = xw
L sat sat
w Pw w exp
RT
" #
L sat sat exp V w (P Pwsat )
xw w Pw w RT
yw =
ˆV
wP

Example 1
Considerations:
1 Pwsat (25o C ) = 3.166 kPa
2 low P, ideal gas phase ( ˆw = 1.0)
3 xw ⇡ 1.0
4 ideal solution ( L = 1.0)
w
xw Pwsat 1.0 ⇥ 3.166 kPa

yw = =
P 101.3 kPa
yw = 0.0312

Example 1
Working with air:
fâV = fâL
" #
V a (P Pasat )
ya ˆV
a P = xa
L sat sat
a Pa a exp
RT
xa Pasat
ya P = xa Pasat
! ya =
P
But Pasat at 25o C can not be found.
Tcair << 25o C , air is no longer a vapor but
a gas. We cannot use Raoult’s law!

Example 1
From Raoults law:
yw = 0.0312 ! ya = 1 0.0312 = 0.9688
Reference state: Henry’s law:
fâV = fâL
"Z 1
#
P
H P ref Va
ya ˆV
a P = xa a Ha/w exp dP
P ref RT

Example 1
"Z 1
#
P
H P ref Va
ya ˆV
a P = xa a Ha/w exp dP
P ref RT
Considerations:
1 Ha/w (25o C ) = 72950 kPa
2 ideal solution H = 1.0
a
3 ideal gas phase ˆV
a = 1.0
ya P
ya P = xa Ha/w ! xa =
xa
0.9688 ⇥ 101.32 kPa 5

xa = = 1.35 ⇥ 10
72950 kPa
Example 2
Example. Calculate the solubility of O2 from air in the atmosphere in

equilibrium with liquid H2 O at 25o C .

Example 2
Example. Calculate the solubility of O2 from air in the atmosphere in

equilibrium with liquid H2 O at 25o C .
fôV = fôL
"Z 1
#
1 bar
Vo
yo ˆV
o P = xo
H 1 bar
o Ho/w exp dP
P ref RT
yo ˆV P
xo = H oP
o Ho/w

Example 2
Considerations:
1 Low pressure: ô = 1.0
2 Liquid diluted in O2 : H = 1.0
o
3 Molar fraction of O2 in air: yo = 0.21
4 Oxygen in water: Ho/w = 44253.9 bar
yo ˆV P 0.21 ⇥ 1.0 ⇥ 1.0 bar

xo = H oP = = 4.75 ⇥ 10 6
o H o/w
1.0 ⇥ 44253.9 bar

Homework: Determine the solubility of nitrogen in water at 300 bar and

25o C . Use:
1 5 m3
V N2 = 3.3 ⇥ 10
mol
oC
HN1.0
2
bar , 25
/H 2O
= 87365 bar

LL Equilibrium

LL Equilibrium

LL Equilibrium

LL Equilibrium

LL Equilibrium

LL Equilibrium

LL Equilibrium

LL Equilibrium

LL Equilibrium

LL Equilibrium
1 Any system at constant T and P, is at equilibrium if it exists in the

state that minimizes its Gibbs free energy.
2 Mixtures inside the dome are not stable and splits into two liquid
phases.
3 To find the composition of phases at equilibrium, we draw a
horizontal tie line as with VLE.
4 A miscible liquid mixture forms a single phase.
5 Miscibility Gap: region inside the dome (immiscible)

LL Equilibrium
Example 1: You mix 80 g methanol plus 20 g cyclohexane at 295 K. Is
the resulting system stable? If not what is the composition (%w) and
amount (grams) of the resulting phases?

LL Equilibrium

80 g
nm g
32.04 mol
xm = = 80 g 20 g
= 0.913
nm + nc g + g
32.04 mol 84.16 mol
20 g
nc g
84.16 mol
xc = = 80 g 20 g
= 0.087
nm + nc g + g
32.04 mol 84.16 mol
Or similarly:
xc = 1 xm = 1 0.913 = 0.087

LL Equilibrium

LL Equilibrium

LL Equilibrium

80 g
nm g
32.04 mol
xm = = 80 g 20 g
= 0.913
nm + nc g + g
32.04 mol 84.16 mol
Stable, miscible phase.

