SHR Chapter 4

Single-Stage Equilibrium
Processes

Degree of Freedom Analysis

Binary Vapor-Liquid Equilibrium
Azeotropes in binary systems
Multicomponent Flash Calculations
Ternary Liquid-Liquid Systems

SHR 4.1

Degrees of Freedom: Gibbs Phase Rule

Example: C=3 components in =2 phases at equilibrium.
yi
T, P

xi

Variables #
yi
xi
T
P
2C+2=

C
C
1
1
8

= - = 3 degrees of freedom!

Equations #
yi = 1
xi = 1
Ki = yi /xi

In general:
Variables #
Equations
#

xi = 1
xi, yi, ... C
Ki = yi /xi C(-1)
T
1
P
1
C(-1)+
C+2

we must specify 3 variables

1
1

Options:
Set T, P and one mole fraction.
Set 3 mole fractions and determine T, P.
Set T and 2 mole fractions
...

C
C+2= 5

Gibbs Phase Rule:

F =C
#degrees
of freedom

#species

P +2
#phases

Note: we may not be able to find a solution if we

set an impossible choice of intensive variables.
Examples???

SHR 4.1.2

Gibbs Phase Rule & Extensive Variables

Example: single-stage equilibrium with C components in =2 phases
F
zi

V
yi

Q
T, P

TF
PF

L
xi

Variables
xi, yi, ...
zi
L, V, ...
F
TF, PF
T, P
Q

In general, we get C++4 extra variables

and C+2 extra equations when we
include extensive quantities.

#
C
C

1
2
2
1
C+C++6

F =V

Equations
#

xi = 1
1
zi = 1
Ki = yi /xi
C(-1)
Fzi = Vyi + Lxi
C
FhF=VhV+LhL
1
C++2
Why arent stream enthalpies
counted as variables?

E =C +4

Could set: C-1 of the zi, TF, PF, T, P

and then determine the remaining
quantities from the equations.

SHR 4.2

Binary Vapor-Liquid
Equilibrium
F
zA

V
yA

Q
T, P

TF
PF

L
xA

SHR 4.2

Tabulated Binary VLE Data

F =C

SHR Table 4.1a

P + 2 = 2-2+2 = 2

Saturated mixture
Water (A) - Glycerol (B) at 1 atm

Often data is obtained by

fixing T or P and xA or yA.
xA(P, yA) at a given T
xA(T, yA) at a given P
what do these
points represent?
SHR Table 4.1c

Para-xylene (A) - Meta-xylene (B) at 1 atm

T (C)

yA

xA

A,B

133.335
138.491

1
0.8033

1
0.8

1.0041

138.644

0.6049

0.6

1.0082

138.795

0.4049

0.4

1.0123

138.943

0.2032

0.2

1.016

139.088

T (C)

yA

xA

A,B

100
104.6

1
0.9996

1
0.8846

333

109.8

0.9991

0.7731

332

128.8

0.998

0.4742

544

148.2

0.9964

0.3077

627

175.2

0.9898

0.1756

456

207

0.9804

0.0945

481

244.5

9341

0.0491

275

282.5

0.8308

0.025

191

290

SHR 4.2

Binary VLE: Methanol/Water

SHR Table 4.1b

SHR Figure 4.2a

Methanol (A) - Water (B) at 1 atm

T (C)
64.5
66
69.3
73.1
78
84.4
89.3
93.5
100

yA
1
0.958
0.87
0.779
0.665
0.517
0.365
0.23
0

xA
1
0.9
0.7
0.5
0.3
0.15
0.08
0.04
0

A,B
2.53
2.87
3.52
4.63
6.07
6.61
7.17
-

this width is directly related

to the relative volatility, .

SHR Figure 4.5

SHR Figure 4.2b

Ki
ij
Kj

This distance is related to

the relative volatility,

SHR 4.2

T-x-y Diagrams
n-hexane, n-octane at P=1 atm

SHR Figure 4.3

Inverse lever-arm rule:

V /L = DE/EF
Given xhexane=0.3,
What is V/L at B-C?
What is V/L at D-F?
What is V/L at G?

What state is G and B?

What state is H and A?
What state is E?

SHR 4.2

Operating Line (q-line)

n-hexane, n-octane at P=1 atm
What does it represent?

SHR Figure 4.4

species mole balance: F zA = V yA + LxA

overall mole balance: F = V + L
Eliminate L and solve for yA...

V /F
1
1
yA =
xA + V
zA q-line
V /F
/F
goes through xA = yA = zA (45 line)
0 V/F 1
Slope is bounded by - (V=0) and 0 (V=F).
V=F gives us point A (always on 45 line).
Given a molar vaporization % (V/F), we can
graphically determine the product compositions.

Example: for zhexane=0.6 and

60% vaporization, find the yi.

