Material and Energy Balances

Vapor-Liquid Equilibria for

Multi-component Systems

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Material and Energy Balances

www.menti.com
code: 91 70 42

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 Team Quiz
A tank in a room at 19oC is initially open to the
atmosphere on a day when the barometric pressure is
Material and Energy Balances

102kPa. A block of dry ice (solid CO2) with a mass of

15.7kg is dropped into the tank, which is then sealed. The
reading on the tank pressure gauge initially rises very
quickly, then much more slowly, eventually reaching a
value of 3.27 MPa. Assume Tfinal= 19oC.
a) How many moles of air were in the tank initially?
Neglect the volume occupied by CO2 in the solid state
and assume that a negligible amount of CO2 escapes
prior to the sealing of the tank.
b) What is the final density (g/liter) of the gas in the
tank?
c) Explain the observed variation of pressure with time.
More specifically, what is happening in the tank during
the initial rapid pressure increase and during the later
slow pressure increase?

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Material and Energy Balances

What are given info? What are to assume? What are the
equations involve?

P1 = ? P2 = ?
V1 = ? V2 = ?
T1 = ? T2 = ?
n1 = ? n2 = ?

CO2 (dry ice) = 15.7kg

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Material and Energy Balances
 Team Quiz 2
Material and Energy Balances

A certain gas has a molecular weight of 30.0,

a critical temperature of 310K, and a critical
pressure of 4.5 MPa. Calculate the density
in kg/m3 of this gas at 465K and 9.0 MPa, if

(a) The gas is ideal

(b) The gas obeys the law of corresponding
states

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 What is your strategy to solve this
problem?
Material and Energy Balances

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Material and Energy Balances
 Objectives
Material and Energy Balances

At the end of this chapter you should be able to

understand the following :

•Use Raoult’s law & Henry’s Law to predict the partial

pressure of a solute and a solvent
•Calculate the composition of multi-component
systems at equilibria between the liquid and vapor
phases
• Understand Partial Saturation & Humidity

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 Introduction
Material and Energy Balances

• If you have a multi-component mixtures says water & ethanol, at

a steady state conditions there is a two-phase vapor-liquid
mixture at equilibrium, a component in one phase is in
equilibrium with the same component in the other phase.

liquid
vapor
id D
A
Sat
va p a t liqu
Temperature

S
L-V L-V

Pressure
Sat va p
liqu
id B
C Sat

x y x y
liquid vapor

0 1 0 1
Mole fraction of one component Mole fraction of one component

Constant Pressure Constant Temperature

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 Introduction
Material and Energy Balances

• The equilibrium relationship depends on the

temperature, pressure & composition of the
mixture
• From the figure it is shown that the overall
composition of the mixture changes, two
phase exist, each having a different
composition for the same component

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 Henry’s Law
Material and Energy Balances

Henry’ Law is used for a component whose mole

fraction approaches zero, such as a dilute gas
dissolved in as liquid. Partial pressure is given as,

pi  H i xi [1]

The value Hi when xi approaches to zero can be

obtained from handbooks. Mole fraction in vapor phase
is given as,
pi H i xi
yi   [2]
ptot ptot

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 Example 1
Material and Energy Balances

• Determine the partial pressure of CO2 when it is

dissolved in water at 40oC having H=69,600 atm/mol
fraction. Given xCO2=4.2 x10-6.

• PCO2=69,600(4.2x10-6)=0.29 atm

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 Raoult’s Law
Material and Energy Balances

Raoult’s Law-used primarily for a component whose mole

fraction approaches to unity. Partial pressure is given as,

pi  pi* xi [3]

The vapor pressure for pure component, p* at any

temperature T, can be determined using Antoine equation.