100 g of single phase at 91.3%mol methanol (80%w methanol)

LL Equilibrium

60 g
nm g
32.04 mol
xm = = 60 g 40 g
= 0.796
nm + nc g + g
32.04 mol 84.16 mol

LL Equilibrium

LL Equilibrium

LL Equilibrium

60 g
nm g
32.04 mol
xm = = 60 g 40 g
= 0.796
nm + nc g + g
32.04 mol 84.16 mol
↵ = 0.1, x = 0.84)
Unstable, miscibility gap, two phases (xm m

LL Equilibrium

60 g
nm g
32.04 mol
xm = = 60 g 40 g
= 0.796
nm + nc g + g
32.04 mol 84.16 mol
↵ = 0.1, x = 0.84)
Unstable, miscibility gap, two phases (xm m
DOF analysis: 2 equations (material balance), two unknowns (N ↵ , N )

Total mole balance: N = N ↵ + N
↵ ⇥ N↵ + x ⇥ N
Mole balance of methanol: xm ⇥ N = xm m
Therefore: N ↵ = 0.135 mol and N = 2.213 mol

LL Equilibrium
Wi↵ = xi↵ ⇥ N ↵ ⇥ Mi
g
Methanol: Wm↵ = 0.1 ⇥ 0.135mol ⇥ 32.04 mol = 0.433g CH3 OH
g
Cyclohexane: Wc↵ = 0.9 ⇥ 0.135mol ⇥ 84.16 mol = 10.225g C6 H12
↵ = Wm↵ ↵
Commpositions in ↵ phase: wm Wm↵ +Wc↵ = 0.04 ! wc = 0.96
Total mass of ↵ phase: W ↵ = Wm↵ + Wc↵ = 10.68 g
g
Methanol: Wm = 0.84 ⇥ 2.213mol ⇥ 32.04 mol = 59.56g CH3 OH
g
Cyclohexane: Wc = 0.16 ⇥ 2.213mol ⇥ 84.16 mol = 29.79g C6 H12
Wm
Commpositions in phase: wm = = 0.667 ! wc = 0.333
Wm +Wc
Total mass of phase: W = Wm + Wc = 89.35 g

LL Equilibrium
1 Liquid/Liquid Equilibrium (LLE) occurs because the mixture can

lower its overall Gibbs free energy by separating into two liquid phases
rather than one.
2 LLE is a weak function of pressure.
3 For the methanol/cyclohexane system
1 at 1 atm UCST = 318 K
2 at 1000 atm UCST = 340 K
4 Note 1000 atm is well outside of any typical operating system pressure
5 Considering UCST as independent of P is normally a reasonable
approximation for most practical purposes

LL Equilibrium
We have said that LLE occurs because the mixture can lower its overall
Gibbs free energy by separating into two liquid phases rather than one.
Now remember that
G =H TS ^ H = U + PV
G = U + PV TS
For the methanol plus cyclohexane system at 310 K and 1 atm, the
following empirical data was found:
G (J/mol) U(J/mol) T S(J/mol) PV (J/mol)

-103 -2408 -2301 4
So the largest impact on the molar Gibbs free energy (G ) occurs through
the molar internal energy (U) and the entropic term ( T S).
LL Equilibrium
G= H T S = ( U + P V) T S= U +P V T S

LL Equilibrium

LL Equilibrium

LL Equilibrium
G = nG  n1 G 1 + n2 G 2
n1 G 1 + n2 G 2
G
n
G  x 1 G 1 + x2 G 2
G (x1 G 1 + x2 G 2 )  0
Remember : G =G (x1 G 1 + x2 G 2 ) ! G 0

LL Equilibrium
GE = G G ID = G [x1 G 1 + x2 G 2 + RTx1 Ln(x1 ) + RTx2 Ln(x2 )]
GE = G (x1 G 1 + x2 G 2 ) RTx1 Ln(x1 ) RTx2 Ln(x2 )
G E + RTx1 Ln(x1 ) + RTx2 Ln(x2 ) = G (x1 G 1 + x2 G 2 )
But : G =G (x1 G 1 + x2 G 2 )
G E + RTx1 Ln(x1 ) + RTx2 Ln(x2 ) = G
G = G E + RTx1 Ln(x1 ) + RTx2 Ln(x2 )

LL Equilibrium
G = G E + RTx1 Ln(x1 ) + RTx2 Ln(x2 )
GE
Margules : = A21 x1 + A12 x2
x1 x2 RT
G = x1 x2 RT (A21 x1 + A12 x2 ) + RTx1 Ln(x1 ) + RTx2 Ln(x2 )
G
= x1 x2 (A21 x1 + A12 x2 ) + x1 Ln(x1 ) + x2 Ln(x2 )
RT

