Chemical Engineering Fundamentals 2A

CEFCHA2

Lecture 10: Multi-Phase Systems I

V Naidoo
JOB 4134
vizellen@uj.ac.za
 Objectives
 Understand how separation processes work
 Understand how to read Phase diagrams
 Understand volatility and vapour pressure concepts
 Be able to use all 3 ways to estimate vapour pressure
 Understand the Clausius-Clapeyron Equation (and be able to derive it)
 Understand the Cox charts & the Antione Equation
 Understand the Gibbs Phase Rule
 Be able to interpret phase and T vs x,y diagrams
 Be able to use tables to get required variables to solve problems
 Introduction

Overall schematic of chemical process industry

Feed Reaction Separation Heat Recovery Product

and
Mixture Pure Utility
component

Characteristic of Separation Process

S epara tion
Agent Separating Agent:
(i) Heat
(ii) Solvent
Mixture
S eparation Pure (iii) Pressure
Device Com ponent
(iv) Gravity or Mechanical Force
 Multiphase Systems

Process 1 Process 2
Ethanol
vapor
Ethanol Benzene solid
Distillation Q out Benzen
Benzene
column Crystallizer e
liqui
liquid
d
Ethano
l

Water Extractor

Ethanol
Decanter
Benzene liquid 1

liquid 2

Process 3
S i n g l e C o m p o n e n t P h a s e E q u i l i b r i u m - P h a s e D i a g r a m s for H 2 O
 Volatility

Volatility: Tendency to transfer from liquid (or solid) to vapor

• High vapor pressure ⇒ high volatility
• Low boiling point ⇒ high volatility
Example: Consider two beakers, one containing n-butane, the other n-octane, at room
temperature.

What would happen if the lids were removed ?

• Many separation processes rely on the high volatility of some species in a mixture and
non-volatility (evaporation, drying) or much lower volatility (flash vaporization,
distillation, condensation) of other species in the mixture.
• To design separation processes based on relative volatility, we need to know or estimate
vapor pressures, pi*(T) for all mixture components (i).
• Highly volatile species tends to be more likely in vapor phase
 Vapor Pressure (p*)

Vapor pressure (p*) – a measure of species volatility

• The higher the vapor pressure for a given temperature the greater the volatility of
species.

• Vapor pressure is related to boiling – liquids with high vapor pressures (volatile
liquids) will boil at lower temperatures.

• The vapor pressure and hence the boiling point of a liquid mixture depends on the
relative amounts of the components in the mixture.
Vapor Pressure (p* ) – Applications in Chemical Engineering

Chap. 6 - 8
 Application of Vapor Pressure in Distillation Process

Distillation occurs because of the differences in the vapor pressure (volatility)

of the components in the liquid mixture
 4 Wa ys to E s t i m a t e Vapor Pressure (p*) F r o m a Given T:

1. Measure it. Reliable but time-consuming and costly.

2. Look it up in Table B.3 for water, Perry’s Chemical Engineers

Handbook, Handbook of Chemistry & Physics, etc.

3. Use graphical correlation.The Cox chart, Fig. 6.1-4, p. 247, has nearly linear
correlations of vapor pressure with temperature (see p. 245–246 to know how it
is constructed and why the plots are nearly linear):
▪ Given T, find vapor pressure p*. Example: (p*) propane (55 0F) = psi
▪ Given p*, find boiling point T. Example: (Tb) acetone (2 psi) = 0F

4. Fit a function to the data. Use it to estimate p* for any T in range of experimental
data.
(a) Clausius-Clapeyron equation (Eq. 6.1-3, p. 244).
(b) Antoine equation (Eq. 6.1-4, p. 246 & Table B.4). More accurate than
Clausius- Clapeyron but harder to estimate parameters (3 instead of 2).
 Vapor Pressure (p*) Estimation
Clausius - Clapeyron equation
- V ˆ ~ Vˆ , (since
V Vˆ >>>> Vˆ
g
)
Hˆ
dp * v
Clapeyron equation
ˆ
Assuming
l
idealgl gas law g
dT = T(Vˆ - applies
Vˆ ) to vapor, g = RT
g p
𝑑𝑝 ∗ ∆ 𝐻𝑣l. 𝑃 ∗ Vˆ *
=
𝑑𝑇 𝑅𝑇
2

