EXERCISE 3: Simple

Distillation and Steam

Distillation

Volatility
Ability of the substance to escape

from the liquid into the vapor phase

strong IMFA, low volatility

Vapor Pressure
the force exerted on the walls of the
container (closed) containing the
liquid at a given temperature
a quantitative measure of volatility
higher vapor pressure, less volatile

Boiling Point
Temperature at which the equilibrium

vapor pressure (the vapor pressure at

which there is no transfer of the liquid
particles in the gas phase and vice
versa) equals the atmospheric
pressure
Normal boiling point boiling point at the
standard atmospheric pressure (1 bar)

Distillation
used for purification and boiling
point determination
TYPES

Simple
Steam
Fractional
Vacuum
Modified

NOTE
Distillate liquid condensate from
distillation
Pot residue / residue substance
remaining in the distilling flask

Simple Distillation
Takes advantage of the very wide

difference
in
volatility
of
the
components of the mixture
Separating liquids boiling BELOW 150
C from nonvolatile impurities or
another liquid boiling at least 70 C
higher than the first (liquids should
dissolve in each another)

Principle Behind Simple

Distillation
Raoults Law
distillation relies on the fact that the vapor above
a liquid mixture is richer in the more volatile
component in the liquid
in an ideal solution the partial pressure (P A) of
component A at a given temperature is equal to
the vapor pressure PoA of pure A multiplied by the
mole fraction of A (XA) in solution.
now consider an ideal solution of A and B:
XA = nA/ (nA + nB)
XB = nB/ (nA + nB)
XA + XB = 1
where nA and nB represent the number of moles
of components A and B.

Principle Behind Simple

Distillation
So that the total vapor pressure will be:
PA = XAPoA
PB = XBPoB

PT (total vapor pressure) = PA + PB

= XAPoA + XBPoB

Simple Distillation

Points to Remember in Simple

Distillation
Position of the thermometer bulb

should be at 5 mm below the side

arm of the flask
For accurate determination of the vapor
temperature
Higher than the 5 mm position: lower vapor
temperature reading
Lower than the 5mm position: higher vapor
temperature reading

Points to Remember in Simple

Distillation
Volume of distilling flask should be at
least twice the volume of the liquid
to be distilled
To allow room for boiling

Water in should be lower than water

out

In order for the condenser to be filled

thoroughly with water

Points to Remember in Simple

Distillation
Condenser should be cold enough to
ensure condensation of the vapor

If solvent to be recovered is volatile, put

receiving flask into an ice bath

Use of boiling chips provide site for

boiling and thus prevent bumping

Steam Distillation
Codistillation of water with a

substance which it is immiscible

Codistillation distillation of 2 or more
liquids

Used to separate slightly volatile

water insoluble substance from nonvolatile materials

Principle Behind Steam

Distillation
Daltons Law of Partial Pressure

When 2 or more gases or vapors which do not

react chemically with one another are mixed at
constant temperature,the sum of their individual
vapor pressure is equal to the the total pressure of
the system.
PT = PT
= P1 + P2 + P3 +
where: PT = total pressure
Pn = vapor pressure of the pure
compound at the same temperature
***PT > Pressure of the most volatile component

Principle Behind Steam

Distillation
The total pressure is dependent only in

the individual vapor pressures and not in

the mole fraction () of each component
of the mixture. The composition of vapor
is constant at a particular temperature.
The vapor pressure of a mixture is
proportional to the number of molecules
of each substance in the vapor phase.

Principle Behind Steam

Distillation

norganic
nH2O

Porganic
PH2O

Sample Problems
Quinoline has a boiling point of 237 C at 1 atm.

At 99.6 C, the vapor pressure of water is 750

mmHg while that of quinoline is only 10 mmHg.
What is the mole ratio of quinoline and water in
the distillate.
At 98 C, the vapor pressure of acetophenone
(MM = 120 g/mol) is 53 mmHg and that of water
is 707 mmHg. If steam distillation was
employed, what will be the weight of
acetophenone that will distill per gram of water?

Assignment
At 80.0 C, the vapor pressure of
substance carlkyne is 61 mmHg
while that of water is 699 mmHg.
Calculate for the molar mass of
carlkyne if 50.00 g carlkyne was
mixed with 200.0 g of water.

Applications of Steam
Distillation
Each substance in an immiscible mixture
exerts vapor pressure independently of
the others. Thus, when the combined
vapor pressures of the immiscible
substances equal the opposing
atmospheric pressure, the mixture will
boil.
The mixture will boil at a temperature
lower than of the boiling point of the
lowest boiling component

Sample for Steam

Distillation
Suitable samples
Liquid at room temperature
Slightly volatile
Water immiscible

Sample cut finely

Increase surface area of contact between
oil and water

Role of Steam
Contributes a relatively high vapor

pressure to the total pressure of the

mixture to allow the mixture to boil
at a lower temperature

OH

OH

linalool

geraniol
O

citral

limonene

Comparison of Simple and

Steam Distillation
SIMPLE

STEAM

Principle

Raoults Law

Daltons Law

Sample used

Solution of
nonvolatile solute
in volatile solvent
(Homogeneous)

Immiscible Liquids
are both volatile
(Heterogeneous)

Comparison of Simple and

Steam Distillation
SIMPLE

STEAM

Distillate
homogeneous Heterogeneou
collected
s
Boiling point
Normal
Less than the
boiling point normal boiling
point of the
lowest boiling
component

Comparison of Simple and

Steam Distillation
application

SIMPLE
Substances with
wide difference
in boiling point
e.g. CHCl3

STEAM
-Volatile and
water
immiscible
-Purification of
substances that
(61-65 C) and
are heat
caffeine (238 C)
sensitive
(decompose at
high T)
-Mixture
contains large
amounts of
nonvolatile

Comparison of Simple and

Steam Distillation
limitations

SIMPLE
STEAM
- mixture whose
-Compounds
components
that react with
have close BP
water or
decompose
- Compounds
that decompose upon prolonged
contact with
at their normal
water
BP
-Nonvolatile
compound (P
5 mmHg at 100
C)

END