LL Equilibrium

LL Equilibrium
!
@2 G
> 0 Then mixture is stable
@x12
T ,P
LL Equilibrium
Stability Criterion for Liquid Mixtures.
!
2
@ G
@x12
T ,P
Note that:
X X
E
G =G xi G i RT xi Ln(xi )
i i
X X
E E
G = G RT xi Ln(xi ) ! G = G + RT xi Ln(xi )
i i
G = G E + RT [x1 Ln(x1 ) + x2 Ln(x2 )]
G GE
= + [x1 Ln(x1 ) + x2 Ln(x2 )]
RT RT
LL Equilibrium
@ ⇣ G⌘ @ ⇣GE ⌘ @
= + [x1 Ln(x1 ) + x2 Ln(x2 )]
@x1 RT @x1 RT @x1
h i! h i! " #
G GE
@ RT @ RT x1 (1 x1 )
= + +Ln(x1 )+ Ln(1 x1 )
@x1 @x1 x1 1 x1
T ,P T ,P
h i! h i!
G GE
@ RT @ RT
= + [Ln(x1 ) Ln(1 x1 )]
@x1 @x1
T ,P T ,P
h i! h i!
G GE
@2RT
2
@ RT @
= + [Ln(x1 ) Ln(1 x1 )]
@x12 @x12 @x1
T ,P T ,P

LL Equilibrium
h i! h i!
GE
@ 2 RTG @ 2 RT 1
= +
@x12 @x12 x1 x 2
T ,P T ,P
!
@2 G
@x12
T ,P
h i!
GE
@ 2 RT 1
+ > 0 Then mixture is stable
@x12 x 1 x2
T ,P
!
@[Ln( 1 )] 1
Similarly : > mixture is stable
@x1 x1
T ,P

LL Equilibrium
Binary Mixture Stability

h i!
GE
@ 2 RT 1
+ >0
@x12 x1 x 2
T ,P
!
@[Ln( 1 )] 1
>
@x1 x1
T ,P

LL Equilibrium
Example: Can the following excess molar Gibbs free energy models
predict a liquid/liquid phase split?
1 Ideal Solution
2 Porter’s Equation

LL Equilibrium
Solution part 1. Intuition ! No!!
GE
=0
RT
h E i!
G
@2RT 1
+ >0
@x12 x1 x2
T ,P
1
0+ >0
x1 x 2
For a mixture to occur x1 6= 0 and x2 6= 0, so the term x11x2 is always
greater than zero. Therefore, stable liquid phase (no miscibility gap)

LL Equilibrium
Solution part 2.
GE
= Ax1 x2 = Ax1 (1 x1 ) = A(x1 x12 )
RT
h E i!
2 G
@ RT 1
+ >0
@x12 x1 x2
T ,P
@2 h i 1
A(x1 x12 ) + >0
@x12 T ,P x 1 x2
1
2A + >0
x1 x2
1
A< Then the mixture is stable
2x1 x2

Modelling LL Equilibrium
fî ↵ = fî
xi↵ ↵ ↵
i fi = xi i fi
Since fi is the pure component fugacity evaluated at T

and P (in the liquid phase), then fi ↵ = fi = fi o , so:
↵ o o
xi↵ i fi = xi i fi ! xi↵ ↵
i = xi i
For a binary system:
x1↵ ↵
1 = x1 1
x2↵ ↵
2 = x2 2 ! (1 x1↵ ) ↵
2 = (1 x1 ) 2

Example 1. Consider the 1-butanol (1) plus water (2) system. The
parameters for this liquid mixture at 60o C using the two-parameter
Margules Model are A12 = 2.7576 and A21 = 1.3064. Determine whether
this system will split into two phases and if so, what will be the
composition of each phase.
x1
x1↵ ↵
1 = x1 1 ! x1↵ = ↵
1
1
x2↵ ↵
2 = x2 2 ! (1 x1↵ ) ↵
2 = (1 x1 ) 2
Ln( 1 ) = x22 (A12 + 2[A21 A12 ]x1 )
Ln( 2 ) = x12 (A21 + 2[A12 A21 ]x2 )

x1↵ ↵
1 = x1 1
(1 x1↵ ) ↵
2 = (1 x1 ) 2
Ln( ↵
1) = (x2↵ )2 (A12 + 2[A21 A12 ]x1↵ )
Ln( 1) = (x2 )2 (A12 + 2[A21 A12 ]x1 )
Ln( ↵
2) = (x1↵ )2 (A21 + 2[A12 A21 ]x2↵ )
Ln( 2) = (x1 )2 (A21 + 2[A12 A21 ]x2 )

Since the activity coefficient expressions are in terms of the given

parameters and the composition of each phase, we have two unknowns
(x1↵ and x1 ) in the two equations.
Solving simultaneously, it can be found that:
x1↵ = 0.093
And
x1 = 0.645
As they are comprised from between 0 and 1, then miscibility gap exists.