𝑑𝑝 ∗ ∆ 𝐻𝑣 𝑑𝑇
= × 2
𝑃∗ 𝑅 𝑇

Integratin

( )
g 𝑃2 − ∆ 𝐻𝑣 1 1
ln = ( − )
𝑃1 𝑅 𝑇 1 𝑇2

Clausius - Clapeyron equation

 Vapor Pressure (p*) Estimation

𝑦 𝑚 𝑥
Clausius-Clapeyron equation
𝑑𝑝 ∗ ∆ 𝐻𝑣 𝑑𝑇
= × 2 ∆ Hv
ln 𝑃 𝑃∗ 𝑅 𝑇 lnp* = - R +
B T

∆ 𝐻𝑣
𝑅

d(lnp*) ∆ Hˆ v
=- R
d( 1 )
T
p* 
-
Rln  p *1 
 2

1  ∆ Hˆv (KJ / mol) =

1 - 1 
𝑇  T
 2 T1
Cox Chart Vapor Pressure Plots
 Vapor Pressure (p* ) Estimation

Antoine Equation

B
log10p* = A
- T +
C
Antoine constants (A, B and C) for many
compounds are available in the literature Table B.4
(pg. 640-641) in the textbook
 Example I

The vapor pressure of an organic solvent is 50 mmHg at 25 0C and 200 mmHg at 45 0C.The solvent is the only species in a
closed flask at 35 0C and is present in both liquid and vapor states.The volume of gas above the liquid is 150 mL. Estimate
the amount of the solvent (mol) contained in the gas phase.

Plot graph ln(p*) vs 1

T
6569K
∆ Hˆ  1  ln p *  = - 308K +
ln p *  = - R v T  +
 p * = 102.7 mm
25.96
B  p 2*  ln
ln  *  200 50 Hg
ˆ
 ∆ H v
 p 2  = -6569 K
298 
=
R
 1
 T - 1
  
318
1 
1
102.7 
T1
 760 atm   0.15L
 -
2
P
n= =
ln 50  =  -6569 K 
1 
+B
....... B = 25.96 V  L.atm 
298K 

 0.08206
mol.K  
R  308K 
6569
ln p *  = -T(K + = T8.02 x 10 - 4 mol
25.96 )
 The Gibbs Phase Rule1

Closed system @ equilibrium T and P

VAPOR
Vv, MA, MB, MC; yA, yB
Extensive variables : M,V
Intensive Variables : x, y,T,
P
LIQUID
Vl, MA, MB, MC; xA, xB
 The Gibbs Phase Rule
The numbers of intensive variables that must be specified independently
for a non-reactive system at equilibrium to calculate all the other intensive
variables, i.e., the numbers of degrees of freedom, F is

F = 2 + C - P

P = number of phases
C = number of chemical species

If R independent reactions occur among the system components and the

reactions proceed to equilibrium, then

F = 2 + C - P - R
 The Gibbs Phase Rule - Example

Specify the number of degrees of freedom of each of the following

equilibrium systems:

1. Pure liquid water.

P = 1; C = 1 s o F =2+1-1= 2
(Specify 2 intensive variables,T, P)

2. A mixture of ice and liquid water.

P = 2, C = 1 s o F = 2 + 1 - 2 = 1
(Specify either T or P)

3. Pure liquid acetone in equilibrium with acetone vapor and

nitrogen.
P = 2, C = 2 s o F=2+2-2=2
(Specify either T and P, or a gas phase mass or mole fraction)
 The Gibbs Phase Rule
Consider the following two closed systems at equilibrium.Think about where
each one is on the phase diagram.

How many of the variables T, P,Vv , and (for System II) ρl would you have to specify
to be able to determine the others for each of these two systems? (Suggestion: Refer
to the phase diagram.)

For System I, you need to specify both T and P (i.e., 2 variables) to know where you
are in the vapor region of the phase diagram. Once you know T and P, you can
calculate Vv = RT/P (or use a real gas equation of state).

How about for System II, how many variable you need to specify?