P,T-Flash Calculations

Purpose of this lecture:

To illustrate how P,T-Flash calculations can be performed either
graphically or numerically

Highlights
P, T -Flash calculations from VLE diagrams
The “lever rule” and its use in calculating extensive variables (V, L)
Step-by-step procedure for numerical P,T-Flash calculations

Reading assignment: Ch. 14, pp. 551-554 (7th edition), or

Ch. 14, pp. 532-535 (6th edition)

CHEE 311 Lecture 3 1

4. P,T-Flash Calculations
If a stream consists of three components with widely differing
volatility, substantial separation can be achieved using a simple
flash unit. Vapour
y1
y2
Feed y3=1-y1-y2
z1 P,T
z2 Liquid
z3=1-z1-z2 x1
Tf, Pf x2
x3=1-x1-x2
Questions often posed:
Given P, T and zi, what are the equilibrium phase compositions?
Given P, T and the overall composition of the system, how much of
each phase will we collect?
CHEE 311 Lecture 3 2
P-T Flash Calculations from a Phase Diagram
For common binary systems, you can often find a phase diagram in
the range of conditions needed.

For example, a Pxy diagram for the

furan/CCl4 system at 30C is
illustrated to the right.

Given
T=30C, P= 300 mmHg, z1= 0.5

Determine
x1, x2, y1, y2 and the fraction of the
system that exists as a vapour (V)

CHEE 311 Lecture 3 3

Flash Calculations from a Phase Diagram
Similarly, a Txy diagram can be used if
available.

Consider the ethanol/toluene system

illustrated here at P = 1atm.

Given
T=90C, P= 760 mmHg, z1= 0.25

Determine
x1, x2, y1, y2 and the fraction of the
system that exists as a liquid (L)

How about:
T=90C, P= 760 mmHg, z1= 0.75?

CHEE 311 Lecture 3 4

Phase Rule for Intensive Variables
For a system of  phases and N species, the degree of freedom is:
F=2-+N
 # variables that must be specified to fix the intensive state of
the system at equilibrium
Phase Rule Variables:
The system is characterized by T, P and (N-1) mole fractions for
each phase
 the masses of the phases are not phase-rule variables,
because they do not affect the intensive state of the system
 Requires knowledge of 2 + (N-1) variables
Phase Rule Equations:
At equilibrium i = i  = i  for all N species
 These relations provide (-1)N equations

The difference is F = [2 + (N-1)] - [(-1)N]

= 2-  +N

CHEE 311 Lecture 3 5

Duhem’s Theorem: Extensive Properties SVNA10.2

Duhem’s Theorem: For any closed system of known composition,

the equilibrium state is determined when any two independent
variables are fixed.
If the system is closed and formed from specified amounts of each
species, then we can write:
Equilibrium equations for chemical potentials (-1)N
Material balance for each species N
 We have a total of N equations
The system is characterized by :
T, P and (N-1) mole fractions for each phase 2 + (N-1)
Masses of each phase 
 Requires knowledge of 2 + N variables

Therefore, to completely determine the equilibrium state we need :

[2 + N] - [N] = 2 variables
This is the appropriate “rule” for flash calculation purposes where
the overall system composition is specified
CHEE 311 Lecture 3 6
Ensuring you have a two-phase system
Duhem’s theorem tells us that if we specify T,P and zi, then we
have sufficient information to solve a flash calculation.

However, before proceeding with a flash calc’n, we must be sure

that two phases exist at this P,T and the given overall composition:
z 1, z 2, z 3
 At a given T, the maximum pressure for which two phases
exist is the BUBL P, for which V = 0
 At a given T, the minimum pressure for which two phases
exist is the DEW P, for which L = 0

To ensure that two phases exist at this P, T, zi:

 Perform a BUBL P using xi = zi
 Perform a DEW P using yi = zi

CHEE 311 Lecture 3 7

Ensuring you have a two-phase system
If we revisit our furan /CCl4 system
at 30C, we can illustrate this point.

Given
T=30C, P= 300 mmHg, z1= 0.25
Is a flash calculation possible?
BUBLP, x1 = z1 = 0.25
DEWP, y1 = z1 = 0.25

Given
T=30C, P= 300 mmHg, z1= 0.75
Is a flash calculation possible?
BUBLP, x1 = z1 = 0.75
DEWP, y1 = z1 = 0.75

CHEE 311 Lecture 3 8

Flash Calculations from Raoult’s Law
Given P,T and zi, calculate the compositions of the vapour and
liquid phases and the phase fractions without the use of a phase
diagram.

Step 1.
Determine Pisat for each component at T (Antoine’s eq’n, handbook)

Step 2.
Ensure that, given the specifications, you have two phases by
calculating DEWP and BUBLP at the composition, zi.

Step 3.
Write Raoult’s Law for each component:
y iP  x iPisat
or
yi  K ixi (A)
where Ki = Pisat/P is the partition coefficient for component i.
CHEE 311 Lecture 3 9
Flash Calculations from Raoult’s Law
Step 4.
Write overall and component material balances on a 1 mole basis
Overall:
L  V  F  1 mole (B)
where L= liquid phase fraction, V= vapour phase fraction.
Component:
z i (1)  x iL  y i V i=1,2,…,n (C)
(B) into (C) gives
z i  x i (1  V )  y i V
which leads to:
z i  x i (1  V )
yi  (D)
V
Step 5.
Substitute Raoult’s Law (A) into (D) and rearrange:
y
z i  i (1  V )
Ki zi K i
yi  y  (E)
1  V(K i  1)
i
V
CHEE 311 Lecture 3 10
Flash Calculations from Raoult’s Law
Step 6:
Overall material balance on the vapour phase:
i n
 yi  1
i 1
into which (E) is substituted to give the general flash equation:
i n zi K i
 1 14.18
i 1 1  V (K i  1)
where,
zi = overall mole fraction of component i
V = vapour phase fraction
Ki = partition coefficient for component i
Step 7:
Solution procedures vary, but the simplest is direct trial and error
variation of V to satisfy equation 14.18.
 Calculate yi’s using equation (E) and xi’s using equation (A)
CHEE 311 Lecture 3 11
 VLE Calculations –Summary

Here is a summary of what we need to know (Lectures 8 & 9):

• How to use the Phase Rule (F=2-+N)
• How to read VLE charts
- Identify bubble point and dew point lines
- Read sat. pressures or temperatures from the chart
- Determine the state and composition of a mixture
• How to perform Bubble Point, Dew Point, and P,T-Flash calculations
- Apply Raoult’s law
- Apply Antoine’s equation
• How to use the Lever Rule (graphically or numerically)
• How to construct VLE (Pxy or Txy ) charts for ideal mixtures

CHEE 311 Lecture 3 12