1. Locate zA on the 45 line (point A)

2. From V/F, calculate the slope of the q-line.
3. Follow the q-line to determine the
equilibrium composition (point B)

SHR 4.3

Azeotropes in Binary
Systems

What is an Azeotrope?
SHR Figure 4.3

Normal
(zeotropic)
system

Maximumboiling
azeotropic
system
1 atm
SHR Figure 4.7

At an azeotrope, KA = KB = 1, = 1.
No separation possible at this point!
If you start on one side of the azeotrope, you can
only recover at best a pure stream and the
azeotrope - not two pure streams!

Typically occur in systems with close boiling

point constituents of different chemical type
(e.g. ethanol/water).
Maximum or minimum boiling points.
zeoptropic systems have a monotonic relationship
between xA and T.

SHR Figure 4.6

Minimumboiling
azeotropic
system (most
common)

1 atm

SHR Figure 4.6

Minimum-boiling Azeotropes
Figure 4.6a:
What can we say about A and

B?
from Raoults
Positive deviation
s
s
law: Ki = Pi /P, (Ki = iPi /P).

T=70 C

P = 1 atm

Figure 4.6b
What can we say about relative
volatility across the azeotrope
point?

Note: we can change the

pressure to shift the
azeotrope a little bit.
Figure 4.6a (70C, 123 kPa)

shows composition of x=0.7.

Figure 4.6b & 4.6c shows x=0.72
(at 66C & 101 kPa).
ethanol-water azeotrope
disappears at P < 9.3 kPa.

1 atm
isopropyl ether,
isopropyl alcohol

SHR Figure 4.7

Maximum-boiling Azeotrope
T = 100 C
P = 1 atm
Figure 4.7a:
What can we say about A and

B?
Negative deviation from Raoults
s
s
law: Ki = Pi /P, (Ki = iPi /P).

Again, we see a shift in the

azeotrope as we change the
operating pressure.
compare 4.7a with 4.7b & 4.7c.

P = 1 atm

Predicting Azeotrope Formation

Pis
Modified Raoults law: Ki = i
P
van-Laar:

ln

ln

For an azeotrope, Ki=1

A12
[1 + (x1 A12 )/(x2 A21 )]
A21

[1 + (x2 A21 )/(x1 A12 )]

P
= s
Pi

Modified Raoults
law at an azeotrope

P
A12
ln s =
2
P1
[1 + (x1 A12 )/(x2 A21 )]
P
A21
ln s =
2
P2
[1 + (x2 A21 )/(x1 A12 )]

Solve these for x1 and x2.

(Note: x2 = 1-x1.)

Example: does ethanol (1) and n-hexane (2) form an azeotrope?

A12=2.409, A21=1.970

Solution:
1. Choose P.
2. Find Tbubble or Tdew and
corresponding x, y.
3. See if Ki = 1.

Up next:
flash calculations to
get Tbubble or Tdew.

SHR 4.4

Multicomponent Flash
Calculations

Flash Concepts
Two modes
partial vaporization (typically add
heat)
partial condensation (typically
remove heat)

Isothermal flash
add/remove heat such that T=TF.
must determine the duty of the
heat exchanger to maintain T.

Adiabatic flash
Q=0, TTF
Temperature drops (vaporization) or
rises (condensation).
T is unknown, so this is more
difficult than isothermal flash.

F
zi

V
yi

Q
T, P

TF
PF

L
xi

SHR 4.4

The Rachford-Rice Equation

F
zi

V
yi

Q
T, P

TF
PF

L
xi

C+4 degrees of freedom

We typically know zi, TF and PF.
2 free variables
F zi
L + V Ki
F zi
=
F V + V Ki
zi
=
1 + (Ki 1) VF

xi =

yi =

K i zi
1 + (Ki 1) VF

combine first two

sets of equations
overall mole balance
to eliminate L

Variables:
xi
C
yi
C
zi
C
F
1
TF
1
PF
1
L
1
V
1
T
1
P
1
Q
1
3C+8

Equations:

F zi = Lxi + V yi

species mole balances

yi = Ki x i

phase equilibrium

i=1 yi
PC
i=1 xi

=1

=1

PC

hF F + Q = hV V + hL L

energy balance

F =V +L

total mole balance

2C+4
Auxiliary Ki (T, P, yj , xj ) hF (TF , PF , zj )
equations: hV (T, P, yj )
hL (T, P, xj )

Substitute
0 into xi and yi and then subtract to1get:
C B
X
K i zi
B
B
V
@
1
+
(K
1)
i
F
i=1
{z
}
|
yi

from second
equation

Still 2C equations just different form.

