Acquirement:
+ Raoult’s Law and Konovalop I applied for liquid-vapor mixture
+ Positive and negative deviations
+ Vapor equilibrium of 2 completely miscible solutions by distillation
+ Construct phase diagram (T-x) and determine coordinate of azeotropic point
+ Using refractometer
Theory:
Assume that the solution has 2 completely miscible liquids A and B, which is in equilibrium with vapor
phase containing 2 components A and B.
With ideal solution, we can apply Raoult’s Law to determine composition of vapor A and B.
Ideal solution:
It is described as a homogeneous solution where the interaction between molecules of components
(solute and solvents) is exactly the same to the interactions between the molecules of each component
itself.
Raoult’s Law:
Raoult’s law states that a solvent’s partial vapor pressure in a solution (or mixture) is equal to the
vapour pressure of the pure solvent multiplied by its mole fraction in the solution.
Psolution = ΧsolventP0solvent
Where,
Psolution = vapour pressure of the solution
Χsolvent = mole fraction of the solvent
P0solvent = vapour pressure of the pure solvent
These phase diagrams of real solution are determined by experimental data.
Binary two-phase diagram:
The horizontal axis represents the composition of each component in the solution. The more to the
right, the greater percentage of component B and the more to the left, the greater percentage of A. The
vertical illustrates the temperature.
Each composition of the solution has its own boiling temperature. The boiling curve consists of all of the
boiling temperature of the corresponding composition.
Choose a composition x and increase the temperature until it reaches the boiling curve, the first gas
begins to appear. Maintain this temperature to bring the solution into 2 phase area. Using Lever’s rule
to determine composition of liquid and vapor phase:
xliquid EF
=
x gas ED
When it reaches the densing curve, it totally change to gas phase.
With real solution, Raoult’s Law can no longer be applied due to negative or positive deviation
compared with Raoult’s Law.
Positive and negative deviation:
If vapor pressure of the solution is greater than the vapor pressure calculated by Raoult’s Law, therefore
we obtain positive deviation solution, for example: benzene- acetone, water-methanol, …
If vapor pressure of the solution is smaller than the vapor pressure calculated by Raoult’s Law, therefore
we obtain negative deviation solution, for example: benzene – chloroform, water – nitric acid, …
There are many causes lead to the deviations compared with Raoult’s Law. One of the main cause is the
differences between interactive force of the molecules from the same component and that of the
molecules from different substances.
If the interactive force between same component molecules is greater than that of different substances’
molecules, when forming the solution, stable connections tend to be broken down to create less stable
connections, therefore it usually is endothermic reaction. The distance between molecules in this
solution tends to be greater than pure substances, hence volume is increased. Moreover, the weaker
connection results in the fact that the solution is easier to evaporate, so total pressure is greater than
Raoult’s Law pressure, creating positive deviation.
On the other hand, the adhesive force is larger than the cohesive force, the solution tends to be
exothermic, therefore total volume decreases and leads to negative deviation compared with ideal
solution.
Azeotropic point:
Azeotrope is a liquid mixture that has a constant boiling point and whose vapor has the same
composition as the liquid.
If we illustrate the dependence of vapor pressure on composition of liquid phase and vapor phase on
the same diagram then two graphs will intersect at the extremum.
Maximum on P-x while minimum on T-x.
With the azeotrope, we have two cases of distillation:
If we distillate the solution with composition of liquid phase is smaller than composition of azeotrope,
we obtain pure A and a azeotrope with composition x.
If we distillate the solution with the composition of liquid phase is greater than the composition of
azeotrope, we obtain pure B and the azeotrope with composition x.
To obtain only pure substance A or B, we change the pressure so the azeotropic point shifts toward the
substance we desire until at a specific pressure the azeotrope only contains 100% substance. Therefore
we can take this substance out of the solution.
Equipment:
+ distillation apparatus: lấy gif này nha https://blog.en.byraki.gr/what-is-distillation/
+ electric heater
+ thermometer
+ septum stoppers
+ beaker
+ filter paper
+ Glass rod
+ refractometer
Chemicals:
+ Chloroform - Acetone
Procedure:
- Construct phase diagram (T-x) by detecting boiling temperature of pure substances, boiling
temperature of different solutions with different concentrations and compositions of liquid and vapor
phase at corresponding boiling temperature.
Step 1: Prepare the solution:
Using pipette (or burette) to take different compositions of chloroform – acetone into 6 flasks.
Close the septum stoppers, shake well. Using the refractometer to obtain the refractive index of pure
components and solutions. Report the data into the table 1.
Step 2: Determine boiling temperature and composition of vapor phase in equilibrium
1. Twin-neck flask
2. Thermometer
3. Condenser
4. Septum stopper
5. Beaker containing condensed vapor
Pouring one solution with corresponding composition into the flask (1) (about 2/3 volume of the flask).
Put some pumices into the flask.
Resemble the distillation apparatus, please note that we should keep the part containing alcohol of
thermometer into at least half of the solution inside to avoid the error in the process. Let water flow
through condenser.
Heat up the heater until it boils at stable state. Record the boiling temperature T 1
Turn the condenser towards the beaker (5). Take 3-5 drops of condensed vapor into the beaker then
close the lid tightly. Continue using the refractometer to get the refractive index value of the condensed
vapor.
Turn the condenser upward and record boiling temperature T 2. If the deviation between T 1 and T 2
exceeds 1o C , we have to set up again.
T 1 +T 2
T average=
2
Repeat those steps with the following solutions.
Experimental data:
Fill the data into these 2 tables:
Table 1
No. 1 2 3 4 5 6
Volume of
chloroform
(ml)
Volume of
acetone
(ml)
Compositio
n
Refractive
index
Table 2:
From the standard curve given, we can use the refractive index to obtain the composition.
Boiling temperature
Before After Average Refractive index Composition
Composition condensation condensation of condensed of condensed
of liquid phase vapor vapor
After obtaining the data, we can construct the phase diagram.
Determine the coordinate of the azeotropic point.
Phần câu hỏi mở rộng (không cần đưa vào slide)