Example 2. A limiting case of a binary LLE is that for which the

↵-phase is very dilute in species 1 and the -phase is very diluted in
species 2. In this event, to a good approximation:
↵-phase (dilute in 1): x1↵ ⇡ 0, ↵ = 1 ↵ ⇡ 1.0

1 1 , 2
-phase (dilute in 2): x2 ⇡ 0, = 1 ⇡ 1.0

2 2 , 1
1
x1↵ ↵
1 = x1 1 ! x1↵ 1 = x1 ⇥ 1.0 (1)
1
(1 x1↵ ) ↵
2 = (1 x1 ) 2 ! (1 x1↵ ) ⇥ 1.0 = (1 x1 ) 2 (2)

1 1
From (1) (2) : (1 x1↵ ) = (1 x1↵ 1 ) 2
1 1
x1↵ = 2
1 1
1 1 2
(1 1 1 x1
2 ) 1
From (1) : x1↵ 11 = x1 ! x1 = 1 1 and 1
1 =
1 1 2 x1↵
1 1 1 x1↵
From (2) : (1 x1↵ ) = (1 x1 ) 2 ! 2 =
1 x1

Example 3. The water (1) plus di-ethyl ether (2) system is almost
totally immiscible across all composition regions. At 307.3 K two liquid
phases exist. The water rich phase has a composition of x1↵ = 0.9889
while the ether rich phase has a composition of x1 = 0.0495. Estimate the
infinite dilution activity coefficients for this mixture at this temperature.
Aqueous (↵) phase: dilute in ether (2): x1↵ = 0.9889, ↵ = 1.0, ↵ = 1

1 2 2
Ether ( ) phase: dilute in water (1): x1 = 0.0495, = 1

1 1 , 2 = 1.0
1
x1↵ ↵
1 = x1 1 ! 0.9889 ⇥ 1.0 = 0.0495 ⇥ 1
1 1
(1 x1↵ ) ↵
2 = (1 x1 ) 2 ! 0.0111 ⇥ 2 = (1 0.0495) ⇥ 1.0
1 1
Solving 1 = 19.98 ^ 2 = 85.63

VLLE Equilibrium

VLLE Equilibrium

VLLE Equilibrium

VLLE Equilibrium
fî V = fî ↵ = fî
RT Ln( i ) = Axj2
fˆ1V = fˆ1↵ ! y1 ˆV ↵
1 P = x1
↵ o
1 f1
h A (x ↵ )2 i
Low P : y1 P = x1↵ exp 2
P1sat
RT
h A (x ↵ )2 i
Low P : y2 P = x2↵ exp 1
P2sat
RT

Modelling VLLE Equilibrium
We have 3 phases (two liquid phases plus one vapor phase):
fî L1 = fî L2 = fî V

Therefore, for a binary mixture:
fˆ1L1 = fˆ1L2 = fˆ1V ! x1L1 L1 L1

1 f1 = x1L2 L2 L2
1 f1 = y1 ˆV
1 P
fˆ2L1 = fˆ2L2 = fˆ2V ! x2L1 L1 L1

2 f2 = x2L2 L2 L2
2 f2 = y2 ˆV
2 P
Notice we have six equations but only four are independent

The two equations for the phase equilibrium between the two liquid phases
are:
x1L1 L1 L1
1 f1 = x1L2 L2 L2
1 f1
x2L1 L1 L1
2 f2 = x2L2 L2 L2
2 f2
The pure component fugacities can be cancelled out since the pure
component fugacities are for the same component, so:
x1L1 L1
1 = x1L2 L2
1
x2L1 L1
2 = x2L2 L2
2 ! (1 x1L1 ) L1
2 = (1 x1L2 ) L2
2