C
X
i=1

zi (Ki
1 + (Ki

1)
1)

C
zi
C
=0
V C
1 + (Ki 1) F A
{z
}
|
xi

=0

RachfordRice
equation

Rachford-Rice equation
C
X
i=1

zi (Ki
1 + (Ki

Typically, convergence
is achieved when

1)
1)

Once we know ,
zi
xi =
1 + (Ki 1)
K i zi
yi =
1 + (Ki 1)

=0

(k+1)

(k)

(k)

< 10

V =

L=F

V = F (1

Q = hV V + hL L

hF F

Ideal Mixtures:

Now what?

For ideal mixtures, Ki(T,p). If we know T, p

we can solve the Rachford-Rice equation for
. After that, we can easily get xi, yi.
For nonideal mixtures, Ki also depends on
composition!
Either go back and solve a bigger system of
equations or use successive substitution.
Successive substitution is not highly robust,
but is usually good enough for these
problems.
If T = TF and P = PF then
we only have one
equation to solve for .

3. Calculate yi & xi

Non-Ideal Mixtures:

Successive
Substitution

1. Determine Ki(T,p) (using Raoults

law, graphical techniques, etc.)
2. Solve for .

1.
2.
3.
4.
5.
6.
7.

Guess a value for Ki (e.g. from charts or Raoults law)

Solve for .
Calculate yi & xi
Calculate Ki using your favorite model.
Solve for .
If changed, return to step 3.
Update yi & xi using calculated in step 6.

SHR 4.4.2

Bubble Point & Dew Point

Rachford-Rice equation
C
X
i=1

zi (Ki
1 + (Ki

1)
1)

Recall Ki = Ki( xi, yi, T, P )

=0

At the bubble point, V=0, L=F

C
X

zi K i = 1

i=1

Given P, find Tbubble

Given T, find Pbubble

At the dew point, V=F, L=0

C
X
zi
=1
Ki
i=1

=0.
Use Newtons method (or
another nonlinear equation
solver) to solve for bubble/dew
point temperature or pressure.

=1.

Given P, find Tdew

Given T, find Pdew

At equilibrium, the vapor is at

its dew point and the liquid is
at its bubble point.

See SHR Example 4.2 for a graphical solution technique.

Example: bubble point calculation

F
zi

V
yi

Q
T, P

Solve

TF
PF

Component
i-Butane
n-Butane
i-Pentane
n-Pentane

L
xi

Feed
kmol/h
8.6
215.8
28.1
17.5
270

Bubble point: V=0, L=F, =0.

C
X

zi Ki = 1 to obtain T.

i=1

Need a model for Ki(T).

zi = xi
0.0319
0.7992
0.1041
0.0648

Empirical Correlation (dePriester Chart):

a1
a2
b2
b3
ln K = 2 +
+ a3 + b1 ln p + 2 +
T
T
p
p
NOTE: T in R and p in psia!
Compound

a1

a2

Isobutane

-1,166,846

n-Butane

-1,280,557

Isopentane
n-Pentane

a3

b1

b2

b3

7.72668 -0.92213

7.94986 -0.96455

-1,481,583

7.58071 -0.93159

-1,524,891

7.33129 -0.89143

M. L. McWilliams, Chemical Engineering, 80(25), 1973 p. 138.

Example: equilibrium diagram

Using Raoults law, obtain a T-x-y diagram of the Propane-Benzene system.
360

liquid
vapor

340

Pis
Raoults law: Ki =
P
Pis
Modified
Ki = i
Raoults law:
P

T (K)

320
300
280

Antoine Equation parameters

260

A
240
220
0

Propane 6.80398 803.81

0.2

0.4
0.6
Mole Fraction

0.8

C
246.99

Benzene 6.90565 1211.033 220.79

SHR 4.4.1

Isothermal Flash
F
zi

V
yi

Q
T, P

TF
PF

Given: T=TF, P=PF,

Find: xi, yi, V, L, Q.

L
xi

Once we know ,
zi
xi =
1 + (Ki 1)

Rachford-Rice equation
C
X
i=1

zi (Ki
1 + (Ki

1)
1)

=0

K i zi
yi = K i x i =
1 + (Ki 1)

V =
L=F

F
V = F (1

Q = hV V + hL L

hF F

hi = hi (T )

1.Choose a model for Ki.

2.Given zi, solve Rachford-Rice to obtain .
3.Calculate xi, yi, V = F, L = F(1-).
4.Calculate hV, hL, hF at T and xi, yi
5.Calculate Q (heat exchanger duty).

h=

C
X

hi x i

i=1

(molar enthalpy)

SHR 4.4.3

Adiabatic Flash
F
zi

V
yi

Q
T, P

TF
PF

L
xi

Given: Q=0, P=PF,

Find: xi, yi, T, V, L.
Energy balance:
Q = hV V + hL L
0 = F (hV

i=1

zi (Ki
1 + (Ki

1)
1)

+ hL (1

hF )

1.Choose a model for Ki.

