EX.
NO : 06
SIMPLE DISTILLATION
DATE :
Aim
To verify Rayleigh’s equation through the differential distillation of a binary mixture
comprising water and methanol.
Apparatus
Distillation Flask (Round-bottom Flask), Thermometer, Receiving Flask (Conical Flask or
Beaker), Condenser (Liebig Condenser), Measuring Jar
Theory
Distillation is a physical separation technique used to separate components of a liquid
mixture based on differences in their volatilities. It is considered a unit operation in chemical
engineering and does not involve any chemical reaction.
The apparatus used to carry out distillation is known as a still. Distillation processes can be
classified as either batch or continuous operations. Typically, laboratory-scale distillations are
carried out in batch mode, whereas industrial distillations are predominantly continuous
processes for efficiency and scalability.
Several types of distillation exist, including: Simple Distillation, Fractional Distillation,
Steam Distillation, Vacuum Distillation, Reactive Distillation
Distillation finds application across various domains such as: Laboratory-scale research and
experimentation, Industrial-scale chemical and petrochemical production, Extraction of
essential oils and medicinal compounds from herbs, Food and beverage processing industries
Rayleigh’s equation specifically applies to differential distillation, a type of batch distillation
where the more volatile component is progressively removed, allowing for theoretical
validation through changes in composition over time.
Figure 1: Simple Distillation setup
The above diagrams represent classical laboratory simple distillation,
attributed to Rayleigh (1903).
Rayleigh’s Equation
F = total kmol solution to start with
W = total kmol solution left in bottoms
xF = starting m. v. c. composition in liquid
xW = finishing m. v. c. composition in liquid
If we plot 1/(y*−x) v/s x the area under the curve is equal to ln (F/W)
Preparation of calibration chart - Procedure:
1. Prepare Mixtures with Varying Volume Ratios Mix methanol and water (or the given
binary mixture) in the following volume ratios (in mL): 0:20, 4:16, 8:12, 12:8, 16:4, 20:0
2. Use a clean and dry specific gravity bottle for each mixture.
3. Weigh the empty bottle (W₁). Fill it with the mixture and record the total weight (W₃).
4. Also weigh the bottle filled with distilled water (W₂).
5. Calculate the density of the mixture using the formula:
ρ=
( W 3−W 1
W 2−W 1 )
× density of water
Convert the volume of methanol and water to moles using:
Volume× Density
Moles=
Molecular Weight
Calculate the mole fraction of the more volatile component (usually
methanol):
moles of methanol
x=
moles of methanol + moles of water
6. Plot density on the Y-axis and mole fraction of methanol on the X-axis. The resulting curve
is your calibration chart, which helps determine unknown compositions from density.
Experimental procedure
1. Pour a known volume of the given binary mixture into a three-necked round-bottom flask.
2. Switch on the heating mantle and begin heating the mixture slowly. Maintain a steady
temperature increase up to approximately 65°C, ensuring a controlled and gradual
distillation process.
3. Continue the distillation until about three-fourths (¾) of the initial liquid volume has been
collected as distillate in the receiving flask.
4. Allow the distillate and the remaining residue to cool to room temperature. Measure the
volumes of both the distillate and the residue accurately.
5. Determine the density of the distillate and the residue using a pycnometer or density
bottle.
6. Using the calibration chart provided, determine the mole fractions of methanol and water
in both the distillate and residue based on their measured densities.
7. Obtain x−y data from the Perry’s Handbook page no 13.2, 7th edition or 8th edition and calculate 1/
(y*−x).
Observations and Calculations
System: Methanol (A) – Water (B)
1. Weight of empty specific gravity bottle, W₁ = g
2. Weight of bottle + water, W₂ = g
3. Weight of bottle + mixture, W₃ = g
4. Weight of water = W₂ − W₁ = g
5. Weight of mixture = W₃ − W₁ = g
6. Density of Water
Density = [(W₂ - W₁) / (W₂ - W₁)] × Y
Where Y= 997.045 is the density of water obtained from Perry’s Handbook.
7. Density of Mixture
Density = [(W₃ - W₁) / (W₂ - W₁)] × Density of water
8. Moles of Methanol
Moles of methanol = (Volume × Density) / Molar Mass of Methanol
9. Moles of Water
Moles of water = (Volume × Density) / Molar Mass of Water
10. Moles of feed
F=¿
11. Mole Fraction of Methanol
moles of methanol
xF=
moles of feed
12. Volume of distillate
3
V D =¿ m
13. Weight of the specific gravity bottle + distillate =
W 4=¿ ¿
14. Density of distillate
ρ D=
( W 4 −W 1
W 2−W 1 )×density of water
15. Mole fraction of distillate, 𝑥𝐷 = to be obtained from the calibration chart based on density of
distillate =
16. Average molecular weight of the distillate
M D ,avg =x D ׿
17. Moles of distillate
V D × ρD
D= =¿ ¿
M D , avg
18. Volume of residue = VR
19. Weight of the specific gravity bottle + residue (W5)
20. Density of residue
ρ R in Kg/m =
3
( W 5−W 1
W 2−W 1)×density of water
21. Mole fraction of residue
xW=to be obtained from the calibration chart based on density of residue=
22. Moles of residue (W)=F−D=____ moles
Table 1: Calibration chart for methanol water mixtures
Sl. Volume Volume of Weight of Weight of Density Mole
No of water methanol in specific the of the fraction of
. in ml ml gravity mixture in mixture methanol,
bottle + g kg/ m3 x
mixture
1
`
2
3
4
5
6
Table 2: Equilibrium Data from Perry’s Hand book
y*
1/y*−x
R.H.S. of Rayleigh’s equation
R.H.S. of Rayleigh’s equation=Area under the curve=
L.H.S. of Rayleigh’s equation
(Left Hand Side of Rayleigh's equation)
( WF )=¿
L.H.S.=ln
Result:
L.H.S. = R.H.S.
Rayleigh’s equation is verified.