For the VLE, we have a choice of equations. One approach is equating the
concentrated liquid phase with the vapor phase, per component. Assuming
L1 is rich in component 1 and L2 rich in component 2:
x1L1 L1 L1
1 f1 = y1 ˆV
1 P
x2L2 L2 L2
2 f2 = y2 ˆV
2 P ! (1 x1L2 ) L2 L2
2 f2 = (1 y1 ) ˆV
2 P
Notice the previous expressions can be rewritten as:

h V (P P sat ) i
x1L1 1L1 P1sat sat
1 exp 1 1
= y1 ˆV
1 P
RT
h V (P P sat ) i
(1 x1L2 ) 2L2 P2sat sat
2 exp 2 2
= (1 y1 ) ˆV
2 P
RT

At low to moderate pressures:
x1L1 L1 sat
1 P1 = y1 P
(1 x1L2 ) L2 sat
2 P2 = (1 y1 )P
Which in conjunction with:
x1L1 L1
1 = x1L2 L2
1
(1 x1L1 ) L1
2 = (1 x1L2 ) L2
2

Note we have 4 equations and 5 unknowns (x1L1 , x1L2 , y1 , T , and P). Note
i = i (xi ) and therefore, are not included.
We have 3 phases (⇡ = 3), for our binary mixture (C = 2), thus according
to the Gibbs phase rule:
f =C ⇡+2=2 3+2=1
We need to specify one degree of freedom. A typical approach might be to
specify the temperature where the VLEE occurs.

VLLE at High P
" #
V 1 (P P1sat )
x1L1 L1 sat sat
1 P1 1 exp = y1 ˆV
1 P
RT
" #
V 2 (P P2sat )
(1 x1L2 ) L2 sat sat
2 P2 2 exp = (1 y1 ) ˆV
2 P
RT
x1L1 L1
1 = x1L2 L2
1
(1 x1L1 ) L1
2 = (1 x1L2 ) L2
2

VLLE at Low to Moderate P

x1L1 L1 sat
1 P1 = y1 P
(1 x1L2 ) L2 sat
2 P2 = (1 y1 )P
x1L1 L1
1 = x1L2 L2
1
(1 x1L1 ) L1
2 = (1 x1L2 ) L2
2

Example Use Porter’s equation (take A = 2.475 for this system) to

estimate the pressure and composition for the VLLE at 308 K for the
methanol (1) and Cyclohexane (2) system. Hint: consider low to mid P
model.

Example Use Porter’s equation (take A = 2.475 for this system) to
estimate the pressure and composition for the VLLE at 308 K for the
methanol (1) and Cyclohexane (2) system. Hint: consider low to mid P
model.
Ln( i ) = Axj2 ! i = exp Axj2
⇥ ⇤
1 = exp A(1 x1 ) 2 ) ^ 2 = exp Ax12
B
Log10 Pisat [mmHg ] = A
T [o C ] + C
Substance A B C Pisat (at 308 K ) [bar ]

Methanol (1) 6.84130 1201.53 222.65 0.27
Cyclohexane (2) 7.89750 1474.08 229.13 0.1996

Setting up the four equations for the VLLE already shown:
x1L1 L1 sat
1 P1 = y1 P
(1 x1L2 ) L2 sat
2 P2 = (1 y1 )P
x1L1 L1
1 = x1L2 L2
1
(1 x1L1 ) L1
2 = (1 x1L2 ) L2
2

⇥ ⇤ ⇥ ⇤
x1L1 exp 2.475(1 x1L1 )2 = x1L2 exp 2.475(1 x1L2 )2
⇥ ⇤ ⇥ ⇤
(1 x1L1 ) exp 2.475(x1L1 )2 = (1 x1L2 ) exp 2.475(x1L2 )2
⇥ ⇤
x1L1 exp 2.475(1 x1L1 )2 ⇥ 0.27 bar = y1 P
⇥ ⇤
(1 x1L2 ) exp 2.475(x1L2 )2 ⇥ 0.1996 bar = (1 y1 )P
Solving: x1L1 = 0.166, x1L2 = 0.834, y1 = 0.579, P = 0.42 bar.

