5.

13

5C.1(c) The Lever Rule

How do we determine the amount in each phase?
Consider benzene:
total g l
nbenzene = nbenzene + nbenzene

However, we can relate the number of moles of benzene in each phase to the total number of moles and
the corresponding mole fractions, i.e.,
n total zbenzene = n g ybenzene + n l xbenzene
total l g
Since, n = n + n , we can replace the number of moles in the liquid to write:
n total zbenzene = n g ybenzene + (n total − n g)xbenzene

or

n total(zbenzene − xbenzene) = n g(ybenzene − xbenzene) [1]

Similarly, we can replace the number of moles in the gas phase to write:
n total zbenzene = (n total − n l )ybenzene + n l xbenzene

or

n total(zbenzene − ybenzene) = n l(xbenzene − ybenzene) [2]

Taking the ratio of [1] and [2], we obtain:

(zbenzene − xbenzene) n g(ybenzene − xbenzene)
=

(zbenzene − ybenzene) n l(xbenzene − ybenzene)

or, rearranging

ng (zbenzene − xbenzene)
= [Lever Rule]

nl (ybenzene − zbenzene)

5C.2 Temperature-composition diagrams

Since the vapour pressure of each component changes with temperature, we must also look at the
behaviour of the boiling temperature as the composition of the liquid solution varies at fixed
pressure. Therefore, as we'll see, it is often much more useful to look at the T/composition plot
[NOTE: liquid phase is now on the bottom and vapour on the top]
 5.14

5C.2(a) Distillation
Consider the diagram above and the following process to separate the two liquids:
(i) Mixture of composition a1 is heated until it reaches it boiling point T2.
(ii) St the boiling point the liquid has composition a 2 = a1 while the vapour has composition
a′2 > a 2 (it is enriched in the more volatile liquid).
(iii) Collect the vapour and then cool to form liquid. Reheat to boiling point and then liquid has
composition a3 = a′2 while the vapour has composition a′3 > a3
(iv) Cycle as many times as needed to obtain desired purity of A.


5C.2(b) Azeotropes
We have seen that positive and negative deviations from Raoult’s law are possible in real
solutions. These deviations have a profound effect on vapour pressure and liquid vapour
equilibria.
(a) Negative deviation from Raoult’s Law, where there is significant interaction (H-bonding)
between the components, e.g., acetone-chloroform

• In the low A content region, gas is leaner in A than the liquid

• In the high A content region, gas is richer in A than the liquid
• The two regions meet at a point called the azeotrope where the gas and the liquid
have the same compositions; call the azeotrope: xchloroform = ychloroform = 0.35 

 5.15

(b) Positive deviation from Raoult’s Law, e.g., 1-propanol-water

• In the low A content region, gas is richer in A than the liquid - at low propanol mol
fraction, vapor is rich in propanol.
• In the high A content region, gas is less rich in A than the liquid - At high propanol mol
fraction, vapor is poor in propanol.
• The two regions meet at a point called the azeotrope where the gas and the liquid have
the same compositions. xpropanol = ypropanol = 0.432