=0
2 equations,
2 unknowns
( , T )

Energy Balance:

F [hV

+ hL (1

See SHR 4.4.3 for an alternative algorithm

Rachford-Rice equation:
C
X

hF F

hF ] = 0

2.Given zi, solve Rachford-Rice &

energy balance simultaneously to
obtain and T.
3.Calculate xi, yi, V = F, L = F(1-).

Note: at each iteration, we must update values

for hV and hL given the current value for T.

Summary - Flash Calculations

D ESCRIPTION

In all cases, we need models for Ki( T, P, xi, yi ).

Bubble point
pressure
Bubble point
temperature
Dew point
pressure
Dew point
temperature

K NOWNS

U NKNOWNS

T, zi

Solve r ( P) = 1

iC=1 zi Ki for P

P, zi

Solve r ( T ) = 1

iC=1 zi Ki for T

T, zi

Solve r ( P) = 1

iC=1 zi/Ki for P

P, zi

Solve r ( T ) = 1

iC=1 zi/Ki for T

P ROBLEM STATEMENT

Solve the Rachford-Rice equation

Isothermal flash

T, P, zi

Y, xi , yi

z i ( Ki
r (Y) =
1 + ( Ki
i =1
together with xi =

zi
1+(Ki 1)Y

1)
1) Y
and yi = Ki xi .

Solve the coupled system of equations

Adiabatic flash

Q, P, zi

Y, T, xi , yi

1)
,
1) Y

r1 (Y, T )

z i ( Ki
1 + ( Ki
i =1

r2 (Y, T )

F [ hV Y + h L (1

together with xi =

zi
1+(Ki 1)Y

Y)

hF ]

and yi = Ki xi .

SHR 4.5

Ternary Liquid-Liquid
Systems
Graphical Methods

SHR 4.5

Introduction
We have a carrier (A) which holds solute (B). We
want to extract the solute into a solvent (C).
A is insoluble in solvent C

A is partly soluble in solvent C

simple mass balance.

need to know phase equilibrium.

SHR 4.5

Case 1: Carrier (A) is insoluble in solvent (C)

(F )

(R)

(F )

(E)

Note: we could do this whole

thing on a mass basis as well.

Carrier (A) mole balance: xA F = xA R

Solute (B) mole balance:

(R)

xB F = xB E + xB R
(E)

Solvent (C) mole balance: S = xC E

(F )

FA = x A F
(F )

FB = x B F

Use A & C balances to eliminate R & E in B balance:

(F )
xB F

(F )

X B FA =

(E)
Distribution
X
0
=
or partition KDB = B
(R)
XB
coefficient

(E)
xB

(E)
xC
(E)
XB S +

(E)

xB

/x(E)
C

(R)
xB

(R)
xA

= K DB

(R)
xB

FA
(R)
xA

Molar ratios of B to other component:

(E)
XB

(R)

X B FA

(R)
XB

(E)

xB E
(E)

xC E

xB

xB

(E)

This is the familiar Kvalue (distribution

coefficient) for liquid-liquid.
(E)
xB
KDB = (R)
xB

(R)
XB
(F )
XB

=
=

xB

(R)

xB R
(R)

xA R

(R)

(E)

xB

(E)

xC

(R)

1+

(R)

xA

in extract,
only B & C
in raffinate,
only B & A

1
0
K DB S
FA

Extraction factor
(large is good)

SHR 4.5

Case 2: Carrier (A) is soluble in solvent (C)

1. Locate feed (M)
2. Follow tie-lines to
miscibility boundary to
determine product
composition (E & R)
3. Inverse lever-arm rule
to determine relative
amount of E & R.
Identify/describe:

How many degrees of

freedom?
Miscibility boundary
Two-phase region
Single-phase region
Tie line
Plait point
How is this diagram
made?

Note: these diagrams

are for a specific T, P.

SHR Figure 4.13a

Example
Determine the extract and raffinate compositions when a 45
wt% glycol, 55 wt% water solution is contacted with twice
its weight of pure furfural solvent at 25 C and 101 kPa.

Assume F =100 g basis of feed

S = 200 g.
Point F indicates F stream
Point S indicates S stream
Inverse lever arm rule to get point M:

(SM)/

(MF) = 1/2 or (SM)/(SF) = 1/3

Follow tie line to get E & R.
Extract: 4% A, 9% B, 88% C
Raffinate: 56% A, 34% B, 10% C
Inverse lever arm rule on tie line to get ratio
of E/M and R/M:
E = M (MR)/(ER) = 300 (5.5 cm / 7.6 cm)
= 220 g (measured from SHR figure 4.14)
R = M (EM)/(ER) = M-E = 300-220 = 80 g.