Immiscible Systems.
L1 rich in component 1 ! x1L1 ⇡ 1.0 (x2L1 ⇡ 0)
L2 rich in component 2 ! x2L2 ⇡ 1.0 (x1L2 ⇡ 0)

The simplification is that we do not need to model LLE since we assume
that each liquid phase only contains one of the components, second the
VLE which is (considering ideal gas phase):
x1L1 L1 sat
1 P1 = y1 ˆV sat
1 P ! 1 ⇥ 1 ⇥ P 1 = y1 P
(1 x1L2 ) L2 sat
2 P2 = (1 y1 ) ˆV
2 P ! (1 0) ⇥ 1 ⇥ P2sat = (1 y1 )P

P1sat
P1sat = y 1 P ! y1 =
P
P2sat = (1 y1 )P
P1sat + P2sat = P
Thus the system pressure for the VLLE for immiscible liquid systems is just
the sum of the of the vapor pressure of the pure components, while the
vapor phase mole fraction, is just the vapor pressure of one of the
components divided by the total pressure of the system.

Solid Liquid Equilibrium (SLE)

fî S = fî L
S S L L
zi i fi = xi i fi
S
S fi L
zi i L = xi i
fi
S L
zi i i = xi i
fi S
Where : i = L
fi

fi S fi S (T , P)
i = L = L
fi fi (T , P)
⇠ ⇠
fi S fi S (T , P) ⇠ (T⇠
fi S⇠ m , P) fi L (Tm , P)
i = L = L ⇥ S ⇥ L
⇠ ⇠ ⇠
fi fi (T , P) fi (Tm , P) f⇠i ⇠(T m , P)
Note that : fi S (Tm , P) = fi L (Tm , P)
fi S fi S (T , P) fi L (Tm , P)
i = L = L ⇥
fi fi (T , P) fi S (Tm , P)
i = L = S ⇥ L
fi fi (Tm , P) fi (T , P)

The quantity i (ratio of pure component fugacities) can be determined
by evaluating the change in fugacity for the pure component i from its
melting point for the system temperature (at the system pressure) for both
liquid and solid phases separately. We have seen that:
⇣ nG R ⌘ nV R nH R X m
d = dP 2
dT + Ln( î )dni
RT RT RT
i
@ ⇣ nG R ⌘ nH R @ ⇣GR ⌘ HR
= ! =
@T RT P,n RT 2 @T RT P,n RT 2
⇣f ⌘
GR GR
i i
Ln( i ) = Ln = ! Ln(fi ) = i + Ln(P)
P RT RT
" # " #
R
@Ln(fi ) @(G i /RT ) HR
i
= =
@T @T RT 2
P P

R
G
Ln( î ) = i
RT
⇣f ⌘ GR
i
Ln( i ) = Ln = i
P RT
GR
Ln(fi ) Ln(P) = i
RT
GR
Ln(fi ) = i + Ln(P)
RT
" # " # " #
R
@Ln(fi ) @(G i /RT ) @Ln(P)
= +
@T @T @T
P P P

" # " #
@Ln(fi ) @(G R
i /RT )
= +0
@T @T
P P
" #
R
@(G i /RT ) HRi
But : =
@T RT 2
P
" #
@Ln(fi ) HR
i
=
@T RT 2
P
HRi
d Ln(fi ) = dT
RT 2

Z Z
Ln(fi ) [T ] T
HRi
d Ln(fi ) = dT
Ln(fi ) [Tm ] Tm RT 2
From which:
" # Z
fi (T , P) T
HRi
Ln(fi ) [T , P] Ln(fi ) [Tm , P] = Ln = dT
fi (Tm , P) Tm RT 2
" Z #
fi (T , P) T
HRi
= exp dT
fi (Tm , P) Tm RT 2
But:
i = L = S ⇥ L
fi fi (Tm , P) fi (T , P)
" Z #
fi S (T , P) T
H R,
i
S
= exp dT
fi S (Tm , P) Tm RT 2
" Z # "Z #
fi L (T , P) T
H R,
i
L
fi L (Tm , P) T
H R,
i
L
= exp dT ! = exp dT
fi L (Tm , P) Tm RT 2 fi L (T , P) Tm RT 2
" Z # "Z #
T
H R,
i
S T
H R,
i
L
i = exp dT ⇥ exp dT
Tm RT 2 Tm RT 2
"Z #
T
H R,
i
L
H R,
i
S
i = exp 2
dT
Tm RT
Where H R,
i
S
= H Si H IG R, L
i and H i = H Li H IG
i

Noting that H fus

i (Tm ) = H i
L
H Si = H R,i
L
H R,
i
S
"Z #
T fus
H i (Tm )
i = exp 2
dT
Tm RT
" Z T #
dT
i = exp H fus
i (Tm ) 2
Tm RT
" #
S fus
fi H i (Tm ) T Tm
i = L = exp ⇥
fi RTm T