∗ 𝑩 [4]
log 𝟏𝟎 𝒑 =¿ 𝑨 − ¿
𝑻 +𝑪
Where A, B & C are constants. p* in mmHg and T in oC

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 Raoult’s Law
Material and Energy Balances

The ratio of yi and xi is known as equilibrium constant, k.

yi
Ki  [5]
xi
Eq 5 provides good estimate of K values at low pressures
for components below their critical temperatures,

Yield values too large for components above the critical

temperatures, at high pressures and or for polar
compounds

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 Raoult’s Law
As recommended by Sandler if Tc,i>1.2, Eq 5 can also rewritten as,
Material and Energy Balances

[ 7.224  7.534 / Tr ,i  2.598 ln Tr ,i ]

pc
Ki  [5]
ptot

The equilibrium constant, Ki can be used to calculate the following:

1. Bubble point temperature of a liquid mixture given the total pressure
and liquid composition.
2. Dew point temperature of a vapor mixture given the total pressure
and vapor composition.
3. Equilibrium vapor-liquid composition over the range mole fractions
from 0 to 1 as a function of temperature given the total pressure

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 Example 2
Material and Energy Balances

Determine the composition of the first vapor formed if a liquid

mixture of 4.0% n-hexane in n-octane vaporised at T = 60 oC.
Given the Antoine equation constants as below:

A B C
n-hexane 6.88555 1175.817 224.867
(C6)
n-octane 6.91874 1351.756 209.100
(C8)

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 What do we need to do to solve
this?
Material and Energy Balances

What information What do we What do we need

is given? know? to determine?

• Xn-hexane= 0.04 • Raoult’s Law • Total pressure,

• Xn-octane = 0.96 pi  pi* xi PT
• N-hexane & N-
• Antoine octane vapour
• T = 60oC
equation pressure, pn-
• Constants of
hexane & pn-octane
Antoine Equation log 𝒑 ∗=¿ 𝑨 − 𝑩 ¿
𝟏𝟎
given 𝑻 +𝑪 • yn-hexane & yn-octane

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 Example 2
Material and Energy Balances

, p* in mmHg, T in oC

Thus,

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 Example 3
Material and Energy Balances

A liquid mixture containing 50.0% mole

hexane, 30.0 % mole n-butane and 20.0%
mole isobutene is stored in a rigid container
at 77°F. The container has a maximum
allowable working pressure of 200 psig. The
head space above the liquid contains only the
vapor of these hydrocarbons. Show that the
container is currently safe using:

• Cox Chart
• Antoine’s equation
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 Cox Chart
Material and Energy Balances

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 Antoine Equation
Material and Energy Balances

B
log10 p  A 
*
p* in mmHg and T in °C
C T
A B C
n-hexane 6.88555 1175.817 224.867
n-butane 6.82485 943.453 239.711
isobutane 6.78866 899.617 241.942

• T(K) = T(oC) + 273.15

• T(oR) = T(oF) + 459.67
• T(oR) = 1.8T(K)
• T(oF) = 1.8T(oC) + 32

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 Partial Saturation & Humidity
Material and Energy Balances

Often, the contact time required in a process for

equilibrium (or saturation) to be attained between the gas
& liquid is too long, and the gas is not completely
saturated with vapor.

Hence, the partial pressure of the vapor is less than the

vapor pressure of the liquid at the given temperature.
This condition is called partial saturation.
http://www.differencebetween.net/science/difference-betwe
en-partial-pressure-and-vapor-pressure/

https://www.youtube.com/watch?v=8EoxIUaFB3w

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 Definition
Material and Energy Balances

1. Relative saturation (relative humidity)- for other than

water vapor-air system
pvapor
RS 
psat

Relative humidity- for water water-air system

pH 2O
RH  * (100)
pH 2O

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 Definition
Material and Energy Balances

2. Molal saturation (molal humidity)- the ratio of the moles

of vapor to the moles of vapor-free gas.

nvapor pi
molal saturation  
nvapor- free ( dry ) gas P  pi

3. Humidity-mass of water vapor per mass of borne-dry

air

(nvapor )( Mrvapor ) massvapor

H 
(ndry gas )( Mrdry gas ) massdry gas

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 Definition
Material and Energy Balances

5. Absolute Saturation (Humidity)- ratio of moles of vapor

per mole per mole of vapor-free gas to the moles of
vapor that would be present per mole of vapor-free gas
if the mixture were completely saturated at the existing
temperature and total pressure

pi /( P  pi )
percentage saturation  * *
100%
pi /( P  pi )

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 Summary
Material and Energy Balances

Today I have learnt the followings:

Cox chart
Antoine Eqn
Raoults Law
Henry’s Law
Humidity
Saturation
Vapour pressure vs partial pressure
Equilibrium state

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