Modelling Solid Liquid Equilibrium

fî S = fî L
S S L L
zi i fi = xi i fi
S
S fi L
zi i L = xi i
fi
fi S
zi iS i = xi iL Where : i = L
fi
" #
fi S H fus
i (Tm ) T Tm
i = = exp ⇥
fi L RTm T

Example. Model SLE phase behaviour for the Cu(1) plus Ni(2) system
by assuming an ideal solution for both the liquid and solid phases.
fî S = fî L
S L
zi i i = xi i
S L
z1 1 1 = x1 1
S L
z2 2 2 = x2 2

S L
z1 1 1 = x1 1
S L
(1 z1 ) 2 2 = (1 x1 ) 2
Ideal solution assumptions for both phases mean that:
S L S L
1 = 1 =1 ^ 2 = 2 =1
z1 ⇥ 1.0 ⇥ 1 = x1 ⇥ 1.0 ! x1 = z1 1 (1)
(1 z1 ) ⇥ 1.0 ⇥ 2 = (1 x1 ) ⇥ 1.0 ! 2 z1 2 =1 x1 (2)

(1) and (2) : 2 z1 2 =1 z1 1
2 1 = z1 ( 2 1)
2 1
z1 =
2 1
Gibbs phase rule, there are two components and two phases, so we must
specify two independent variables, usually T and P. Here P doesn’t appear
explicitly (but it is included in the activity coefficients).
1( 2 1)
x1 = z 1 1 =
2 1

1( 2 1) 2 1
x1 = ^ z1 =
2 1 2 1
In order to calculate ’s we require H fus and melting point temperature.
J
Ni ! TmNi = 1728 K , H fus
Ni = 17500
mol
J
Cu ! TmCu = 1356 K , H fus
Cu = 13000
mol
" #
fi S H fus
i (Tm ) T Tm
i = = exp ⇥
fi L RTm T


LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium
Example: It is desired to remove some of the acetone from a mixture that

contains 60 wt % acetone and 40 wt % water by extraction with methyl
isobutyl ketone (MIK). If 3 kg of MIK are contacted with 1 kg of the
acetone/water mixture, what will be the amounts and compositions of the
equilibrium phases?

LLL Equilibrium
Example: It is desired to remove some of the acetone from a mixture that

contains 60 wt % acetone and 40 wt % water by extraction with methyl
isobutyl ketone (MIK). If 3 kg of MIK are contacted with 1 kg of the
acetone/water mixture, what will be the amounts and compositions of the
equilibrium phases?
S(Acetone, MIK, Water): S1 (60, 0, 40), S2 (0, 100, 0)
S3 = 1.0 kg S1 (60% Acetone+40% Water) + 3kg S2 (100% MIK)
S3 = 3.0 kg MIK + 0.6 kg Acetone + 0.4 kg Water
⇣ ⌘
0.6 kg Acetone 3 kg MIK 0.4 kg H2 O
S3 (0.6+3+0.4)kg , 4.0 kg , 4.0 kg
S3 (15, 75, 10)

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium

LLL Equilibrium
Mass balance: E1 + E2 = 4.0 kg ! E2 = 4.0 E1

Water balance: 0.045 ⇥ E2 + 0.84 ⇥ E1 = 0.4
Solving simultaneously: E1 = 0.28 ^ E2 = 3.72

LLL Equilibrium
E1 = 0.28 ^ E2 = 3.72

Question 1
Type Calculate Given
BUBLE P yi , P xi , T
DEW P xi , P yi , T
BUBLE T yi , T xi , P
DEW T xi , T yi , P
" #
V i (P Pisat )
fî V = fî L ! yi ˆV sat
i P = xi i P i
sat
i exp
RT
Or equivalently:
ˆV
yi iP = xi i Pisat where i = h i
V i (P Pisat )
i
sat exp
i RT

Question 2
fî V = fî L
" #
V i (P Pisat )
yi ˆV
i P = xi
L sat sat
i i Pi exp
RT
L yi ˆV
i"P
i = #
V i (P Pisat )
xi Pisat sat
i exp RT
yi P ˆV
L " i #
i = ⇥
xi Pisat V i (P Pisat )
sat exp
i RT
yi P ˆV
L i
i = sat ⇥ sat
xi P i i
References
Dahm, Kevin D., and Donald P. Visco. Fundamentals of Chemical

Engineering Thermodynamics. Nelson Education. 2014.
Koretsky, Milo D. Engineering and chemical thermodynamics.
Second Edition. John Wiley & Sons, 2013.
J.M. Smith, H.C. Van Ness and M. M. Abbott. Introduction To
Chemical Engineering Thermodynamics.
Elliott, J. Richard, and Carl T. Lira. Introductory Chemical
Engineering Thermodynamics. Vol. 184. Upper Saddle River, NJ:
Prentice Hall PTR, 1999.
Peter Atkins and Julio de Paula. Atkins’ Physical Chemistry.
Sandler, Stanley I. Chemical, Biochemical, and Engineering
Thermodynamics. John Wiley & Sons, 2017.

Chemical Thermodynamics: Chapter 6. Equilibrium Applications

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Chemical Thermodynamics

Chapter 6. Equilibrium Applications

Jorge Omar Gil Posada

Jorge Omar Gil Posada Chemical Thermodynamics 1 / 138

This modules covers applications of phase equilibrium mixtures, and it

Jorge Omar Gil Posada Chemical Thermodynamics 2 / 138

identify di↵erent types of equilibrium situations of interest to chemical

Jorge Omar Gil Posada Chemical Thermodynamics 3 / 138

2 Henry’s Law Revisited

4 Solid Liquid Equilibrium (SLE)

Jorge Omar Gil Posada Chemical Thermodynamics 4 / 138

Jorge Omar Gil Posada Chemical Thermodynamics 5 / 138

Jorge Omar Gil Posada Chemical Thermodynamics 6 / 138

Jorge Omar Gil Posada Chemical Thermodynamics 7 / 138

Henry 0 s Law Ref . State : yi ˆV

At low to mid P values: i ⇡ ˆV

Jorge Omar Gil Posada Chemical Thermodynamics 8 / 138

Ideal solution (Redlich Kister with B = C = D = ... = 0)

Jorge Omar Gil Posada Chemical Thermodynamics 9 / 138

Henrys Law Constants for Various Gases in Water at 25o C

Jorge Omar Gil Posada Chemical Thermodynamics 10 / 138

Henrys Constants in [bar] of H2 , N2 , O2 , CO, and CO2 in Four Di↵erent

For multicomponents (solute i and solvent j):

Jorge Omar Gil Posada Chemical Thermodynamics 11 / 138

Consider a binary system of dissolved gas (solute) a in liquid (solvent) b.

Jorge Omar Gil Posada Chemical Thermodynamics 13 / 138

Jorge Omar Gil Posada Chemical Thermodynamics 14 / 138

For high pressure and ideal liquid:

But we have seen:

Where normally P ref = 1 bar

Jorge Omar Gil Posada Chemical Thermodynamics 15 / 138

Where normally P ref = 1 bar

Jorge Omar Gil Posada Chemical Thermodynamics 16 / 138

For high pressure and non ideal liquid:

But we have seen:

Where normally P ref = 1 bar

Jorge Omar Gil Posada Chemical Thermodynamics 17 / 138

Where normally P ref = 1 bar

Jorge Omar Gil Posada Chemical Thermodynamics 18 / 138

Find compositions in the liquid and vapor

Jorge Omar Gil Posada Chemical Thermodynamics 19 / 138

xw Pwsat 1.0 ⇥ 3.166 kPa

Jorge Omar Gil Posada Chemical Thermodynamics 20 / 138

Working with air:

Jorge Omar Gil Posada Chemical Thermodynamics 21 / 138

From Raoults law:

yw = 0.0312 ! ya = 1 0.0312 = 0.9688

Reference state: Henry’s law:

Jorge Omar Gil Posada Chemical Thermodynamics 22 / 138

0.9688 ⇥ 101.32 kPa 5

Example. Calculate the solubility of O2 from air in the atmosphere in

Jorge Omar Gil Posada Chemical Thermodynamics 24 / 138

Example. Calculate the solubility of O2 from air in the atmosphere in

Jorge Omar Gil Posada Chemical Thermodynamics 25 / 138

yo ˆV P 0.21 ⇥ 1.0 ⇥ 1.0 bar

Jorge Omar Gil Posada Chemical Thermodynamics 26 / 138

Homework: Determine the solubility of nitrogen in water at 300 bar and

Jorge Omar Gil Posada Chemical Thermodynamics 27 / 138